JP3412078B2 - Optical recording medium - Google Patents

Optical recording medium

Info

Publication number
JP3412078B2
JP3412078B2 JP18160596A JP18160596A JP3412078B2 JP 3412078 B2 JP3412078 B2 JP 3412078B2 JP 18160596 A JP18160596 A JP 18160596A JP 18160596 A JP18160596 A JP 18160596A JP 3412078 B2 JP3412078 B2 JP 3412078B2
Authority
JP
Japan
Prior art keywords
recording medium
group
layer
optical recording
dye
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP18160596A
Other languages
Japanese (ja)
Other versions
JPH106651A (en
Inventor
泰伸 植野
勉 佐藤
辰也 戸村
登 笹
勝次 丸山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ricoh Co Ltd
Original Assignee
Ricoh Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ricoh Co Ltd filed Critical Ricoh Co Ltd
Priority to JP18160596A priority Critical patent/JP3412078B2/en
Publication of JPH106651A publication Critical patent/JPH106651A/en
Application granted granted Critical
Publication of JP3412078B2 publication Critical patent/JP3412078B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/249—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds
    • 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
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/2467—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes azo-dyes
    • 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
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B2007/24612—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes two or more dyes in one layer
    • 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
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/247—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes
    • G11B7/2472—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes cyanine
    • 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
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/248—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes porphines; azaporphines, e.g. phthalocyanines

Landscapes

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

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、記録媒体に関する
ものであって、特に光ビームを照射することにより、記
録材料の透過率、反射率等の光学的な変化を生じさせ、
情報の記録、再生を行ない、且つ追記が可能な光記録媒
体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium, and in particular, by irradiating a light beam, an optical change such as transmittance and reflectance of a recording material is caused,
The present invention relates to an optical recording medium capable of recording / reproducing information and additionally recording.

【０００２】[0002]

【従来の技術】現在の追記光型ディスクシステム（ＷＯ
ＲＭ、ＣＤ−Ｒ）では、使用レーザの発振波長が７７０
ｎｍ〜７９０ｎｍにあり、記録媒体は上記波長で記録、
再生が可能なように構成されている。今後、情報量の増
大に伴い記録媒体の大容量化への流れは必須である。従
って、記録、再生に用いるレーザ波長が短波長化するこ
とも必然的に起ってくることが容易に予想される。た
ゞ、データ用追記光型ディスクとして、シアニン色素や
フタロシアニン色素を記録材料として用いた数多くの提
案がなされている（例えば、シアニン色素を記録材料と
して用いたものには、特開昭５７−８２０９３号、特開
昭５８−５６８９２号、特開昭５８−１１２７９０号、
特開昭５８−１１４９８９号、特開昭５９−８５７９１
号、特開昭６０−８３２３６号、特開昭６０−８９８４
２号、特開昭６１−２５８８６号各公報等が、また、フ
タロシアニン色素を記録材料として用いたものには、特
開昭６１−１５０２４３号、特開昭６１−１７７２８７
号、特開昭６１−１５４８８８号、特開昭６１−２４６
０９１号、特開昭６２−３９２８６号、特開昭６３−３
７７９１号、特開昭６３−３９８８８号各公報等があ
る）が、耐光性、保存安定性に優れ、且つ７００ｎｍ以
下のレーザを用いた光ピックアップで記録、再生が可能
な記録材料は、未だ開発されていないのが現状である。2. Description of the Related Art The current write-once optical disc system (WO
RM, CD-R), the oscillation wavelength of the laser used is 770
nm to 790 nm, the recording medium records at the above wavelength,
It is configured to be playable. In the future, it is essential to increase the capacity of recording media as the amount of information increases. Therefore, it is easily expected that the laser wavelength used for recording and reproduction will be shortened inevitably. As a write-once optical disc for data, many proposals have been made using a cyanine dye or a phthalocyanine dye as a recording material (for example, a disc using a cyanine dye as a recording material is disclosed in JP-A-57-82093). JP-A-58-56892, JP-A-58-112790,
JP-A-58-114989, JP-A-59-85791
No. 60-83236, 60-8984.
No. 2, JP-A No. 61-25886, and those using a phthalocyanine dye as a recording material, JP-A No. 61-150243 and JP-A No. 61-177287.
No. 6/154888 / 61-246
091, JP-A-62-39286, JP-A-63-3
No. 7791, JP-A-63-39888, etc.), but a recording material which is excellent in light resistance and storage stability and which can be recorded and reproduced by an optical pickup using a laser of 700 nm or less has not yet been developed. The current situation is that it has not been done.

【０００３】現在のＣＤ−Ｒディスクシステムも、使用
レーザの発振波長である７７０ｎｍ〜７９０ｎｍで、記
録、再生が可能なように構成されている。このシステム
も上記同様に、大容量化、記録・再生波長の短波長化は
必須である。この点、現在のＣＤ及びＣＤ−ＲＯＭは、
基板自体の凹凸上にＡｌがコーティングしてあり、Ａｌ
の反射率の波長依存性が小さいため、将来、レーザ波長
が短波長化されても再生は可能である。しかしながら、
ＣＤ−Ｒは記録層に６８０ｎｍ〜７５０ｎｍに最大吸収
波長を有する色素を用い、その光学定数及び膜厚構成か
ら７７０ｎｍ〜７９０ｎｍに高い反射率が得られる様設
定してあるため、７００ｎｍ以下の波長域では反射率は
極めて低く、レーザ波長の短波長化に対応できず、現在
のＣＤ−Ｒシステムで記録、再生している情報が、将来
のシステムでは再生出来ない事態を招く。これまでＣＤ
−Ｒとして、シアニン色素／金属反射層、フタロシアニ
ン色素／金属反射層又はアゾ金属キレート色素／金属反
射層などを記録材料として用いた数多くの提案がなされ
ている（例えば、シアニン色素／金属反射層を記録材料
として用いたものには、特開平１−１５９８４２号、特
開平２−４２６５２号、特開平２−１３６５６号、特開
平２−１６８４４６号各公報等が、フタロシアニン色素
を記録材料として用いたものには、特開平１−１７６５
８５号、特開平３−２１５４６６号、特開平４−１１３
８８６号、特開平４−２２６３９０号、特開平５−１２
７２号、特開平５−１７１０５２号、特開平５−１１６
４５６号、特開平５−６９８６０号、特開平５−１３９
０４４号各公報等が、またアゾ金属キレート色素を記録
材料として用いたものには、特開平４−４６１８６号、
特開平４−１４１４８９号、特開平４−３６１０８８
号、特開平５−２７９５８０号各公報等がある）が、こ
のような点に解決を与えるものは未だ見出されていな
い。The current CD-R disc system is also configured to be capable of recording and reproducing at the oscillation wavelength of the laser used, that is, 770 nm to 790 nm. This system is also required to have a large capacity and a short recording / reproducing wavelength, similarly to the above. In this regard, current CDs and CD-ROMs are
Al is coated on the unevenness of the substrate itself.
Since the wavelength dependency of the reflectance of the is small, it is possible to reproduce even if the laser wavelength is shortened in the future. However,
The CD-R uses a dye having a maximum absorption wavelength in the recording layer of 680 nm to 750 nm, and is set to obtain a high reflectance in the range of 770 nm to 790 nm due to its optical constant and film thickness. Since the reflectance is extremely low, it cannot cope with the shortening of the laser wavelength, and the information recorded and reproduced by the current CD-R system cannot be reproduced by the future system. So far CD
As -R, many proposals have been made using a cyanine dye / metal reflection layer, a phthalocyanine dye / metal reflection layer, an azo metal chelate dye / metal reflection layer, or the like as a recording material (for example, a cyanine dye / metal reflection layer is used). The materials used as recording materials are those disclosed in JP-A-1-159842, JP-A-2-42652, JP-A-2-13656, JP-A-2-168446, etc., which use a phthalocyanine dye as a recording material. Japanese Patent Application Laid-Open No. 1-1765
85, JP-A-3-215466, JP-A-4-113.
886, JP-A-4-226390, JP-A-5-12
72, JP-A-5-171052, and JP-A-5-116.
456, JP-A-5-69860, and JP-A-5-139.
No. 044, JP-A-4-46186, and those using an azo metal chelate dye as a recording material.
JP-A-4-141489 and JP-A-4-361088
No. 5,271,580, etc.), but no solution to such a point has been found yet.

