JP3604427B2 - Phthalocyanine compound and optical recording medium containing the same - Google Patents

Description

〔式（１）中、Ｍは２個の水素原子、２価の金属原子、３価１置換金属原子、４価２置換金属原子、オキシ金属原子を表し、Ｌ^１は式（ａ）または式（ｂ）
【００１２】
【化６】

（式（ａ）または式（ｂ）中、Ｒ^１は、各々独立に炭素数３〜１０の直鎖または分岐のアルケニル基を表し、ＯＲ^２は、炭素数１〜１０の直鎖または分岐のアルコキシ基を表す。）を表す。〕で示されるフタロシアニン化合物。
▲２▼ 下記一般式（２）で表されるフタロシアニン化合物、
【００１３】
【化７】

〔式（２）中、Ｍは２個の水素原子、２価の金属原子、３価１置換金属原子、４価２置換金属原子、オキシ金属原子を表し、Ｌ^２は式（ｃ）
【００１４】
【化８】

（式（ｃ）中、ＯＲ^３は、炭素数１〜１０の直鎖または分岐のアルコキシ基を表し、Ｒ^４及びＲ^５は、各々独立に炭素数３〜１０の直鎖または分岐のアルケニル基を表す。）を表す。〕で示されるフタロシアニン化合物。
【００１５】
▲３▼ 一般式（１）または（２）において、Ｍで表される中心金属が、Ｐｄ，Ｃｕ，Ｒｕ，Ｐｔ，Ｎｉ，Ｃｏ，Ｒｈ，Ｚｎ，ＶＯ，ＴｉＯ，Ｓｉ（Ｙ）_２，Ｓｎ（Ｙ）_２，Ｇｅ（Ｙ）_２，（Ｙはハロゲン原子、アルコキシ基、アリールオキシ基、アシルオキシ基、ヒドロキシ基、アルキル基、アリール基、アルキルチオ基、アリールチオ基、トリアルキルシリルオキシ基、トリアルキルスズオキシ基、またはトリアルキルゲルマニウムオキシ基を表す。）であるフタロシアニン化合物。
▲４▼ 一般式（１）または（２）のフタロシアニン化合物を含有してなる光記録媒体。
▲５▼ 基板上に、一般式（１）または（２）のフタロシアニン化合物を含有する記録層、その上に金またはアルミニウムからなる反射層、さらにその上に保護層を積層した構成である光記録媒体に関するものである。
【００１６】
本発明のフタロシアニン化合物は、アルコキシ基及びアルケニル基がフタロシアニン環に置換したため、基板にスピンコート法により塗布する際に使用する溶剤への溶解性が向上した。また、フタロシアニン環に置換したアルケニル基は、フタロシアニン環と共役するために、吸収波長領域の制御がし易くなると共に、記録時に色素の分解・溶融が制御され精度の高いピット形成が行われたこと、分解発熱量の減少により記録媒体の樹脂基板へのダメージが減少したこと、反射層を有する記録媒体の場合は記録層と反射層である金属層との密着性向上に寄与し、従来の記録法のみならず、従来に比較して高速である記録、あるいは高密度の記録法においても光記録媒体の感度、記録特性の向上に効果を上げた。
【００１７】
本発明のフタロシアニン化合物は、６５０〜９００ｎｍにシャープな吸収を有し、分子吸光係数も高く、長期安定性および耐光性にも優れるため、半導体レーザーを用いる光記録媒体（光ディスク、光カード等）の記録材料に好適である。
【００１８】
以下に本発明の好ましい態様を詳述する。
【００１９】
一般式（１）、（２）中、Ｒ^１、Ｒ^４、Ｒ^５で示される炭素数３〜１０の直鎖または分岐のアルケニル基の具体例としては、プロペニル基、２−プロペニル基、１−メチルプロペニル基、１−メチル−２−プロペニル基、１−エチルプロペニル基、１−エチル−２−プロペニル基、１−プロピルプロペニル基、１−プロピル−２−プロペニル基、１，１−ジメチル−２−プロペニル基、ブテニル基、２−ブテニル基、１−メチル−２−ブテニル基、１−メチルブテニル基、２−メチル−２−ブテニル基、２−メチルブテニル基、３−メチル−２−ブテニル基、３−メチルブテニル基、２，３−ジメチル−２−ブテニル基、２，３−ジメチルブテニル基、１，１−ジメチル−２−ブテニル基、１−エチル−２−メチル−２−ブテニル基、１−エチル−２−メチルブテニル基、ペンテニル基、２−ペンテニル基、１−メチル−２−ペンテニル基、１−メチルペンテニル基、２−メチル−２−ペンテニル基、２−メチルペンテニル基、３−メチル−２−ペンテニル基、３−メチルペンテニル基、４−メチル−２−ペンテニル基、４−メチルペンテニル基、２，４−ジメチル−２−ペンテニル基、２，４−ジメチルペンテニル基、１，４−ジメチル−２−ペンテニル基、１，４−ジメチルペンテニル基、１−エチル−２−メチル−２−ペンテニル基、１−エチル−２−メチルペンテニル基、２−ヘキセニル基、ヘキセニル基、１−メチル−２−ヘキセニル基、１−メチルヘキセニル基、３−メチル−２−ヘキセニル基、３−メチルヘキセニル基、２−ヘプテニル基、ヘプテニル基、２−メチル−２−ヘプテニル基、２−メチルヘプテニル基、３，４，４−トリメチル−２−ヘプテニル基、３，４，４−トリメチルヘプテニル基、２−オクテニル基、オクテニル基、２−ノネニル基、ノネニル基、２−デケニル基、デケニル基等が挙げられる。
【００２０】
一般式（１）、（２）中、ＯＲ^２、ＯＲ^３で示される炭素数１〜１０の直鎖または分岐のアルコキシ基の具体例としては、メトキシ基、エトキシ基、ｎ−プロピルオキシ基、ｉｓｏ−プロピルオキシ基、ｎ−ブチルオキシ基、ｉｓｏ−ブチルオキシ基、ｓｅｃ−ブチルオキシ基、ｔ−ブチルオキシ基、ｎ−ペンチルオキシ基、ｉｓｏ−ペンチルオキシ基、ｎｅｏ−ペンチルオキシ基、２−メチルブチル−３−オキシ基、ペンチル−２−オキシ基、ペンチル−３−オキシ基、ｎ−ヘキシルオキシ基、ｃｙｃｌｏ−ヘキシルオキシ基、２−メチルペンチル−４−オキシ基、２−メチルペンチル−３−オキシ基、３−メチルペンチル−４−オキシ基、ｎ−ヘプチルオキシ基、ヘキシル−３−オキシ基、２−メチルヘキシル−５−オキシ基、２，４−ジメチルペンチル−３−オキシ基、２−メチルヘキシル−３−オキシ基、ヘプチル−４−オキシ基、ｎ−オクチルオキシ基、２−エチルヘキシル−１−オキシ基、２，５−ジメチルヘキシル−３−オキシ基、２，４−ジメチルヘキシル−３−オキシ基、２，２，４−トリメチルペンチル−３−オキシ基、ｎ−ノニルオキシ基、３，５−ジメチルヘプチル−４−オキシ基、２，６−ジメチルヘプチル−３−オキシ基、２，４−ジメチルヘプチル−３−オキシ基、２，２，５，５−テトラメチルヘキシル−３−オキシ基、１−ｃｙｃｌｏ−ペンチル−２，２−ジメチルプロピル−１−オキシ基、１−ｃｙｃｌｏ−ヘキシル−２，２−ジメチルプロピル−１−オキシ基等が挙げられる。
【００２１】
また、一般式（１）、（２）中、Ｍで示される２価金属の例としては、Ｃｕ，Ｚｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｒｕ，Ｒｈ，Ｐｄ，Ｐｔ，Ｍｎ，Ｓｎ，Ｍｇ，Ｐｂ，Ｈｇ，Ｃｄ，Ｂａ，Ｔｉ，Ｂｅ，Ｃａ等が挙げられ、１置換の３価金属の例としては、Ａｌ−Ｆ，Ａｌ−Ｃｌ，Ａｌ−Ｂｒ，Ａｌ−Ｉ，Ｇａ−Ｆ，Ｇａ−Ｃｌ，Ｇａ−Ｂｒ，Ｇａ−Ｉ，Ｉｎ−Ｆ，Ｉｎ−Ｃｌ，Ｉｎ−Ｂｒ，Ｉｎ−Ｉ，Ｔｌ−Ｆ，Ｔｌ−Ｃｌ，Ｔｌ−Ｂｒ，Ｔｌ−Ｉ，Ａｌ−Ｃ_６Ｈ_５，Ａｌ−Ｃ_６Ｈ_４（ＣＨ_３），Ｉｎ−Ｃ_６Ｈ_５，Ｉｎ−Ｃ_６Ｈ_４（ＣＨ_３），Ｍｎ（ＯＨ），Ｍｎ（ＯＣ_６Ｈ_５），Ｍｎ〔ＯＳｉ（ＣＨ_３）_３〕，Ｆｅ−Ｃｌ，Ｒｕ−Ｃｌ等が挙げられ、２置換の４価金属の例としては、ＣｒＣｌ_２，ＳｉＦ_２，ＳｉＣｌ_２，ＳｉＢｒ_２，ＳｉＩ_２，ＳｎＦ_２，ＳｎＣｌ_２，ＳｎＢｒ_２，ＺｒＣｌ_２，ＧｅＦ_２，ＧｅＣｌ_２，ＧｅＢｒ_２，ＧｅＩ_２，ＴｉＦ_２，ＴｉＣｌ_２，ＴｉＢｒ_２，Ｓｉ（ＯＨ）_２，Ｓｎ（ＯＨ）_２，Ｇｅ（ＯＨ）_２，Ｚｒ（ＯＨ）_２，Ｍｎ（ＯＨ）_２，ＴｉＡ_２，ＣｒＡ_２，ＳｉＡ_２，ＳｎＡ_２，ＧｅＡ_２〔Ａはアルキル基、フェニル基、ナフチル基およびその誘導体を表す〕，Ｓｉ（ＯＡ’）_２，Ｓｎ（ＯＡ’）_２，Ｇｅ（ＯＡ’）_２，Ｔｉ（ＯＡ’）_２，Ｃｒ（ＯＡ’）_２〔Ａ’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およびその誘導体を表す〕，Ｓｉ（ＳＡ”）_２，Ｓｎ（ＳＡ”）_２，Ｇｅ（ＳＡ”）_２〔Ａ”はアルキル基、フェニル基、ナフチル基およびその誘導体を表す〕等が挙げられ、オキシ金属の例としては、ＶＯ，ＭｎＯ，ＴｉＯ等が挙げられる。好ましくは、Ｐｄ、Ｃｕ，Ｒｕ，Ｐｔ，Ｎｉ，Ｃｏ，Ｒｈ，Ｚｎ，ＶＯ，ＴｉＯ，Ｓｉ（Ｙ）_２，Ｓｎ（Ｙ）_２，Ｇｅ（Ｙ）_２，（Ｙはハロゲン原子、アルコキシ基、アリールオキシ基、アシルオキシ基、ヒドロキシ基、アリキル基、アリール基、アルキルチオ基、アリールチオ基、トリアルキルシリルオキシ基、トリアルキルスズオキシ基またはトリアルキルゲルマニウムオキシ基を表す。）であり、特に好ましい例としては、Ｃｕ，Ｎｉ，Ｃｏ，Ｍｇ，Ｚｎ，Ｐｄ，Ｐｔ，ＶＯ等である。
【００２２】
一般式（１）で示されるフタロシアニン化合物の合成法としては、下式（３）または（４）、
【００２３】
【化９】