【０００４】[0004]

【発明が解決しようとする課題】従って、本発明は上記
のような状況に鑑みてなされたものであって、上記従来
システムに比べて、短波長に発振波長を有する半導体レ
ーザを用いる高密度光ディスクシステムに適用可能な耐
光性、保存安定性に優れた光記録媒体用の記録材料を提
供するとともに、現状システムで記録、再生が可能で且
つ次世代の高密度光ディスクシステムにおいても再生可
能なＣＤ−Ｒ媒体用の記録材料を提供すること目的とす
る。Therefore, the present invention has been made in view of the above situation, and is a high density optical disc using a semiconductor laser having an oscillation wavelength in a shorter wavelength than the conventional system. A CD-recordable material that can be applied to a system and is excellent in light resistance and storage stability for an optical recording medium, and that can be recorded and reproduced in the current system and can be reproduced in a next-generation high-density optical disc system. It is an object of the present invention to provide a recording material for R medium.

【０００５】[0005]

【課題を解決するための手段】本発明者らは鋭意検討を
重ねた結果、特定の構造を有する色素を主成分とする記
録層を設けることにより、発振波長７００ｎｍ以下の半
導体レーザを用いる高密度光ディスクシステムに適用可
能なことを見出し、更には本色素を現在ＣＤ−Ｒ用記録
材料として用いられている有機色素と混合して用いるこ
とにより、７００ｎｍ以下の波長域にも高い反射率を得
ることが可能であることを見出し、本発明を完成するに
至った。As a result of intensive investigations by the present inventors, a high density using a semiconductor laser having an oscillation wavelength of 700 nm or less is provided by providing a recording layer containing a dye having a specific structure as a main component. It has been found that it can be applied to optical disk systems, and by using this dye mixed with an organic dye currently used as a recording material for CD-R, a high reflectance can be obtained even in a wavelength range of 700 nm or less. It was found that the above was possible, and the present invention was completed.

【０００６】即ち、本発明によれば、第一に、基板上に
少なくとも記録層を設けてなる光記録媒体において、前
記記録層中に下記一般式（Ｉ）で示されるアゾ系錯体化
合物の少なくとも１種を含有してなることを特徴とする
光記録媒体が提供される。That is, according to the present invention, firstly, in an optical recording medium in which at least a recording layer is provided on a substrate, at least an azo complex compound represented by the following general formula (I) is contained in the recording layer. There is provided an optical recording medium containing one kind.

【化１】 〔式中、Ｍ、Ｘ、Ｒ1〜Ｒ16及びＹはそれぞれ以下のも
のを表す。 Ｍ：２価の金属原子又は３価の金属原子、 Ｘ：水素原子又はメチル基、 Ｘ：水素原子又はメチル基、 Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、
Ｒ10、Ｒ11、Ｒ12、Ｒ13、Ｒ14、Ｒ15、Ｒ16：それぞれ
独立に水素原子、ニトロ基、ハロゲン原子、アミノ基、
モノアルキルアミノ基、ジアルキルアミノ基、水酸基、
又はアルコキシ基、 Ｙ：水素原子、金属イオン、アンモニウムイオン、置換
若しくは未置換の脂肪族アンモニウムイオン、又は下記
一般式（II）で表わされる四級ピリジニウム誘導体、[Chemical 1] [In the formula, M, X, R 1 to R 16 and Y each represent the following. M: divalent metal atom or trivalent metal atom, X: hydrogen atom or methyl group, X: hydrogen atom or methyl group, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 ,
R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a hydrogen atom, a nitro group, a halogen atom, an amino group,
Monoalkylamino group, dialkylamino group, hydroxyl group,
Or an alkoxy group, Y: a hydrogen atom, a metal ion, an ammonium ion, a substituted or unsubstituted aliphatic ammonium ion, or a quaternary pyridinium derivative represented by the following general formula (II),

【化２】 Ｒ17、Ｒ18：それぞれ独立に水素原子、置換若しくは未
置換のアルキル基、置換若しくは未置換のビニル基、置
換若しくは未置換のアルコキシ基、又はハロゲン原子、 Ｒ19：置換若しくは未置換のアルキル基。〕 第二に、前記記録層上に更に反射層と保護層とをその順
に設けてなり、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
する上記第一に記載した光記録媒体が提供される。第三
に、前記記録層が前記一般式（Ｉ）で示される化合物の
少なくとも１種と６８０ｎｍ〜７５０ｎｍに最大吸収波
長を有する有機色素とを含有してなることを特徴とする
上記第一又は第二に記載した光記録媒体が提供される。
第四に、前記６８０ｎｍ〜７５０ｎｍに最大吸収波長を
有する有機色素がシアニン色素、フタロシアニン色素及
びアゾ金属キレート色素の少なくとも１種である上記第
三に記載した光記録媒体が提供される。第五に、前記記
録層が波長６３０〜７２０ｎｍのレーザ光によって記録
されるものである上記第一〜第四のいずれかに記載した
光記録媒体が提供される。第六に、前記記録層が波長７
７０〜８３０ｎｍのレーザ光によって記録されるもので
ある上記第三又は第四に記載した光記録媒体が提供され
る。[Chemical 2] R 17 and R 18 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted alkoxy group, or a halogen atom, R 19 : a substituted or unsubstituted alkyl group . Secondly, the recording medium is a write-once compact disc type recording medium which is further provided with a reflective layer and a protective layer in this order on the recording layer and records a CD format signal. An optical recording medium is provided. Thirdly, the recording layer contains at least one kind of the compound represented by the general formula (I) and an organic dye having a maximum absorption wavelength at 680 nm to 750 nm. An optical recording medium according to item 2 is provided.
Fourth, there is provided the optical recording medium described in the third, wherein the organic dye having the maximum absorption wavelength in the range of 680 nm to 750 nm is at least one of cyanine dye, phthalocyanine dye and azo metal chelate dye. Fifth, there is provided the optical recording medium according to any one of the first to fourth, wherein the recording layer is recorded by laser light having a wavelength of 630 to 720 nm. Sixth, the recording layer has a wavelength of 7
There is provided an optical recording medium as described in the above third or fourth, which is recorded by a laser beam of 70 to 830 nm.

【０００７】本発明の光記録媒体は、前記一般式（Ｉ）
で示されるアゾ系錯体化合物の少なくとも１種を含有す
る記録層を設けたことから、７００ｎｍ以下の波長域の
レーザ光で記録、再生が可能で、しかも耐光性且つ保存
安定性に優れたものとなり、また別の態様では、前記一
般式（Ｉ）で示される化合物の少なくとも１種と、６８
０〜７５０ｎｍに最大吸収波長を有する有機色素との混
合物からなる記録層を設けたことから、現状システムで
のＣＤ−Ｒ媒体として使用でき、しかも次世代の高密度
光ディスクシステムとなっても、記載された情報を再生
することが可能なものとなる。The optical recording medium of the present invention has the above general formula (I).
Since the recording layer containing at least one of the azo complex compounds shown in 1 is provided, recording and reproduction can be performed with a laser beam in a wavelength range of 700 nm or less, and further, light resistance and storage stability are excellent. In another embodiment, at least one compound represented by the general formula (I) above,
Since a recording layer made of a mixture with an organic dye having a maximum absorption wavelength of 0 to 750 nm is provided, it can be used as a CD-R medium in the current system, and even if it becomes a next-generation high-density optical disc system. The information thus reproduced can be reproduced.

【０００８】[0008]

【発明の実施の形態】以下、本発明を詳しく説明する。
本発明の光記録媒体は、記録層中に下記一般式（Ｉ）で
示されるアゾ系錯体化合物の少なくとも１種を含有して
なることを特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The optical recording medium of the present invention is characterized in that the recording layer contains at least one azo complex compound represented by the following general formula (I).

【化１】 [Chemical 1]

【０００９】まず、本発明で使用する上記一般式（Ｉ）
で示されるアゾ系錯体化合物について説明する。上記一
般式（Ｉ）において、Ｍの具体例としては、Ｃａ、Ｍ
ｇ、Ｚｎ、Ｃｕ、Ｎｉ、Ｐｄ、Ｆｅ、Ｐｂ、Ｃｏ、Ｐ
ｔ、Ｃｄ、Ｒｕなどの２価の金属原子、Ａｌ、Ｉｎ、Ｆ
ｅ、Ｃｒ、Ｇａ、Ｔｌ、Ｍｎなどの３価の金属原子が挙
げられる。First, the above general formula (I) used in the present invention is used.
The azo complex compound represented by will be described. In the general formula (I), specific examples of M include Ca and M.
g, Zn, Cu, Ni, Pd, Fe, Pb, Co, P
Divalent metal atom such as t, Cd, Ru, Al, In, F
Examples include trivalent metal atoms such as e, Cr, Ga, Tl, and Mn.

【００１０】Ｘは、水素原子又はメチル基を表わし、Ｒ
1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、
Ｒ11、Ｒ12、Ｒ13、Ｒ14、Ｒ15、Ｒ16は、それぞれ独立
に水素原子、ニトロ基、ハロゲン原子、アミノ基、モノ
アルキルアミノ基、ジアルキルアミノ基、水酸基、又は
アルコキシ基を表わす。X represents a hydrogen atom or a methyl group, and R
1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 ,
R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 each independently represent a hydrogen atom, a nitro group, a halogen atom, an amino group, a monoalkylamino group, a dialkylamino group, a hydroxyl group, or an alkoxy group. .

【００１１】Ｙは、水素原子、金属イオン、アンモニウ
ムイオン、置換若しくは未置換の脂肪族アンモニウムイ
オン、又は下記一般式（II）で表わされる四級ピリジニ
ウム誘導体を表わす。Y represents a hydrogen atom, a metal ion, an ammonium ion, a substituted or unsubstituted aliphatic ammonium ion, or a quaternary pyridinium derivative represented by the following general formula (II).

【化２】 但し、上式中、Ｒ17、Ｒ18はそれぞれ独立に水素原子、
置換若しくは未置換のアルキル基、置換若しくは未置換
のビニル基、置換若しくは未置換のアルコキシ基、又は
ハロゲン原子を表わし、Ｒ19は置換若しくは未置換のア
ルキル基を表わす。[Chemical 2] However, in the above formula, R 17 and R 18 are each independently a hydrogen atom,
It represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted alkoxy group, or a halogen atom, and R 19 represents a substituted or unsubstituted alkyl group.

【００１２】本発明の前記一般式（Ｉ）で示されるアゾ
系錯体化合物の具体例は、例えば表１−（１）〜表１−
（８）で示されるものが挙げられる。なお、表１中、Ｍ
ｅはメチル基を表わす。Specific examples of the azo complex compound represented by the general formula (I) of the present invention are shown in Table 1- (1) to Table 1-.
Examples include those shown in (8). In Table 1, M
e represents a methyl group.