〔式（３）または式（４）中、Ｒ^１およびＯＲ^２は一般式（１）と同じ意味を表す。〕で示される化合物を、例えば１，８−ジアザビシクロ［５，４，０］−７−ウンデセン（ＤＢＵ）存在下に、金属誘導体とアルコール中で加熱反応させる、あるいは、金属化合物とクロルナフタレン、ブロムナフタレン、トリクロルベンゼン等の高沸点溶媒中で加熱反応させる方法等が挙げられる。また、一般式（３）または（４）で示される化合物を、アルコール中、ナトリウムメチラートを触媒にアンモニアと反応させて得られる一般式（５）または（６）で示されるジイミノイソインドリンを中間体として同様に反応させる方法等が挙げられる。
【００２４】
【化１０】

〔式（５）または式（６）中、Ｒ^１およびＯＲ^２は一般式（１）と同じ意味を表す。〕
また、一般式（３）または（４）で示される化合物は、以下に示した経路で製造することができる。
【００２５】
【化１１】

市販されている４−ニトロフタロニトリル（Ａ）を、塩基の存在下、Ｒ^１ＯＨ〔Ｒ^１は前記と同じ意味を表す。〕で示されるアリルアルコール誘導体と反応させてアルコキシフタロニトリル（Ｂ）を得る。更に（Ｂ）をクライゼン転移反応後、塩基の存在下、Ｒ^２Ｘ〔Ｒ^２は一般式（１）のＯＲ^２で表されるアルコキシ基の相当するアルキル基を表し、Ｘはハロゲン原子を表す。〕で示されるアルキルハライド誘導体と反応させることで目的とする一般式（３）または（４）で示される化合物の混合物が製造され、カラムクロマト等の方法により分離し、目的とする一般式（３）または（４）で示される化合物の単品を得ることができる。
【００２６】
また、一般式（２）で示されるフタロシアニン化合物の合成法としては、下式（７）
【００２７】
【化１２】

〔式（７）中、ＯＲ^３、Ｒ^４及びＲ^５は一般式（２）と同じ意味を表す。〕
で示される化合物を、例えば１，８−ジアザビシクロ［５，４，０］−７−ウンデセン（ＤＢＵ）存在下に、金属誘導体とアルコール中で加熱反応させる、あるいは、金属化合物とクロルナフタレン、ブロムナフタレン、トリクロルベンゼン等の高沸点溶媒中で加熱反応させる方法等が挙げられる。また、一般式（８）で示される化合物を、アルコール中、ナトリウムメチラートを触媒にアンモニアと反応させて得られる一般式（８）で示されるジイミノイソインドリンを中間体として同様に反応させる方法等が挙げられる。
【００２８】
【化１３】

〔式（８）中、ＯＲ^３、Ｒ^４及びＲ^５は一般式（２）と同じ意味を表す。〕
また、一般式（７）で示される化合物は、以下に示した経路で製造することができる。
【００２９】
【化１４】

【００３０】
市販されている３−ニトロフタロニトリル（Ｃ）を、塩基の存在下、Ｒ^４ＯＨ〔Ｒ^４は一般式（２）と同じ意味を表す。〕で示されるアリルアルコール誘導体と反応させてアルコキシフタロニトリル（Ｄ）を得る。更に（Ｄ）をクライゼン転移反応後、塩基の存在下、Ｒ^５Ｘ〔Ｒ^５は一般式（２）と同じ意味を表し、Ｘはハロゲン原子を表す。〕で示されるアリルハライド誘導体と反応させて３−アルコキシ−４−アルケニルフタロニトリル（Ｅ）を得る。更に（Ｅ）をクライゼン転移反応後、塩基の存在下、Ｒ^３Ｘ〔Ｒ^３は一般式（２）のＯＲ^３で表されるアルコキシ基の相当するアルキル基を表し、Ｘはハロゲン原子を表す。〕で示されるアルキルハライド誘導体と反応させることで目的とする一般式（７）で示される化合物が製造される。
【００３１】
Ｒ^１ＯＨ、Ｒ^４ＯＨで示されるアリルアルコール誘導体の例としては、アリルアルコール、２−ブテノール、３−メチル−２−ブテノール、２−メチル−３−ブテン−２−オール、３−メチル−３−ブテン−２−オール、２−ペンテノール、３−ペンテン−２−オール、１−ペンテン−３−オール、２，３−ジメチル−３−ブテン−２−オール、１−ヘキセン−３−オール、４−ヘキセン−３−オール、４−メチル−３−ペンテン−２−オール、２−メチル−１−ペンテン−３−オール、３−メチル−１−ペンテン−３−オール、４−メチル−１−ペンテン−３−オール、２，４−ジメチル−１−ペンテン−３−オール、１−ヘプテン−３−オール、２−ヘプテン−４−オール、３−メチル−３−ヘキセン−２−オール、３−メチル−１−ヘキセン−３−オール、２−メチル−４−ヘキセン−３−オール、２−メチル−１−ヘプテン−３−オール、４−チル−４−ヘプテン−３−オール、１−オクテン−３−オール、２−オクテン−４−オール、３，４，４，−トリメチル−１−ペンテン−３−オール、１−ノネン−３−オール等の所望のアルケニル基を導入できるものが挙げられる。
【００３２】
Ｘで表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられ、中でも、塩素、臭素が好ましい。
【００３３】
本発明のフタロシアニン化合物を用いて光記録媒体を製造する方法には、透明基板上に本発明のフタロシアニン化合物を含む１〜３種の化合物を１層または２層に塗布、あるいは蒸着する方法がある。塗布法としては、バインダー樹脂２０重量％以下、好ましくは０％と、本発明のフタロシアニン化合物０．０５〜２０重量％、好ましくは０．５〜２０重量％となるように溶媒に溶解し、スピンコーターで塗布する方法等がある。また、蒸着方法としては１０^−５〜１０^−７ｔｏｒｒ、１００〜３００℃にて基板上にフタロシアニン化合物を堆積させる方法等がある。
【００３４】
基板としては、光学的に透明な樹脂であればよい。例えば、アクリル樹脂、ポリエチレン樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、ポリカーボネート樹脂、ポリオレフィン共重合樹脂、塩化ビニル共重合樹脂、塩化ビニリデン共重合樹脂、スチレン共重合樹脂等が挙げられる。また基板は熱硬化性樹脂または紫外線硬化性樹脂により表面処理がなされていてもよい。
【００３５】
光記録媒体（光ディスク、光カード等）を作製する場合、コストの面、ユーザーの取り扱いの面より、基板はポリアクリレート基板またはポリカーボネート基板を用い、かつスピンコート法により塗布されるのが好ましい。
【００３６】
基板の耐溶剤性より、スピンコートに用いる溶剤は、ハロゲン化炭化水素（例えば、ジクロロメタン、クロロホルム、四塩化炭素、テトラクロロエチレン、ジクロロジフルオロエタン等）、エーテル類（例えば、テトラヒドロフラン、ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、ジオキサン等）、アルコール類（例えば、メタノール、エタノール、プロパノール等）、セロソルブ類（例えば、メチルセロソルブ、エチルセロソルブ等）、炭化水素類（例えば、ヘキサン、シクロヘキサン、エチルシクロヘキサン、シクロオクタン、ジメチルシクロヘキサン、オクタン、ベンゼン、トルエン、キシレン等）、あるいはこれらの混合溶媒が好適に用いられる。
【００３７】
記録媒体として加工するには、上記の様に基板で覆う、あるいは２枚の記録層を設けた基板に、エアーギャップを設けて対向させて張り合わせる、または、記録層上に反射層（アルミニウムまたは金）を設け、熱硬化性または光硬化性樹脂の保護層を積層する方法などがある。保護層として、Ａｌ_２Ｏ_３，ＳｉＯ_２，ＳｉＯ，ＳｎＯ_２等の無機化合物を利用してもよい。
【００３８】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明の実施の態様はこれにより限定されるものではない。
【００３９】
実施例１
下記構造式（３−１）
【００４０】
【化１５】