【００１３】[0013]

【表１−（１）】 [Table 1- (1)]

【００１４】[0014]

【表１−（２）】 [Table 1- (2)]

【００１５】[0015]

【表１−（３）】 [Table 1- (3)]

【００１６】[0016]

【表１−（４）】 [Table 1- (4)]

【００１７】[0017]

【表１−（５）】 [Table 1- (5)]

【００１８】[0018]

【表１−（６）】 [Table 1- (6)]

【００１９】[0019]

【表１−（７）】 [Table 1- (7)]

【００２０】[0020]

【表１−（８）】 [Table 1- (8)]

【００２１】また、記録層においては、前記したよう
に、前記一般式（Ｉ）で示される少なくとも１種の化合
物と、６８０〜７５０ｎｍに最大吸収波長を有する有機
色素との混合物を主成分とすることにより、現状システ
ムで記録再生が可能であるとともに、次世代システムに
おいても再生のみは可能なＣＤ−Ｒ記録媒体となる。こ
の場合の６８０〜７５０ｎｍに最大吸収波長を有する色
素としては、シアニン色素（特にペンタメチンのシアニ
ン色素）、フタロシアニン色素及びアゾ金属キレート色
素が好ましい。Further, in the recording layer, as described above, the main component is a mixture of at least one compound represented by the general formula (I) and an organic dye having a maximum absorption wavelength at 680 to 750 nm. As a result, the CD-R recording medium can be recorded and reproduced by the current system and can be reproduced only by the next-generation system. In this case, the dye having the maximum absorption wavelength at 680 to 750 nm is preferably a cyanine dye (particularly, a cyanine dye of pentamethine), a phthalocyanine dye and an azo metal chelate dye.

【００２２】シアニン色素の好ましい例としては、下記
一般式（III）で示されるものが挙げられる。Preferred examples of cyanine dyes include those represented by the following general formula (III).

【化３】 式中、Ｒ21、Ｒ22は炭素数１〜３のアルキル基、Ｒ23、
Ｒ24は炭素数１〜６の置換又は未置換のアルキル基、Ｚ
は酸アニオンを表わす。なお、芳香族環は他の芳香族環
と縮合されていてもよく、また、アルキル基、ハロゲン
原子、アルコキシ基又はアシル基で置換されていてもよ
い。[Chemical 3] In the formula, R 21 and R 22 are each an alkyl group having 1 to 3 carbon atoms, R 23 ,
R 24 is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, Z
Represents an acid anion. The aromatic ring may be condensed with another aromatic ring, and may be substituted with an alkyl group, a halogen atom, an alkoxy group or an acyl group.

【００２３】フタロシアニン色素の好ましい例として
は、下記一般式（IV−１）若しくは（IV−２）で示され
るものが挙げられる。Preferred examples of the phthalocyanine dye include those represented by the following general formula (IV-1) or (IV-2).

【化４】 式中、Ｍ1はＮｉ、Ｐｄ、Ｃｕ、Ｚｎ、Ｃｏ、Ｍｎ、Ｆ
ｅ、ＴｉＯ又はＶＯを、Ｘ5〜Ｘ8はそれぞれ独立に置換
位置α位の−ＯＲ又は−ＳＲを、Ｒは置換されていても
よい炭素数３〜１２の直鎖、分岐若しくは脂環式アルキ
ル基又は同じく置換されていてもよいアリール基を表わ
す。Ｘ5〜Ｘ8以外のベンゼン環の置換基は水素原子又は
ハロゲン原子である。[Chemical 4] In the formula, M 1 is Ni, Pd, Cu, Zn, Co, Mn, F
e, TiO or VO, X 5 to X 8 are each independently —OR or —SR at the substitution position α-position, and R is an optionally substituted linear, branched or alicyclic group having 3 to 12 carbon atoms. It represents an alkyl group or an aryl group which may also be substituted. Substituents on the benzene ring other than X 5 to X 8 are hydrogen atoms or halogen atoms.

【００２４】[0024]

【化５】 式中、Ｍ2は、Ｓｉ、Ｇｅ、Ｉｎ、又はＳｎを、Ｘ9〜Ｘ
12はそれぞれ独立に置換位置α位の−ＯＲ又は−ＳＲ
を、Ｒは置換されていてもよい炭素数３〜１２の直鎖、
分岐若しくは脂環式アルキル基又は同じく置換されてい
てもよいアリール基を、Ｙ5、Ｙ6は−ＯＳｉＲ25Ｒ26Ｒ
27、−ＯＣＯＲ25Ｒ26Ｒ27、又は−ＯＰＯＲ25Ｒ26Ｒ27
を表わし、Ｒ25〜Ｒ27はそれぞれ独立に炭素数１〜１０
のアルキル基又はアリール基を表わす。Ｘ9〜Ｘ12以外
のベンゼン環の置換基は、水素原子又はハロゲン原子で
ある。[Chemical 5] In the formula, M 2 is Si, Ge, In, or Sn, and is X 9 to X.
12 are each independently -OR or -SR at the substitution position α position.
R is a straight chain having 3 to 12 carbon atoms which may be substituted,
Branched or alicyclic alkyl group, or also an optionally substituted aryl group, Y 5, Y 6 is -OSiR 25 R 26 R
27 , -OCOR 25 R 26 R 27 , or -OPOR 25 R 26 R 27
And R 25 to R 27 each independently have 1 to 10 carbon atoms.
Represents an alkyl group or an aryl group. Substituents on the benzene ring other than X 9 to X 12 are hydrogen atoms or halogen atoms.

【００２５】また、アゾ金属キレート色素の好ましい例
としては、下記一般式（Ｖ）で示されるアゾ系化合物と
金属とのアゾ金属キレート化合物の１種又は２種以上が
挙げられ、、金属の好ましい例としては、Ｎｉ、Ｐｔ、
Ｐｄ、Ｃｏ、Ｃｕ、Ｚｎなどが挙げられる。Preferred examples of the azo metal chelate dye include one or more azo metal chelate compounds of an azo compound represented by the following general formula (V) and a metal, and the metal is preferable. Examples include Ni, Pt,
Pd, Co, Cu, Zn etc. are mentioned.

【化６】 式中、Ａはそれが結合している炭素原子及び窒素原子と
一緒になって複素環を形成する残基を表わし、Ｂはそれ
が結合している二つの炭素原子と一緒になって芳香環又
は複素環を形成する残基を表わし、またＸは活性水素を
有する基を表わす。[Chemical 6] In the formula, A represents a residue which forms a heterocyclic ring together with the carbon atom and nitrogen atom to which it is bonded, and B represents an aromatic ring together with the two carbon atoms to which it is bonded. Or represents a residue forming a heterocycle, and X represents a group having active hydrogen.

【００２６】本発明の前記一般式（Ｉ）で示される少な
くとも１種の色素と前記一般式（III）〜（Ｖ）で示さ
れる少なくとも１種の色素とを併用する場合の重量組成
比は、本発明色素／〔（III）〜（Ｖ）の色素〕＝１０
／１００〜９０／１００、好ましくは４０／１００〜２
０／１００である。また、両色素を併用した場合の記録
層の膜厚は５００Å〜５μｍ、好ましくは１０００Å〜
５０００Åである。When the at least one dye represented by the general formula (I) of the present invention and the at least one dye represented by the general formulas (III) to (V) are used in combination, the weight composition ratio is Inventive dye / [dye of (III) to (V)] = 10
/ 100 to 90/100, preferably 40/100 to 2
It is 0/100. When both dyes are used in combination, the thickness of the recording layer is 500Å to 5 μm, preferably 1000Å to
It is 5000Å.

【００２７】次に、本発明の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、これは追記型光ディスクの例である。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が設けられている。ま
た、必要に応じて基板１の下にハードコート層５を設け
ることができる。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、これはＣＤ−Ｒメ
ディアの例である。図１の構成の記録層２の上に反射層
６が設けられている。なお、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。Next, the structure of the recording medium of the present invention will be described. FIG. 1 is a diagram showing an example of a layer structure applicable to the recording medium of the present invention, which is an example of a write-once optical disc. The recording layer 2 is formed on the substrate 1 through the undercoat layer 3 if necessary.
And a protective layer 4 is further provided if necessary. Further, the hard coat layer 5 can be provided under the substrate 1 as needed. FIG. 2 is a diagram showing another type of layer structure example applicable to the recording medium of the present invention, which is an example of a CD-R medium. A reflective layer 6 is provided on the recording layer 2 having the structure shown in FIG. The recording medium of the present invention is shown in FIG.
Also, an air sandwich structure in which the recording layer (organic thin film layer) having the structure shown in FIG. 2 is placed inside and sealed with another substrate through a space, or a laminated structure in which a recording layer (organic thin film layer) is adhered through a protective layer is used. May be.

【００２８】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。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, it must be transparent to the laser light used, but it is not necessary to be transparent when recording / reproducing is performed from the recording layer side. As the substrate material, for example, polyester, acrylic resin, polyamide, polycarbonate resin, polyolefin resin, phenol resin, epoxy resin, plastic such as polyimide, glass, ceramic or metal can be used. In addition, a guide groove or a guide pit for tracking and a preformat such as an address signal may be formed on the surface of the substrate.

【００２９】２）記録層 記録層はレーザ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）で示される化合物の
少なくとも１種が含有されていることが必要で、記録層
の形成に当たって前記一般式（Ｉ）で示される化合物を
１種又は２種以上の組合せで用いてもよい。更に、これ
らの色素は光学特性、記録感度、信号特性の向上のた
め、他の有機色素及び金属、金属化合物と混合又は積層
化して用いることも、もちろん可能である。この場合の
他の有機色素としては、ポリメチン色素、ナフタロシア
ニン系、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、及び金属錯
体化合物などが挙げられる。また、金属、金属化合物例
としては、Ｉｎ、Ｔｅ、Ｂｉ、Ｓｅ、Ｓｂ、Ｇｅ、Ｓ
ｎ、Ａｌ、Ｂｅ、ＴｅＯ2、ＳｎＯ、Ａｓ、Ｃｄなどが
挙げられ、それぞれを分散混合あるいは積層の形態で用
いることができる。更に、上記染料中に高分子材料、例
えばアイオノマー樹脂、ポリアミド樹脂、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も
良いし、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。2) Recording Layer The recording layer is capable of recording some information by causing some kind of optical change by irradiation of laser light, and
It is necessary that at least one kind of the compound represented by the general formula (I) is contained in the recording layer. When forming the recording layer, one or two compounds represented by the general formula (I) are contained. You may use it in combination of 2 or more types. Further, these dyes can be used as a mixture or layered with other organic dyes and metals or metal compounds in order to improve optical characteristics, recording sensitivity and signal characteristics. Other organic dyes in this case include polymethine dyes, naphthalocyanine dyes, phthalocyanine dyes, squarylium dyes, croconium dyes, pyrylium dyes, naphthoquinone dyes, anthraquinone (indanthrene) dyes, xanthene dyes, triphenylmethane dyes, azulene dyes. , Tetrahydrocholine-based dyes, phenanthrene-based dyes, triphenothiazine-based dyes, and metal complex compounds. Examples of metals and metal compounds include In, Te, Bi, Se, Sb, Ge and S.
Examples thereof include n, Al, Be, TeO 2 , SnO, As, and Cd, and each of them can be used in the form of dispersion mixing or lamination. Further, various materials such as ionomer resins, polyamide resins, vinyl resins, natural polymers, silicones, liquid rubbers, or silane coupling agents may be dispersed and mixed in the above dye, and the characteristics thereof may be mixed. For the purpose of improvement, it can be used together with a stabilizer (for example, a transition metal complex), a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer and the like.

【００３０】記録層の形成は蒸着、スパッタリング、Ｃ
ＶＤ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、上記染料などを有
機溶剤に溶解して、スプレー、ローラーコーティング、
ディッピング又はスピンコーティングなどの慣用のコー
ティング法で行なうことができる。用いられる有機溶剤
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、あるいはメトキシエタノール、
エトキシエタノール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
炭化水素類などが挙げられる。記録層の膜厚は、１００
Å〜１０μｍ、好ましくは２００Å〜２０００Åが適当
である。The recording layer is formed by vapor deposition, sputtering, C
It can be done by conventional means such as VD or solvent coating. When the coating method is used, the dye or the like is dissolved in an organic solvent, spraying, roller coating,
It can be carried out by a conventional coating method such as dipping or spin coating. As the organic solvent to be used, 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, 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,
Aromatic compounds such as benzene, xylene, monochlorobenzene, dichlorobenzene, or methoxyethanol,
Examples thereof include cellosolves such as ethoxyethanol, hydrocarbons such as hexane, pentane, cyclohexane and methylcyclohexane. The thickness of the recording layer is 100
Å-10 μm, preferably 200 Å-2000 Å are suitable.