で示されるフタロニトリル誘導体２５．４ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）、及びｎ−アミルアルコール１２５ｇよりなる混合物を、窒素雰囲気下で、１００℃まで昇温させた。次に、同温度で塩化パラジウム５．３ｇ（０．０３モル）を添加し、９５〜１００℃で２０時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記構造式（１−１）で示されるフタロシアニン化合物１４．６ｇ（収率５２％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００４１】

【００４２】
【化１６】

【００４３】
上記フタロシアニン化合物のｎ−オクタン溶液（１０ｇ／ｌ）をスパイラルグルーブ（ピッチ１．６μｍ、溝幅０．６μｍ、溝深０．１８μｍ）付きの外形１２０ｍｍ、厚さ１．２ｍｍのＣＤ−Ｒ用ポリカーボネート基板上に５００〜１０００ｒｐｍでスピンコート成膜した。その上に３０ｎｍの金をスパッタ蒸着して反射層を形成し、続いて光硬化型ポリアクリル樹脂によりオーバーコート後光硬化させ保護層を形成してＣＤ−Ｒ型媒体を作製した。この媒体に、波長７８０ｎｍの半導体レーザーを用いて、線速１．４ｍ／ｓでＥＦＭ信号を６．０ｍＷのパワーで書き込んだときのエラーレートは０．２％未満であり、カ−ボンア−ク灯６３℃、２００時間の耐久試験においても変化はなかった。
【００４４】
実施例２
下記構造式（３−２）
【００４５】
【化１７】

で示されるフタロニトリル誘導体２５．４ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）、及びｎ−アミルアルコール１２５ｇよりなる混合物を、窒素雰囲気下で、１００℃まで昇温させた。次に、同温度で塩化第一銅３．０ｇ（０．０３モル）を添加し、９５〜１００℃で２０時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記構造式（１−２）で示されるフタロシアニン化合物１７．６ｇ（収率６５％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００４６】

【００４７】
【化１８】

【００４８】
上記フタロシアニン化合物のジブチルエ−テル溶液（１０ｇ／ｌ）を実施例１と同様にスピンコーターによりＣＤ−Ｒ用ポリカーボネート基板上に塗布し、その上に金をスパッタ蒸着し、続いてＵＶ硬化樹脂を用いて保護層を形成し、ＣＤ−Ｒ型媒体を作製した。この媒体に７８０ｎｍの半導体レーザーを用いて線速１．４ｍ／ｓでＥＦＭ信号を６．０ｍＷのパワーで書き込んだときのエラーレートは０．２％未満であり、０．５ｍＷの再生光で百万回再生を行っても変化がなかった。また８０℃／８５％の条件で１０００時間経過後も記録・再生に支障はなかった。
【００４９】
実施例３
下記構造式（３−３）
【００５０】
【化１９】

で示されるフタロニトリル誘導体２９．６ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）、及びｎ−アミルアルコール１２５ｇよりなる混合物を、窒素雰囲気下で、１００℃まで昇温させた。次に、同温度で塩化第一銅３．０ｇ（０．０３モル）を添加し、９５〜１００℃で２０時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記構造式（１−３）で示されるフタロシアニン化合物１９．１ｇ（収率６１％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００５１】

【００５２】
【化２０】

【００５３】
上記フタロシアニン化合物１０ｇをジブチルエ−テルとジイソプロピルエーテルの３：１（体積比）混合溶媒５００ｍｌに溶解し、スピンコーターによりポリカ−ボネート製光カード基板上に厚み１００ｎｍで塗布し、続いて塗布面にＵＶ硬化樹脂を用いて保護層を形成し、光カ−ドを作製した。この媒体に７８０ｎｍ、線速２ｍ／ｓ，４ｍＷの半導体レーザー光により記録したとき、ＣＮ比は６１ｄＢであった。また、線速２ｍ／ｓ，０．８ｍＷのレーザ−光により再生可能で、再生光安定性を調べたところ、１０^５回の再生が可能であった。さらにこの光カ−ドは保存安定性も良好なものであった。
【００５４】
実施例４
下記構造式（３−４）
【００５５】
【化２１】

で示されるフタロニトリル誘導体２９．６ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）、及びｎ−アミルアルコール１２５ｇよりなる混合物を、窒素雰囲気下で、１００℃まで昇温させた。次に、同温度で三塩化バナジウム４．７ｇ（０．０３モル）を添加し、９５〜１００℃で２０時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記構造式（１−４）で示されるフタロシアニン化合物１４．１ｇ（収率４５％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００５６】

【００５７】
【化２２】

【００５８】
上記フタロシアニン化合物を用いて実施例１と同様にしてＣＤ−Ｒ型媒体を作製した。この媒体に、波長７８０ｎｍのレーザーを用いて、線速１．４ｍ／ｓでＥＦＭ信号を６．０ｍＷのパワーで書き込んだときのエラーレートは、０．２％未満であった。
【００５９】
実施例５
下記構造式（３−５）
【００６０】
【化２３】

で示されるフタロニトリル誘導体２８．２ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）、及びｎ−アミルアルコール１２５ｇよりなる混合物を、窒素雰囲気下で、１００℃まで昇温させた。次に、同温度で塩化第一銅３．０ｇ（０．０３モル）を添加し、９５〜１００℃で２０時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記構造式（１−５）で示されるフタロシアニン化合物１７．９ｇ（収率６０％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００６１】

【００６２】
【化２４】

【００６３】
上記フタロシアニン化合物を用いて実施例１と同様にしてＣＤ−Ｒ型媒体を作製した。この媒体に、波長７８０ｎｍのレーザーを用いて、線速１．４ｍ／ｓでＥＦＭ信号を６．０ｍＷのパワーで書き込んだときのエラーレートは、０．２％未満であった。
【００６４】
実施例６
下記構造式（３−６）
【００６５】
【化２５】

で示されるフタロニトリル誘導体２８．２ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）、及びｎ−アミルアルコール１２５ｇよりなる混合物を、窒素雰囲気下で、１００℃まで昇温させた。次に、同温度で塩化第一銅３．０ｇ（０．０３モル）を添加し、９５〜１００℃で２０時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記構造式（１−６）で示されるフタロシアニン化合物２０．９ｇ（収率７０％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００６６】

【００６７】
【化２６】

【００６８】
上記フタロシアニン化合物を用いて実施例１と同様にしてＣＤ−Ｒ型媒体を作製した。この媒体に、波長７８０ｎｍのレーザーを用いて、線速１．４ｍ／ｓでＥＦＭ信号を６．０ｍＷのパワーで書き込んだときのエラーレートは、０．２％未満であった。
【００６９】
実施例７
撹拌器、還流冷却器および窒素導入管を備えた容器に、３−（２−ペントキシ）−４，６−ビス（１−プロペニル）フタロニトリル２９．４ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）、及びｎ−アミルアルコール１２５ｇを装入し、窒素雰囲気下で、１００℃まで昇温させた。次に、同温度で塩化パラジウム５．３ｇ（０．０３モル）を添加し、９５〜１００℃で２０時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記式（２−１）で示されるフタロシアニン化合物２０．２ｇ（収率６３％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００７０】