【００３１】３）下引き層 下引き層は、接着性の向上、水又はガスなどに対す
るバリヤー、記録層の保存安定性の向上、反射率の
向上、溶剤からの基板の保護、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。の目的に対しては高分子材料、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化合物
及びシランカップリング剤などを用いることができ、
及びの目的に対しては、上記高分子材料以外に無機化
合物、例えばＳｉＯ2、ＭｇＦ2、ＳｉＯ、ＴｉＯ2、Ｚ
ｎＯ、ＴｉＮ、ＳｉＮなどがあり、更に金属又は半金
属、例えばＺｎ、Ｃｕ、Ｎｉ、Ｃｒ、Ｇｅ、Ｓｅ、Ａ
ｕ、Ａｇ、Ａｌなどを用いることができる。また、の
目的に対しては、金属、例えばＡｌ、Ａｕ、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、及びの目
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。3) Undercoat layer The undercoat layer is an adhesive layer, a barrier against water or gas, an improved storage stability of the recording layer, an improved reflectance, protection of the substrate from a solvent, a guide groove, and a guide. It is used to form pits and preformats. For the purpose of, it is possible to use various polymer compounds such as ionomer resins, polyamides, vinyl resins, natural resins, natural polymers, silicones, liquid rubbers, and silane coupling agents.
For the purpose of and, in addition to the above polymer materials, inorganic compounds such as SiO 2 , MgF 2 , SiO, TiO 2 , Z
nO, TiN, SiN, etc., and further metal or semimetal, for example, Zn, Cu, Ni, Cr, Ge, Se, A
u, Ag, Al or the like can be used. For the purpose of (1), a metal such as Al, Au, Ag or the like, or an organic thin film having a metallic luster such as a methine dye or a xanthene dye can be used, and for the purpose of A curable resin, a thermosetting resin, a thermoplastic resin or the like can be used. The thickness of the undercoat layer is 0.
01 to 30 μm, preferably 0.05 to 10 μm is suitable.

【００３２】４）反射層 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。材料例としては、Ａｕ、
Ａｇ、Ａｌ、Ｃｒ、Ｎｉ、Ｆｅ、Ｓｎなどが挙げられ、
反射率、生産性の点からＡｕ、Ａｇ、Ａｌが最も好まし
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５０〜５０
００Å、好ましくは１００〜３０００Åである。4) Reflective layer The reflective layer may be made of a metal or semi-metal which is highly resistant to corrosion and which has a high reflectance. Examples of materials include Au,
Ag, Al, Cr, Ni, Fe, Sn, etc. are mentioned,
From the viewpoint of reflectance and productivity, Au, Ag and Al are most preferable. These metals and semi-metals may be used alone or 2
It may be an alloy of at least one kind. Examples of the film forming method include vapor deposition and sputtering, and the film thickness is 50 to 50.
It is 00Å, preferably 100 to 3000Å.

【００３３】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、記録層（反射
吸収層）を傷、埃、汚れなどから保護する、記録層
（反射吸収層）の保存安定性の向上、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、ＳｉＯ2なども用いること
もでき、有機材料としてポリメチルアクリレート、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、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０．０５〜１
０μｍが適当である。5) Protective Layer, Substrate Surface Hard Coat Layer The protective layer or substrate surface hard coat layer protects the recording layer (reflective / absorptive layer) from scratches, dust, dirt, etc. It is used for the purpose of improving stability and reflectance. For these purposes,
The materials shown for the undercoat layer can be used. Further, SiO, SiO 2, etc. can be used as the inorganic material, and polymethyl acrylate, polycarbonate, epoxy resin, polystyrene, polyester resin, vinyl resin, cellulose, aliphatic hydrocarbon resin, natural rubber, styrene-butadiene as the organic material. Resins, chloroprene rubber, waxes, alkyd resins, drying oils, heat-softening and heat-melting resins such as rosin can also be used. The most preferable material among the above materials is an ultraviolet curable resin having excellent productivity. The thickness of the protective layer or the hard coat layer on the substrate surface is 0.01 to 30 μm, preferably 0.05 to 1
0 μm is suitable.

【００３４】本発明において、前記の下引き層、保護層
及び基板表面ハードコート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。In the present invention, the undercoat layer, the protective layer and the substrate surface hard coat layer are the same as in the case of the recording layer, such as a stabilizer, a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, A plasticizer and the like can be included.

【００３５】[0035]

【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。The present invention will be described below with reference to examples, but the present invention is not limited thereto.

【００３６】実施例１ 実施例１ 厚さ１．２μｍのポリメチルメタクリレート基板上にフ
ォトポリマーにて、深さ１２００Å、半値幅０．４μ
ｍ、トラックピッチ１．４μｍの案内溝を形成した基板
上に、化合物具体例Ｎｏ．１のクロロホルム溶液をスピ
ンナー塗布し、厚さ８００Åの記録層を設けて記録媒体
を得た。Example 1 Example 1 A photopolymer was formed on a polymethylmethacrylate substrate having a thickness of 1.2 μm and a depth of 1200Å and a half value width of 0.4 μ.
m, the compound specific example No. 2 was formed on the substrate having the guide groove with the track pitch of 1.4 μm. The chloroform solution of No. 1 was applied to a spinner and a recording layer having a thickness of 800 Å was provided to obtain a recording medium.

【００３７】実施例２〜８ 実施例１において、化合物具体例Ｎｏ．１の代わりに、
化合物具体例Ｎｏ．２、Ｎｏ．３、Ｎｏ．４、Ｎｏ．
５、Ｎｏ．６、Ｎｏ．７、Ｎｏ．８を用いたこと以外
は、実施例１と同様にして実施例２〜８の記録媒体を得
た。Examples 2 to 8 In Example 1, specific examples of compounds No. Instead of 1.
Specific compound No. 2, No. 3, No. 4, No.
5, No. 6, No. 7, No. Recording media of Examples 2 to 8 were obtained in the same manner as in Example 1 except that No. 8 was used.

【００３８】比較例１ 実施例１において、化合物具体例Ｎｏ．１の代わりに下
記式（VI）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。Comparative Example 1 In Example 1, the compound specific example 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 (VI) was used in place of 1.