【００７１】
【化２７】

【００７２】
上記フタロシアニン化合物のｎ−オクタン溶液（１０ｇ／ｌ）をスパイラルグルーブ（ピッチ１．６μｍ、溝幅０．６μｍ、溝深０．１８μｍ）付きの外形１２０ｍｍ、厚さ１．２ｍｍのＣＤ−Ｒ用ポリカーボネート基板上に５００〜１０００ｒｐｍでスピンコート成膜した。その上に３０ｎｍの金をスパッタ蒸着して反射層を形成し、続いて光硬化型ポリアクリル樹脂によりオーバーコート後光硬化させ保護層を形成してＣＤ−Ｒ型媒体を作製した。この媒体に、波長７８０ｎｍの半導体レーザーを用いて、線速１．４ｍ／ｓでＥＦＭ信号を６．０ｍＷのパワーで書き込んだときのエラーレートは０．２％未満であり、カ−ボンア−ク灯６３℃、２００時間の耐久試験においても変化はなかった。
【００７３】
実施例８
実施例７と同様の容器に、３−（３−ヘキソキシ）−４，６−ビス（１−プロペニル）フタロニトリル３０．８ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）およびｎ−アミルアルコール１２０ｇを装入し、窒素雰囲気下で１００℃まで昇温させた。次に、同温度で塩化パラジウム５．３ｇ（０．０３モル）を添加し、９５〜１００℃で２０時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記式（２−２）で示されるフタロシアニン化合物２１．８ｇ（収率６５％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００７４】

【００７５】
【化２８】

【００７６】
上記フタロシアニン化合物のジブチルエ−テル溶液（１０ｇ／ｌ）を実施例７と同様にスピンコーターによりＣＤ−Ｒ用ポリカーボネート基板上に塗布し、その上に金をスパッタ蒸着し、続いてＵＶ硬化樹脂を用いて保護層を形成し、ＣＤ−Ｒ型媒体を作製した。この媒体に７８０ｎｍの半導体レーザーを用いて線速１．４ｍ／ｓでＥＦＭ信号を６．０ｍＷのパワーで書き込んだときのエラーレートは０．２％未満であり、０．５ｍＷの再生光で百万回再生を行っても変化がなかった。また８０℃／８５％の条件で１０００時間経過後も記録・再生に支障はなかった。
【００７７】
実施例９
実施例７と同様の容器に、３−（２−ペントキシ）−４，６−ビス（１−プロペニル）フタロニトリル２９．４ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）、及びｎ−アミルアルコール１２５ｇを装入し、窒素雰囲気下で、１００℃まで昇温させた。次に、同温度で塩化第一銅３．０ｇ（０．０３モル）を添加し、９５〜１００℃で１０時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記式（２−３）で示されるフタロシアニン化合物２４．８ｇ（収率８０％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００７８】

【００７９】
【化２９】

【００８０】
上記フタロシアニン化合物１０ｇをジブチルエ−テルとジイソプロピルエーテルの３：１（体積比）混合溶媒５００ｍｌに溶解し、スピンコーターによりポリカ−ボネート製光カード基板上に厚み１００ｎｍで塗布し、続いて塗布面にＵＶ硬化樹脂を用いて保護層を形成し、光カ−ドを作製した。この媒体に７８０ｎｍ、線速２ｍ／ｓ，４ｍＷの半導体レーザー光により記録したとき、ＣＮ比は６１ｄＢであった。また、線速２ｍ／ｓ，０．８ｍＷのレーザ−光により再生可能で、再生光安定性を調べたところ、１０^５回の再生が可能であった。さらにこの光カ−ドは保存安定性も良好なものであった。
【００８１】
実施例１０
実施例７と同様の容器に、３−（３−メチル−ブトキシ）−４−（１−メチル−１−プロペニル）−６−（１−プロペニル）フタロニトリル３０．８ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）およびｎ−アミルアルコール１２０ｇを装入し、窒素雰囲気下で１００℃まで昇温させた。次に、同温度で塩化マグネシウム４．７ｇ（０．０３モル）を添加し、９５〜１００℃で１５時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記式（２−４）で示されるフタロシアニン化合物１７．６ｇ（収率５６％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００８２】

【００８３】
【化３０】

【００８４】
上記フタロシアニン化合物を用いて実施例７と同様にしてＣＤ−Ｒ型媒体を作製した。この媒体に、波長７８０ｎｍのレーザーを用いて、線速１．４ｍ／ｓでＥＦＭ信号を６．０ｍＷのパワーで書き込んだときのエラーレートは、０．２％未満であった。
【００８５】
実施例１１
実施例７と同様の容器に、３−（２−ペントキシ）−４，６−ビス（１−プロペニル）フタロニトリル２９．４ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）、及びｎ−アミルアルコール１２５ｇを装入し、窒素雰囲気下で、１００℃まで昇温させた。次に、同温度で塩化亜鉛４．１ｇ（０．０３モル）を添加し、９５〜１００℃で２５時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記式（２−５）で示されるフタロシアニン化合物２０．８ｇ（収率６７％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００８６】

【００８７】
【化３１】

【００８８】
上記フタロシアニン化合物を用いて実施例７と同様にしてＣＤ−Ｒ型媒体を作製した。この媒体に、波長７８０ｎｍのレーザーを用いて、線速１．４ｍ／ｓでＥＦＭ信号を６．０ｍＷのパワーで書き込んだときのエラーレートは、０．２％未満であった。
【００８９】
実施例１２
実施例７と同様の容器に、３−（２，４−ジメチル−３−ペントキシ）−４，６−ビス（１−プロペニル）フタロニトリル３２．２ｇ（０．１モル）、ＤＢＵ１５．２ｇ（０．１モル）、及びｎ−アミルアルコール１２５ｇを装入し、窒素雰囲気下で、１００℃まで昇温させた。次に、同温度で塩化パラジウム５．３ｇ（０．０３モル）を添加し、９５〜１００℃で２５時間反応させた。反応終了後、冷却し、不溶物を濾別した。濾液を減圧濃縮して溶媒を回収した後、カラム精製（シリカゲル５００ｇ、溶媒トルエン）し、下記式（２−６）で示されるフタロシアニン化合物２０．９ｇ（収率６０％）を得た。
可視吸光スペクトル及び元素分析の結果は以下の通りであった。
【００９０】

【００９１】
【化３２】

【００９２】
上記フタロシアニン化合物を用いて実施例７と同様にしてＣＤ−Ｒ型媒体を作製した。この媒体に、波長７８０ｎｍのレーザーを用いて、線速１．４ｍ／ｓでＥＦＭ信号を６．０ｍＷのパワーで書き込んだときのエラーレートは、０．２％未満であった。
【００９３】
比較例１
下記構造式（Ｆ）で示される特開平３−６２８７８号公報（ＵＳＰ５１２４０６７）の例示化合物を用いて実施例１と同様にして作製した媒体を評価した。
【００９４】
【化３３】

【００９５】
本発明のフタロシアニン化合物を用いた光記録媒体は、通常記録の６．０ｍＷレーザーパワー及び３．６ｍＷ低レーザー、高速記録及び高密度記録において良好な感度、記録特性を示した。なお、条件は以下の通りである。
通常記録：線速度１．４ｍ／ｓ（１倍速）で６３分の情報を記録する。
高速記録：線速度５．６ｍ／ｓ（４倍速）で６３分の情報を記録する。
高密度記録：線速度１．２ｍ／ｓで７４分の情報を記録する。
【００９６】
尚、通常記録の時のみ６．０と３．６ｍＷの２つのレーザーパワーで記録し、他の記録方法の時は６．０ｍＷで記録した。
【００９７】
さらに、記録感度（Ｃ／Ｎ比）、ジッター及びデビエイションをそれぞれＣＤデコーダーＤＲ３５５２（ケンウッド社製）、ＬＪＭ−１８５１ジッターメーター（リーダー電子製）及びＴＩＡ−１７５タイムインターバルアナライザー（ＡＤＣ社製）を用いて計測した。
【００９８】
評価基準
感度（Ｃ／Ｎ比）
○： ≧５５ｄＢ
×： ＜５５ｄＢ
ジッター
○： ３Ｔピットジッター及び３Ｔランドジッターが ＜３５ｎｓ
×： ３Ｔピットジッター又は３Ｔランドジッターが ≧３５ｎｓ
デビエイション
○： −５０ｎｓ＜ ３Ｔ及び１１Ｔデビエイション ＜５０ｎｓ
×： ３Ｔ又は１１Ｔデビエイション≧５０ｎｓ又は３Ｔ又は１１Ｔデビエイション≦−５０ｎｓ
結果を表−１、表−２に示した。
【００９９】
【表１】

【０１００】
【表２】

【０１０１】
【発明の効果】
本発明のフタロシアニン化合物は、アルコキシ基及びアルケニル基がフタロシアニン環に置換したため、基板にスピンコート法により塗布する際に使用する溶剤への溶解性が向上した。また、フタロシアニン環に置換したアルケニル基は、フタロシアニン環と共役するために、吸収波長領域の制御がし易くなると共に、記録時に色素の分解・溶融が制御され精度の高いピット形成が行われたこと、分解発熱量の減少により記録媒体の樹脂基板へのダメージが減少したこと、反射層を有する記録媒体の場合は記録層と反射層である金属層との密着性が向上に寄与し、従来の記録法のみならず、従来に比較して高速である記録、あるいは高密度の記録法においても光記録媒体の感度、記録特性の向上に効果を上げた。[0001]
[Industrial applications]
The present invention relates to a novel recording material for optical disks, information recording, a display sensor, a compound useful as a near-infrared absorber that plays an important role in optoelectronics such as safety glasses, and a recording layer containing the compound. And optical recording media such as optical cards.
[0002]
[Prior art]
Laser light is used for writing and reading in optical disks, optical card devices, and the like. In particular, as a recording method of an optical recording medium used in these apparatuses, as a practical level, heat mode recording (thermal recording) through light-to-heat conversion is usually adopted. Various organic polymers and organic dyes that cause physical or chemical changes such as melting, evaporation, decomposition, or sublimation have been proposed. Among them, organic dyes having low melting and decomposition temperatures are preferable from the viewpoint of recording sensitivity. Therefore, cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, and azo dyes have been developed as recording layers.
[0003]
For example, JP-A-2-147286 proposes an optical recording medium containing a cyanine dye in a recording layer. However, this medium system was inferior in long-term storage properties and light fastness, and was also insufficient in recording characteristics.
[0004]
Optical recording media containing an anthraquinone dye (for example, JP-A-58-224448) and a naphthoquinone dye (for example, JP-A-58-224793) in the recording layer have been proposed. Similarly, it was inferior in long-term storage property and light fastness, and was also insufficient in recording characteristics.
[0005]
JP-A-61-25886, JP-A-2-43269 (USP 4,960,538), JP-A-2-296885, and the like propose optical recording media containing a naphthalocyanine dye in a recording layer. In this medium system, the light resistance was excellent, but the reflectance of the recording layer was low, and the recording characteristics were insufficient.
[0006]
Further, techniques for using a phthalocyanine dye, particularly an alkoxy-substituted phthalocyanine, in the recording layer of an optical recording medium are disclosed in JP-A-61-154888 (EP 186404), JP-A-61-197280, and JP-A-61-246091. It is widely known in JP-A-62-39286 (USP 4,769,307), JP-A-63-37991, JP-A-63-39388, and the like. The optical recording media using phthalocyanine dyes disclosed in these patents have not been said to have sufficient performance in sensitivity and recording characteristics. Japanese Patent Laid-Open Publication No. Hei 3-62878 (US Pat. No. 5,240,067) has improved this. However, even with the improved compound, errors at the time of high-speed recording and high-density recording with a laser beam are large and are not yet practically sufficient. JP-A-2-43269 (U.S. Pat. No. 4,960,538) JP-A-2-502099 and JP-A-2-296885 disclose an alkoxy-substituted naphthalocyanine, JP-A-63-37991 disclose an aliphatic hydrocarbon oxy-substituted phthalocyanine, JP-A-63-39388 proposes the use of an alkenylthio-substituted phthalocyanine for an optical recording medium, but does not disclose that it has an effect on sensitivity and recording characteristics.
[0007]
It should be noted that none of the recording characteristics of optical recording media using other known dyes have been found to have sufficient performance.
[0008]
Since writing and reading to and from the optical recording medium uses a laser beam of 400 to 900 nm, it is important to control the absorption coefficient and refractive index of the recording material in the vicinity of the used laser oscillation wavelength and to form pits with high accuracy during writing. . This is particularly important in high-speed recording and high-density recording recently desired. Therefore, it is necessary to develop a dye for an optical recording medium having high structural stability, a high refractive index for light near the laser oscillation wavelength, good decomposition characteristics, and high sensitivity. However, conventionally developed dyes for optical recording media have drawbacks when used in recording media, particularly in terms of sensitivity (C / N ratio, optimum recording power) and recording characteristics (jitter, deviation) of high-speed recording and high-density recording. There was a problem of having.
[0009]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to provide a dye which can improve the above-mentioned drawbacks, has high sensitivity even at the time of high-speed recording and high-density recording, and can provide an optical recording medium having good recording characteristics and light resistance.
[0010]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problem, and as a result, completed the present invention. That is, the present invention
(1) a phthalocyanine compound represented by the following general formula (1),
[0011]
Embedded image

[In the formula (1), M represents two hydrogen atoms, a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom; ¹ Is the formula (a) or (b)
[0012]
Embedded image

(In the formula (a) or the formula (b), R ¹ Each independently represents a linear or branched alkenyl group having 3 to 10 carbon atoms; ² Represents a linear or branched alkoxy group having 1 to 10 carbon atoms. ). A phthalocyanine compound represented by the formula:
(2) a phthalocyanine compound represented by the following general formula (2),
[0013]
Embedded image

[In the formula (2), M represents two hydrogen atoms, a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom; ² Is the formula (c)
[0014]
Embedded image

(In the formula (c), OR ³ Represents a linear or branched alkoxy group having 1 to 10 carbon atoms; ⁴ And R ⁵ Each independently represents a linear or branched alkenyl group having 3 to 10 carbon atoms. ). A phthalocyanine compound represented by the formula:
[0015]
{Circle around (3)} In the general formula (1) or (2), the central metal represented by M is Pd, Cu, Ru, Pt, Ni, Co, Rh, Zn, VO, TiO, Si (Y). _2, Sn (Y) _2, Ge (Y) _2, (Y represents a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a hydroxy group, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a trialkylsilyloxy group, a trialkyltinoxy group, or a trialkylgermaniumoxy group. Represents a phthalocyanine compound.
(4) An optical recording medium containing the phthalocyanine compound of the general formula (1) or (2).
{Circle around (5)} Optical recording having a configuration in which a recording layer containing a phthalocyanine compound of the general formula (1) or (2) is formed on a substrate, a reflective layer made of gold or aluminum is further formed thereon, and a protective layer is further formed thereon. It is about media.
[0016]
In the phthalocyanine compound of the present invention, the alkoxy group and the alkenyl group have been substituted by the phthalocyanine ring, so that the solubility in the solvent used when applying to the substrate by the spin coating method is improved. In addition, since the alkenyl group substituted on the phthalocyanine ring is conjugated to the phthalocyanine ring, it is easy to control the absorption wavelength region, and the decomposition / melting of the dye is controlled during recording to form pits with high accuracy. In the case of a recording medium having a reflective layer, it contributes to improving the adhesion between the recording layer and the metal layer serving as the reflective layer, thereby reducing the amount of heat generated by decomposition and reducing the amount of heat generated by decomposition. In addition to the conventional method, not only in the high-speed recording but also in the high-density recording method as compared with the conventional method, the effect of improving the sensitivity and the recording characteristics of the optical recording medium was improved.
[0017]
Since the phthalocyanine compound of the present invention has a sharp absorption at 650 to 900 nm, a high molecular extinction coefficient, and excellent long-term stability and light resistance, it is useful for optical recording media (optical disks, optical cards, etc.) using a semiconductor laser. Suitable for recording materials.
[0018]
Hereinafter, preferred embodiments of the present invention will be described in detail.
[0019]
In the general formulas (1) and (2), R ¹ , R ⁴ , R ⁵ Specific examples of the linear or branched alkenyl group having 3 to 10 carbon atoms represented by are a propenyl group, a 2-propenyl group, a 1-methylpropenyl group, a 1-methyl-2-propenyl group, and a 1-ethylpropenyl group. , 1-ethyl-2-propenyl group, 1-propylpropenyl group, 1-propyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, butenyl group, 2-butenyl group, 1-methyl-2- Butenyl group, 1-methylbutenyl group, 2-methyl-2-butenyl group, 2-methylbutenyl group, 3-methyl-2-butenyl group, 3-methylbutenyl group, 2,3-dimethyl-2-butenyl group, 2,3 -Dimethylbutenyl group, 1,1-dimethyl-2-butenyl group, 1-ethyl-2-methyl-2-butenyl group, 1-ethyl-2-methylbutenyl group, pentenyl group 2-pentenyl group, 1-methyl-2-pentenyl group, 1-methylpentenyl group, 2-methyl-2-pentenyl group, 2-methylpentenyl group, 3-methyl-2-pentenyl group, 3-methylpentenyl group, 4-methyl-2-pentenyl group, 4-methylpentenyl group, 2,4-dimethyl-2-pentenyl group, 2,4-dimethylpentenyl group, 1,4-dimethyl-2-pentenyl group, 1,4-dimethyl Pentenyl group, 1-ethyl-2-methyl-2-pentenyl group, 1-ethyl-2-methylpentenyl group, 2-hexenyl group, hexenyl group, 1-methyl-2-hexenyl group, 1-methylhexenyl group, 3 -Methyl-2-hexenyl group, 3-methylhexenyl group, 2-heptenyl group, heptenyl group, 2-methyl-2-heptenyl group, 2-methylheptenyl Group, 3,4,4-trimethyl-2-heptenyl group, 3,4,4-trimethylheptenyl group, 2-octenyl group, octenyl group, 2-nonenyl group, nonenyl group, 2-decenyl group, decenyl group, etc. Is mentioned.
[0020]
In the general formulas (1) and (2), OR ² , OR ³ Specific examples of the linear or branched alkoxy group having 1 to 10 carbon atoms represented by methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, iso-pentyloxy group, neo-pentyloxy group, 2-methylbutyl-3-oxy group, pentyl-2-oxy group, pentyl-3-oxy group , N-hexyloxy group, cyclo-hexyloxy group, 2-methylpentyl-4-oxy group, 2-methylpentyl-3-oxy group, 3-methylpentyl-4-oxy group, n-heptyloxy group, hexyl -3-oxy group, 2-methylhexyl-5-oxy group, 2,4-dimethylpentyl-3-oxy group, Ruhexyl-3-oxy group, heptyl-4-oxy group, n-octyloxy group, 2-ethylhexyl-1-oxy group, 2,5-dimethylhexyl-3-oxy group, 2,4-dimethylhexyl-3- Oxy group, 2,2,4-trimethylpentyl-3-oxy group, n-nonyloxy group, 3,5-dimethylheptyl-4-oxy group, 2,6-dimethylheptyl-3-oxy group, 2,4- Dimethylheptyl-3-oxy group, 2,2,5,5-tetramethylhexyl-3-oxy group, 1-cyclo-pentyl-2,2-dimethylpropyl-1-oxy group, 1-cyclo-hexyl-2 , 2-dimethylpropyl-1-oxy group and the like.
[0021]
In the general formulas (1) and (2), examples of the divalent metal represented by M include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Sn, Mg, and Pb. , Hg, Cd, Ba, Ti, Be, Ca and the like, and examples of the monosubstituted trivalent metal include Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga- Cl, Ga-Br, Ga-I, In-F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C ₆ H ₅ , Al-C ₆ H ₄ (CH ₃ ), In-C ₆ H ₅ , In-C ₆ H ₄ (CH ₃ ), Mn (OH), Mn (OC ₆ H ₅ ), Mn [OSi (CH ₃ ) ₃ ], Fe-Cl, Ru-Cl and the like. Examples of disubstituted tetravalent metals include CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , ZrCl ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , TiF ₂ , TiCl ₂ , TiBr ₂ , Si (OH) ₂ , Sn (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , TiA ₂ , CrA ₂ , SiA ₂ , SnA ₂ , GeA ₂ [A represents an alkyl group, a phenyl group, a naphthyl group and derivatives thereof], Si (OA ') ₂ , Sn (OA ') ₂ , Ge (OA ') ₂ , Ti (OA ') ₂ , Cr (OA ') ₂ [A ′ represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group and a derivative thereof], Si (SA ″) ₂ , Sn (SA ") ₂ , Ge (SA ") ₂ [A "represents an alkyl group, a phenyl group, a naphthyl group and derivatives thereof], and examples of the oxymetal include VO, MnO, TiO. Preferably, Pd, Cu, Ru, Pt is used. , Ni, Co, Rh, Zn, VO, TiO, Si (Y) _2, Sn (Y) _2, Ge (Y) _2, (Y represents a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a hydroxy group, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a trialkylsilyloxy group, a trialkyltinoxy group or a trialkylgermaniumoxy group ), And particularly preferable examples include Cu, Ni, Co, Mg, Zn, Pd, Pt, and VO.
[0022]
As a method for synthesizing the phthalocyanine compound represented by the general formula (1), the following formula (3) or (4):
[0023]
Embedded image