【化７】 [Chemical 7]

【００３９】前記の実施例１〜８及び比較例１の記録媒
体を用い、下記の記録条件で基板から光を入射して記録
し、その後記録位置を再生光によりＣ／Ｎ比及び反射率
を測定した。その結果を表２に示す。 記録条件： レーザ発振波長 ６８０ｎｍ 記録周波数 １．２５ＭＨｚ 記録線速 １．２ｍ／ｓｅｃ 再生条件： レーザ発振波長 ６８０ｎｍ 再生パワー ０．２５〜０．３ｍＷの連続光 スキャニングバンド巾 ３０ＫＨｚ 耐光テスト条件： 耐光テスト ４万Ｌｕｘ、Ｘｅ光、５０時間連続照射 保存テスト ８５℃、８５％、７２０時間放置Using the recording media of Examples 1 to 8 and Comparative Example 1 described above, light was incident from the substrate for recording under the following recording conditions, and then the recording position was measured by reproducing light to measure the C / N ratio and reflectance. It was measured. The results are shown in Table 2. Recording conditions: Laser oscillation wavelength 680 nm Recording frequency 1.25 MHz Recording linear velocity 1.2 m / sec Reproduction conditions: Laser oscillation wavelength 680 nm Reproduction power 0.25 to 0.3 mW continuous light scanning bandwidth 30 KHz Light resistance test conditions: Light resistance test 4 10,000 Lux, Xe light, 50 hours continuous irradiation storage test 85 ℃, 85%, leave for 720 hours

【００４０】[0040]

【表３】 [Table 3]

【００４１】実施例９ 深さ１０００Å、半値幅０．４μｍ、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、化合物具体例Ｎｏ．９をメ
チルシクロヘキサン、２−メトキシエタノール、メチル
エチルケトン、テトラヒドロフランの混合溶液に溶解し
た液をスピンナー塗布し、厚さ１８００Åの記録層を形
成し、次いでその上にスパッタ法により金２０００Åの
反射層を設け、更にその上にアクリル系フォトポリマー
にて５μｍの保護層を設け、記録媒体を得た。Example 9 On a 1.2 mm thick injection-molded polycarbonate substrate having guide grooves with a depth of 1000 Å, a half-value width of 0.4 μm and a track pitch of 1.6 μm, the compound No. 9 was dissolved in a mixed solution of methylcyclohexane, 2-methoxyethanol, methylethylketone and tetrahydrofuran by spinner coating to form a recording layer having a thickness of 1800Å, and then a reflective layer of 2000Å gold was formed on the recording layer by sputtering. Further, a protective layer of 5 μm was formed thereon by an acrylic photopolymer to obtain a recording medium.

【００４２】実施例１０〜１６ 実施例９において、化合物具体例Ｎｏ．９の代わりにそ
れぞれ化合物具体例Ｎｏ．１０、Ｎｏ．１１、Ｎｏ．１
２、Ｎｏ．１３、Ｎｏ．１４、Ｎｏ．１５、Ｎｏ．１６
を用いたこと以外は、実施例９と同様にして実施例１０
〜１６の記録媒体を得た。Examples 10 to 16 In Example 9, compound specific examples No. Compound Specific Example No. 10, No. 11, No. 1
2, No. 13, No. 14, No. 15, No. 16
Example 10 was conducted in the same manner as in Example 9 except that
-16 recording media were obtained.

【００４３】比較例２ 実施例９において、化合物具体例Ｎｏ．９の代わりに比
較例１で用いた前記式（VI）で示される化合物を用いた
こと以外は、実施例９と同様にして比較例２の記録媒体
を得た。Comparative Example 2 In Example 9, compound specific example No. A recording medium of Comparative Example 2 was obtained in the same manner as in Example 9 except that the compound represented by the formula (VI) used in Comparative Example 1 was used instead of 9.

【００４４】実施例９〜１６及び比較例２の記録媒体に
発振波長６８０ｎｍ、ビーム径１．４μｍの半導体レー
ザ光を用い、トラッキングしながらＥＦＭ信号を記録し
（線速１．４ｍ／ｓｅｃ）、同じレーザの連続光で再生
し、再生波形を観察した。その結果を表３に示す。Using the semiconductor laser light having an oscillation wavelength of 680 nm and a beam diameter of 1.4 μm on the recording media of Examples 9 to 16 and Comparative Example 2, an EFM signal was recorded while tracking (linear velocity 1.4 m / sec). The reproduced waveform was observed by reproducing with the continuous light of the same laser. The results are shown in Table 3.

【００４５】[0045]

【表３】 [Table 3]

【００４６】実施例１７ 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、下記の式（VII）で示され
る化合物と化合物具体例Ｎｏ．１７とを、重量比（１／
１）のメチルシクロヘキサン、２−メトキシエタノー
ル、メチルエチルケトン、テトラヒドロフラン混合溶媒
に溶解し、スピンナー塗布して、厚さ１７００Åの記録
層を形成し、次いで、スパッタ法により金２０００Åの
反射層を形成して、更にその上にアクリル系フォトポリ
マーにて５μｍの保護層を設け、記録媒体を得た。Example 17 A compound represented by the following formula (VII) was formed on a 1.2 mm thick injection-molded polycarbonate substrate having guide grooves with a depth of 1000 Å, a half value width of 0.45 μm and a track pitch of 1.6 μm. Specific compound No. 17 and the weight ratio (1 /
1) Dissolved in a mixed solvent of methylcyclohexane, 2-methoxyethanol, methylethylketone, and tetrahydrofuran, spinner applied to form a recording layer having a thickness of 1700Å, and then a reflective layer of gold 2000Å was formed by a sputtering method. Further, a protective layer of 5 μm was formed thereon by an acrylic photopolymer to obtain a recording medium.

【００４７】[0047]

【化８】 [Chemical 8]

【００４８】実施例１８及び１９ 実施例１７において、化合物具体例Ｎｏ．１７の代わり
にそれぞれ化合物具体例Ｎｏ．１８、Ｎｏ．１９を用い
たこと以外は、実施例１７と同様にして実施例１８及び
１９の記録媒体を得た。Examples 18 and 19 In Example 17, specific compound No. Compound Example No. 17 instead of Compound No. 17 18, No. Recording media of Examples 18 and 19 were obtained in the same manner as in Example 17, except that No. 19 was used.

【００４９】実施例２０及び２１ 実施例１７において、化合物具体例Ｎｏ．１７の代わり
にそれぞれ化合物具体例Ｎｏ．２０、Ｎｏ．２１を用
い、且つ前記式（VII）で示される化合物の代わりに下
記式（VIII）で示される化合物を用いたこと以外は、実
施例１７と同様にして実施例２０及び２１の記録媒体を
得た。Examples 20 and 21 In Example 17, compound specific examples No. Compound Example No. 17 instead of Compound No. 17 20, No. Recording media of Examples 20 and 21 were obtained in the same manner as in Example 17, except that 21 was used and the compound of the following formula (VIII) was used instead of the compound of the above formula (VII). It was

【００５０】[0050]

【化９】 [Chemical 9]