[In the formula (3) or the formula (4), R ¹ And OR ² Has the same meaning as in formula (1). Is reacted with a metal derivative in the presence of 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) in an alcohol, or a metal compound and chloronaphthalene, bromo A method of performing a heating reaction in a high-boiling solvent such as naphthalene or trichlorobenzene may be used. Further, a diiminoisoindoline represented by the general formula (5) or (6) obtained by reacting a compound represented by the general formula (3) or (4) with ammonia using sodium methylate as a catalyst in an alcohol is used. As an intermediate, a method of causing a similar reaction and the like can be mentioned.
[0024]
Embedded image

[In the formula (5) or the formula (6), R ¹ And OR ² Has the same meaning as in formula (1). ]
Further, the compound represented by the general formula (3) or (4) can be produced by the following route.
[0025]
Embedded image

Commercially available 4-nitrophthalonitrile (A) is reacted with R in the presence of a base. ¹ OH [R ¹ Represents the same meaning as described above. To give alkoxyphthalonitrile (B). Further, after the Claisen rearrangement reaction of (B), in the presence of a base, R ² X [R ² Is the OR of general formula (1) ² Represents an alkyl group corresponding to an alkoxy group represented by X, and X represents a halogen atom. To produce a desired mixture of compounds represented by the general formula (3) or (4), and separated by a method such as column chromatography to obtain the desired compound of the general formula (3) ) Or (4) alone.
[0026]
As a method for synthesizing the phthalocyanine compound represented by the general formula (2), the following formula (7)
[0027]
Embedded image

[In the equation (7), OR ³ , R ⁴ And R ⁵ Has the same meaning as in formula (2). ]
Is reacted with a metal derivative and an alcohol in the presence of, for example, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), or a metal compound is reacted with chlornaphthalene or bromonaphthalene. And a method of performing a heat reaction in a high boiling point solvent such as trichlorobenzene. A method in which a compound represented by the general formula (8) is reacted with ammonia in alcohol using sodium methylate as a catalyst, and a diiminoisoindoline represented by the general formula (8) is similarly reacted as an intermediate. And the like.
[0028]
Embedded image

[In the equation (8), OR ³ , R ⁴ And R ⁵ Has the same meaning as in formula (2). ]
The compound represented by the general formula (7) can be produced by the following route.
[0029]
Embedded image

[0030]
Commercially available 3-nitrophthalonitrile (C) is reacted with R in the presence of a base. ⁴ OH [R ⁴ Has the same meaning as in formula (2). To give alkoxyphthalonitrile (D). Further, after the Claisen rearrangement reaction of (D), R ⁵ X [R ⁵ Represents the same meaning as in the general formula (2), and X represents a halogen atom. To give 3-alkoxy-4-alkenylphthalonitrile (E). Further, after the Claisen rearrangement reaction of (E), R ³ X [R ³ Is the OR of general formula (2) ³ Represents an alkyl group corresponding to an alkoxy group represented by X, and X represents a halogen atom. To produce the desired compound represented by the general formula (7).
[0031]
R ¹ OH, R ⁴ Examples of the allyl alcohol derivative represented by OH include allyl alcohol, 2-butenol, 3-methyl-2-butenol, 2-methyl-3-buten-2-ol, and 3-methyl-3-buten-2-ol. , 2-pentenol, 3-penten-2-ol, 1-penten-3-ol, 2,3-dimethyl-3-buten-2-ol, 1-hexen-3-ol, 4-hexen-3-ol All, 4-methyl-3-penten-2-ol, 2-methyl-1-penten-3-ol, 3-methyl-1-penten-3-ol, 4-methyl-1-penten-3-ol, 2,4-dimethyl-1-penten-3-ol, 1-hepten-3-ol, 2-hepten-4-ol, 3-methyl-3-hexen-2-ol, 3-methyl-1-hexen- 3-o , 2-methyl-4-hexen-3-ol, 2-methyl-1-hepten-3-ol, 4-tyl-4-hepten-3-ol, 1-octen-3-ol, 2-octene- Those which can introduce a desired alkenyl group such as 4-ol, 3,4,4, -trimethyl-1-penten-3-ol and 1-nonen-3-ol are exemplified.
[0032]
Examples of the halogen atom represented by X include fluorine, chlorine, bromine and iodine, and among them, chlorine and bromine are preferable.
[0033]
As a method for producing an optical recording medium using the phthalocyanine compound of the present invention, there is a method of coating or vapor-depositing one or two layers of one to three compounds containing the phthalocyanine compound of the present invention on a transparent substrate. . As a coating method, a binder resin is dissolved in a solvent so as to be 20% by weight or less, preferably 0%, and 0.05 to 20% by weight, preferably 0.5 to 20% by weight of the phthalocyanine compound of the present invention. There is a method of applying with a coater. In addition, as a vapor deposition method, 10 ^-5 -10 ^-7 There is a method of depositing a phthalocyanine compound on a substrate at 100 to 300 ° C. torr.
[0034]
The substrate may be any optically transparent resin. For example, acrylic resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polycarbonate resin, polyolefin copolymer resin, vinyl chloride copolymer resin, vinylidene chloride copolymer resin, styrene copolymer resin and the like can be mentioned. The substrate may be subjected to a surface treatment with a thermosetting resin or an ultraviolet curable resin.
[0035]
When an optical recording medium (such as an optical disk or an optical card) is manufactured, it is preferable to use a polyacrylate substrate or a polycarbonate substrate and apply the substrate by a spin coating method in terms of cost and handling by a user.
[0036]
From the viewpoint of the solvent resistance of the substrate, solvents used for spin coating include halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene, dichlorodifluoroethane, etc.) and ethers (eg, tetrahydrofuran, diethyl ether, dipropyl ether, Dibutyl ether, dioxane, etc.), alcohols (eg, methanol, ethanol, propanol, etc.), cellosolves (eg, methyl cellosolve, ethyl cellosolve, etc.), hydrocarbons (eg, hexane, cyclohexane, ethylcyclohexane, cyclooctane, dimethyl) Cyclohexane, octane, benzene, toluene, xylene, etc.) or a mixed solvent thereof is preferably used.
[0037]
To process as a recording medium, the substrate is covered with a substrate as described above, or bonded to a substrate provided with two recording layers with an air gap provided therebetween, or a reflective layer (aluminum or aluminum) is formed on the recording layer. Gold) and laminating a protective layer of a thermosetting or photocurable resin. Al as a protective layer ₂ O ₃ , SiO ₂ , SiO, SnO ₂ And the like may be used.
[0038]
【Example】
Hereinafter, the present invention will be described specifically with reference to examples, but embodiments of the present invention are not limited thereto.
[0039]
Example 1
The following structural formula (3-1)
[0040]
Embedded image

A mixture consisting of 25.4 g (0.1 mol) of the phthalonitrile derivative, 15.2 g (0.1 mol) of DBU, and 125 g of n-amyl alcohol was heated to 100 ° C. under a nitrogen atmosphere. Next, 5.3 g (0.03 mol) of palladium chloride was added at the same temperature, and reacted at 95 to 100 ° C for 20 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed to obtain 14.6 g (yield 52%) of a phthalocyanine compound represented by the following structural formula (1-1).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0041]

[0042]
Embedded image

[0043]
An n-octane solution (10 g / l) of the above phthalocyanine compound is coated with a spiral groove (pitch: 1.6 μm, groove width: 0.6 μm, groove depth: 0.18 μm) with an outer shape of 120 mm and a thickness of 1.2 mm for CD-R polycarbonate. Spin coating was performed on the substrate at 500 to 1000 rpm. A reflective layer was formed by sputtering and depositing 30 nm of gold thereon, followed by overcoating with a photocurable polyacrylic resin and photocuring to form a protective layer, thereby producing a CD-R type medium. An error rate of less than 0.2% when writing an EFM signal at a linear velocity of 1.4 m / s at a power of 6.0 mW using a semiconductor laser having a wavelength of 780 nm on this medium is less than 0.2%. There was no change in the durability test at 63 ° C. for 200 hours.
[0044]
Example 2
The following structural formula (3-2)
[0045]
Embedded image

A mixture consisting of 25.4 g (0.1 mol) of the phthalonitrile derivative, 15.2 g (0.1 mol) of DBU, and 125 g of n-amyl alcohol was heated to 100 ° C. under a nitrogen atmosphere. Next, 3.0 g (0.03 mol) of cuprous chloride was added at the same temperature, and reacted at 95 to 100 ° C. for 20 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification was performed (silica gel 500 g, solvent toluene) to obtain 17.6 g (yield 65%) of a phthalocyanine compound represented by the following structural formula (1-2).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0046]

[0047]
Embedded image

[0048]
A dibutyl ether solution (10 g / l) of the phthalocyanine compound was applied on a polycarbonate substrate for CD-R by a spin coater in the same manner as in Example 1, gold was sputter-deposited thereon, and then a UV curable resin was used. Thus, a protective layer was formed to produce a CD-R type medium. The error rate when writing an EFM signal with a power of 6.0 mW at a linear velocity of 1.4 m / s using a semiconductor laser of 780 nm at a speed of 6.0 mW is less than 0.2%, There was no change even if it was played a million times. Further, there was no problem in recording / reproducing even after 1000 hours at 80 ° C./85%.
[0049]
Example 3
The following structural formula (3-3)
[0050]
Embedded image

A mixture consisting of 29.6 g (0.1 mol) of the phthalonitrile derivative, 15.2 g (0.1 mol) of DBU, and 125 g of n-amyl alcohol represented by the formula was heated to 100 ° C. under a nitrogen atmosphere. Next, 3.0 g (0.03 mol) of cuprous chloride was added at the same temperature, and reacted at 95 to 100 ° C. for 20 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification was performed (500 g of silica gel, solvent of toluene) to obtain 19.1 g (yield: 61%) of a phthalocyanine compound represented by the following structural formula (1-3).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0051]

[0052]
Embedded image

[0053]
10 g of the above phthalocyanine compound is dissolved in 500 ml of a mixed solvent of 3: 1 (volume ratio) of dibutyl ether and diisopropyl ether, and applied on a polycarbonate optical card substrate with a thickness of 100 nm by a spin coater. A protective layer was formed using a cured resin, and an optical card was manufactured. The CN ratio was 61 dB when recorded on this medium with a semiconductor laser beam of 780 nm, linear velocity 2 m / s, 4 mW. In addition, reproduction was possible with a laser beam having a linear velocity of 2 m / s and 0.8 mW. ⁵ It was possible to regenerate it twice. Further, this light card had good storage stability.
[0054]
Example 4
The following structural formula (3-4)
[0055]
Embedded image

A mixture consisting of 29.6 g (0.1 mol) of the phthalonitrile derivative, 15.2 g (0.1 mol) of DBU, and 125 g of n-amyl alcohol represented by the formula was heated to 100 ° C. under a nitrogen atmosphere. Next, 4.7 g (0.03 mol) of vanadium trichloride was added at the same temperature, and the mixture was reacted at 95 to 100 ° C. for 20 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. The filtrate was concentrated under reduced pressure to recover the solvent, and then purified by column (500 g of silica gel, solvent of toluene) to obtain 14.1 g (yield: 45%) of a phthalocyanine compound represented by the following structural formula (1-4).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0056]

[0057]
Embedded image

[0058]
A CD-R type medium was produced in the same manner as in Example 1 using the above phthalocyanine compound. The error rate when writing an EFM signal at a linear velocity of 1.4 m / s with a power of 6.0 mW using a laser having a wavelength of 780 nm on this medium was less than 0.2%.
[0059]
Example 5
The following structural formula (3-5)
[0060]
Embedded image

A mixture consisting of 28.2 g (0.1 mol) of the phthalonitrile derivative, 15.2 g (0.1 mol) of DBU, and 125 g of n-amyl alcohol represented by the following formula was heated to 100 ° C. under a nitrogen atmosphere. Next, 3.0 g (0.03 mol) of cuprous chloride was added at the same temperature, and reacted at 95 to 100 ° C. for 20 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed to obtain 17.9 g (yield 60%) of a phthalocyanine compound represented by the following structural formula (1-5).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0061]

[0062]
Embedded image

[0063]
A CD-R type medium was produced in the same manner as in Example 1 using the above phthalocyanine compound. The error rate when writing an EFM signal at a linear velocity of 1.4 m / s with a power of 6.0 mW using a laser having a wavelength of 780 nm on this medium was less than 0.2%.
[0064]
Example 6
The following structural formula (3-6)
[0065]
Embedded image

A mixture consisting of 28.2 g (0.1 mol) of the phthalonitrile derivative, 15.2 g (0.1 mol) of DBU, and 125 g of n-amyl alcohol represented by the following formula was heated to 100 ° C. under a nitrogen atmosphere. Next, 3.0 g (0.03 mol) of cuprous chloride was added at the same temperature, and reacted at 95 to 100 ° C. for 20 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification was performed (silica gel 500 g, solvent toluene) to obtain 20.9 g (yield 70%) of a phthalocyanine compound represented by the following structural formula (1-6).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0066]

[0067]
Embedded image

[0068]
A CD-R type medium was produced in the same manner as in Example 1 using the above phthalocyanine compound. The error rate when writing an EFM signal at a linear velocity of 1.4 m / s with a power of 6.0 mW using a laser having a wavelength of 780 nm on this medium was less than 0.2%.
[0069]
Example 7
In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 29.4 g (0.1 mol) of 3- (2-pentoxy) -4,6-bis (1-propenyl) phthalonitrile, 15.2 g of DBU ( 0.1 mol), and 125 g of n-amyl alcohol, and heated to 100 ° C. under a nitrogen atmosphere. Next, 5.3 g (0.03 mol) of palladium chloride was added at the same temperature, and reacted at 95 to 100 ° C for 20 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed to obtain 20.2 g (yield 63%) of a phthalocyanine compound represented by the following formula (2-1).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0070]

[0071]
Embedded image

[0072]
An n-octane solution (10 g / l) of the above phthalocyanine compound is coated with a spiral groove (pitch: 1.6 μm, groove width: 0.6 μm, groove depth: 0.18 μm) with an outer shape of 120 mm and a thickness of 1.2 mm for CD-R polycarbonate. Spin coating was performed on the substrate at 500 to 1000 rpm. A reflective layer was formed by sputtering and depositing 30 nm of gold thereon, followed by overcoating with a photocurable polyacrylic resin and photocuring to form a protective layer, thereby producing a CD-R type medium. An error rate of less than 0.2% when writing an EFM signal at a linear velocity of 1.4 m / s at a power of 6.0 mW using a semiconductor laser having a wavelength of 780 nm on this medium is less than 0.2%. There was no change in the durability test at 63 ° C. for 200 hours.
[0073]
Example 8
In a container similar to that of Example 7, 30.8 g (0.1 mol) of 3- (3-hexoxy) -4,6-bis (1-propenyl) phthalonitrile, 15.2 g (0.1 mol) of DBU and n 120 g of amyl alcohol was charged and heated to 100 ° C. under a nitrogen atmosphere. Next, 5.3 g (0.03 mol) of palladium chloride was added at the same temperature, and reacted at 95 to 100 ° C for 20 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. The filtrate was concentrated under reduced pressure to recover the solvent, and then purified by column (500 g of silica gel, solvent of toluene) to obtain 21.8 g (yield 65%) of a phthalocyanine compound represented by the following formula (2-2).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0074]

[0075]
Embedded image

[0076]
A dibutyl ether solution (10 g / l) of the phthalocyanine compound was applied on a polycarbonate substrate for CD-R by a spin coater in the same manner as in Example 7, gold was sputter-deposited thereon, and then a UV-curable resin was used. Thus, a protective layer was formed to prepare a CD-R type medium. The error rate when writing an EFM signal with a power of 6.0 mW at a linear velocity of 1.4 m / s using a semiconductor laser of 780 nm at a speed of 6.0 mW is less than 0.2%, There was no change even if it was played a million times. Further, there was no problem in recording / reproducing even after 1000 hours at 80 ° C./85%.
[0077]
Example 9
In a container similar to that of Example 7, 3- (2-pentoxy) -4,6-bis (1-propenyl) phthalonitrile 29.4 g (0.1 mol), DBU 15.2 g (0.1 mol), and 125 g of n-amyl alcohol was charged and heated to 100 ° C. under a nitrogen atmosphere. Next, 3.0 g (0.03 mol) of cuprous chloride was added at the same temperature, and reacted at 95 to 100 ° C. for 10 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. The filtrate was concentrated under reduced pressure to recover the solvent, and then purified by column (500 g of silica gel, solvent of toluene) to obtain 24.8 g (yield: 80%) of a phthalocyanine compound represented by the following formula (2-3).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0078]

[0079]
Embedded image

[0080]
10 g of the above phthalocyanine compound is dissolved in 500 ml of a mixed solvent of 3: 1 (volume ratio) of dibutyl ether and diisopropyl ether, and applied on a polycarbonate optical card substrate with a thickness of 100 nm by a spin coater. A protective layer was formed using a cured resin, and an optical card was manufactured. The CN ratio was 61 dB when recorded on this medium with a semiconductor laser beam of 780 nm, linear velocity 2 m / s, 4 mW. In addition, reproduction was possible with a laser beam having a linear velocity of 2 m / s and 0.8 mW. ⁵ It was possible to regenerate it twice. Further, this light card had good storage stability.
[0081]
Example 10
In a container similar to that of Example 7, 30.8 g (0.1 mol) of 3- (3-methyl-butoxy) -4- (1-methyl-1-propenyl) -6- (1-propenyl) phthalonitrile, 15.2 g (0.1 mol) of DBU and 120 g of n-amyl alcohol were charged and heated to 100 ° C. under a nitrogen atmosphere. Next, 4.7 g (0.03 mol) of magnesium chloride was added at the same temperature, and reacted at 95 to 100 ° C. for 15 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed to obtain 17.6 g (yield 56%) of a phthalocyanine compound represented by the following formula (2-4).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0082]

[0083]
Embedded image

[0084]
A CD-R type medium was produced in the same manner as in Example 7 using the phthalocyanine compound. The error rate when writing an EFM signal at a linear velocity of 1.4 m / s with a power of 6.0 mW using a laser having a wavelength of 780 nm on this medium was less than 0.2%.
[0085]
Example 11
In a container similar to that of Example 7, 3- (2-pentoxy) -4,6-bis (1-propenyl) phthalonitrile 29.4 g (0.1 mol), DBU 15.2 g (0.1 mol), and 125 g of n-amyl alcohol was charged and heated to 100 ° C. under a nitrogen atmosphere. Next, 4.1 g (0.03 mol) of zinc chloride was added at the same temperature, and the mixture was reacted at 95 to 100 ° C. for 25 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed to obtain 20.8 g (yield 67%) of a phthalocyanine compound represented by the following formula (2-5).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0086]

[0087]
Embedded image

[0088]
A CD-R type medium was produced in the same manner as in Example 7 using the phthalocyanine compound. The error rate when writing an EFM signal at a linear velocity of 1.4 m / s with a power of 6.0 mW using a laser having a wavelength of 780 nm on this medium was less than 0.2%.
[0089]
Example 12
In a container similar to that of Example 7, 32.2 g (0.1 mol) of 3- (2,4-dimethyl-3-pentoxy) -4,6-bis (1-propenyl) phthalonitrile and 15.2 g of DBU (0 mol) were used. .1 mol), and 125 g of n-amyl alcohol, and heated to 100 ° C. under a nitrogen atmosphere. Next, 5.3 g (0.03 mol) of palladium chloride was added at the same temperature and reacted at 95 to 100 ° C. for 25 hours. After the completion of the reaction, the mixture was cooled and insolubles were removed by filtration. After the filtrate was concentrated under reduced pressure to recover the solvent, column purification (silica gel 500 g, solvent toluene) was performed to obtain 20.9 g (yield 60%) of a phthalocyanine compound represented by the following formula (2-6).
The results of the visible absorption spectrum and the elemental analysis were as follows.
[0090]

[0091]
Embedded image

[0092]
A CD-R type medium was produced in the same manner as in Example 7 using the phthalocyanine compound. The error rate when writing an EFM signal at a linear velocity of 1.4 m / s with a power of 6.0 mW using a laser having a wavelength of 780 nm on this medium was less than 0.2%.
[0093]
Comparative Example 1
A medium prepared in the same manner as in Example 1 using the exemplified compound of JP-A-3-62878 (US Pat. No. 5,240,067) represented by the following structural formula (F) was evaluated.
[0094]
Embedded image

[0095]
The optical recording medium using the phthalocyanine compound of the present invention exhibited good sensitivity and recording characteristics at 6.0 mW laser power and 3.6 mW low laser for normal recording, high speed recording and high density recording. The conditions are as follows.
Normal recording: Information of 63 minutes is recorded at a linear velocity of 1.4 m / s (1 × speed).
High-speed recording: Information of 63 minutes is recorded at a linear velocity of 5.6 m / s (4 times speed).
High-density recording: Information of 74 minutes is recorded at a linear velocity of 1.2 m / s.
[0096]
It should be noted that recording was performed with two laser powers of 6.0 and 3.6 mW only during normal recording, and recording was performed at 6.0 mW during other recording methods.
[0097]
Further, the recording sensitivity (C / N ratio), jitter and deviation were measured using a CD decoder DR3552 (manufactured by Kenwood), an LJM-1851 jitter meter (manufactured by Reader Electronics) and a TIA-175 time interval analyzer (manufactured by ADC), respectively. Measured.
[0098]
Evaluation criteria
Sensitivity (C / N ratio)
：: ≧ 55 dB
×: <55 dB
jitter
：: 3T pit jitter and 3T land jitter are <35 ns
×: 3T pit jitter or 3T land jitter ≧ 35 ns
Deviation
：: −50 ns <3T and 11T deviation <50 ns
×: 3T or 11T deviation ≧ 50 ns or 3T or 11T deviation ≦ −50 ns
The results are shown in Tables 1 and 2.
[0099]
[Table 1]

[0100]
[Table 2]

[0101]
【The invention's effect】
In the phthalocyanine compound of the present invention, the alkoxy group and the alkenyl group have been substituted by the phthalocyanine ring, so that the solubility in the solvent used when applying to the substrate by the spin coating method is improved. In addition, since the alkenyl group substituted on the phthalocyanine ring is conjugated with the phthalocyanine ring, it is easy to control the absorption wavelength range, and the decomposition / melting of the dye is controlled during recording, and pit formation with high accuracy has been performed. In the case of a recording medium having a reflective layer, the adhesion between the recording layer and the metal layer that is the reflective layer contributes to the improvement of the conventional method. Not only in the recording method but also in recording at a higher speed compared to the conventional method or in a high-density recording method, the effect of improving the sensitivity and recording characteristics of the optical recording medium was improved.

Claims (5)

The following general formula (1)

[In the formula (1), M represents two hydrogen atoms, a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom, and L ¹ represents the formula (a) or the formula (B)

(In the formula (a) or the formula (b), R ¹ represents a linear or branched alkenyl group having 3 to 10 carbon atoms, and OR ² represents a linear or branched alkoxy group having 1 to 10 carbon atoms. Represents). A phthalocyanine compound represented by the formula: The following general formula (2)

[In the formula (2), M represents two hydrogen atoms, a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, and an oxymetal atom, and L ² represents the formula (c)

(In the formula (c), OR ³ represents a linear or branched alkoxy group having 1 to 10 carbon atoms, and R ⁴ and R ⁵ each independently represent a linear or branched alkenyl group having 3 to 10 carbon atoms. Represents.). A phthalocyanine compound represented by the formula: In the general formula (1) or (2), the central metal represented by M is Pd, Cu, Ru, Pt, Ni, Co, Rh, Zn, VO, TiO, Si (Y) ₂ , Sn (Y) ₂ , Ge (Y) ₂ , (Y is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a hydroxy group, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a trialkylsilyloxy group, a trialkyltinoxy group Or a trialkylgermanium oxy group). An optical recording medium comprising the phthalocyanine compound according to claim 1. A recording layer comprising the phthalocyanine compound according to any one of claims 1 to 3 on a substrate, a reflective layer made of gold or aluminum thereon, and a protective layer further laminated thereon. Optical recording medium.