【００５１】実施例２２〜２４ 実施例１７において、化合物具体例Ｎｏ．１７の代わり
にそれぞれ化合物具体例Ｎｏ．２２、Ｎｏ．２３、Ｎ
ｏ．２４を用い、且つ前記式（VII）で示される化合物
の代わりに下記式（IX）で示される化合物を用いたこと
以外は、実施例１７と同様にして実施例２２〜２４の記
録媒体を得た。Examples 22 to 24 In Example 17, compound specific examples No. Compound Example No. 17 instead of Compound No. 17 22, No. 23, N
o. Recording media of Examples 22 to 24 were obtained in the same manner as in Example 17 except that the compound represented by the formula (VII) was used instead of the compound represented by the formula (VII). It was

【００５２】[0052]

【化１０】 [Chemical 10]

【００５３】比較例３〜５ 実施例１７において、記録層をそれぞれ前記一般式（VI
I）で示される化合物のみ、前記一般式（VIII）で示さ
れる化合物のみ、前記一般式（IX）で示される化合物の
みとしたこと以外は、実施例１７と同様にして比較例３
〜５の記録媒体を得た。Comparative Examples 3 to 5 In Example 17, the recording layers were each formed by the above general formula (VI
Comparative Example 3 in the same manner as in Example 17 except that only the compound represented by I), only the compound represented by the general formula (VIII), and only the compound represented by the general formula (IX) were used.
Recording media of ~ 5 were obtained.

【００５４】実施例１７〜２４及び比較例３〜５の記録
媒体に発振波長７８０ｎｍ、ビーム径１．６μｍの半導
体レーザ光を用い、トラッキングしながらＥＦＭ信号を
記録し（線速１．４ｍ／ｓｅｃ）、前記レーザ及び発振
波長６８０ｎｍ、ビーム径１．４μｍの半導体レーザの
連続光で再生し、再生波形を観察した。その結果を表４
に示す。EFM signals were recorded on the recording media of Examples 17 to 24 and Comparative Examples 3 to 5 with a semiconductor laser beam having an oscillation wavelength of 780 nm and a beam diameter of 1.6 μm (linear velocity 1.4 m / sec). ), Reproduction was performed with continuous light of the laser and a semiconductor laser having an oscillation wavelength of 680 nm and a beam diameter of 1.4 μm, and the reproduction waveform was observed. The results are shown in Table 4.
Shown in.

【００５５】[0055]

【表４】 [Table 4]

【００５６】[0056]

【発明の効果】請求項１の光記録媒体は、前記一般式
（Ｉ）で示されるアゾ系錯体化合物の少なくとも１種を
記録層中に含有してなるものとしたことから、波長７０
０ｎｍ以下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７００ｎｍ以下の波長域のレー
ザ光で記録、再生が可能であり、しかも耐光性、保存安
定性に優れている。According to the optical recording medium of the present invention, at least one azo complex compound represented by the general formula (I) is contained in the recording layer.
Since it has high light absorption and light reflectivity below 0 nm, it can record and reproduce with laser light in the wavelength range below 700 nm, which enables high density recording, and has excellent light resistance and storage stability. ing.

【００５７】請求項２の光記録媒体は、記録層上に反射
層を積層したＣＤ−Ｒ記録媒体の記録層中に前記一般式
（Ｉ）で示されるアゾ系錯体化合物を含有してなるもの
としたことから、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記録媒体が提供
できる。The optical recording medium of claim 2 is a CD-R recording medium in which a reflective layer is laminated on the recording layer, and the recording layer contains the azo complex compound represented by the general formula (I). Therefore, since it has a high refractive index at a wavelength of 770 to 830 nm and high stability, it is possible to provide a CD-R recording medium having high reflectance and excellent storage stability and reproduction stability.

【００５８】請求項３の光記録媒体は、前記一般式
（Ｉ）で示される化合物の少なくとも１種と６８０〜７
５０ｎｍに最大吸収波長を有する有機色素とを記録層中
に含有してなるものとしたことから、現状システムで記
録、再生が可能で、しかも次世代の高密度光ディスクシ
ステムでも、記録された情報を再生することが可能にな
る。An optical recording medium according to claim 3 comprises at least one compound represented by the general formula (I) and 680-7.
Since the recording layer contains an organic dye having a maximum absorption wavelength of 50 nm, recording and reproduction can be performed with the current system, and even in the next-generation high-density optical disc system, the recorded information can be recorded. It becomes possible to reproduce.

【００５９】請求項４の光記録媒体は、６８０〜７５０
ｎｍに最大吸収波長を有する有機色素として、シアニン
色素、フタロシアニン色素及びアゾ金属キレート色素の
少なくとも一種を選択したことから、高品位の信号特性
が記録可能となる。An optical recording medium according to claim 4 is 680 to 750.
Since at least one of the cyanine dye, the phthalocyanine dye and the azo metal chelate dye is selected as the organic dye having the maximum absorption wavelength in nm, high quality signal characteristics can be recorded.

【００６０】請求項５の光記録媒体は、記録層が波長６
３０〜７２０ｎｍのレーザ光によって記録されるもので
あるため、７７０〜８３０ｎｍ対応の光記録媒体に比べ
１．６〜１．８倍の高密度化追記型光記録媒体が得られ
る。In the optical recording medium of claim 5, the recording layer has a wavelength of 6
Since the recording is performed with a laser beam of 30 to 720 nm, a high density write-once write-once optical recording medium having a density of 1.6 to 1.8 times that of an optical recording medium compatible with 770 to 830 nm can be obtained.

【００６１】請求項６の光記録媒体は、前記記録層が波
長７７０〜８３０ｎｍのレーザ光によって記録されるも
のであることから、現行システムでの優れたＣＤ−Ｒ記
録媒体が提供できる。According to the optical recording medium of the sixth aspect, since the recording layer is recorded by laser light having a wavelength of 770 to 830 nm, an excellent CD-R recording medium in the existing system can be provided.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明の記録媒体に適用し得る通常の追記型光
記録媒体としての層構成例を示す図である。FIG. 1 is a diagram showing an example of a layer structure as an ordinary write-once type optical recording medium applicable to the recording medium of the present invention.

【図２】本発明の記録媒体に適用し得るＣＤ−Ｒ用とし
ての層構成例を示す図である。FIG. 2 is a diagram showing an example of a layer structure for a CD-R that can be applied to the recording medium of the present invention.

【符号の説明】[Explanation of symbols]

１ 基板 ２ 記録層（有機色素層） ３ 下引き層 ４ 保護層 ５ ハードコート層 ６ 反射層 1 substrate 2 Recording layer (organic dye layer) 3 subbing layer 4 protective layer 5 Hard coat layer 6 reflective layer

───────────────────────────────────────────────────── フロントページの続き (72)発明者 笹 登 東京都大田区中馬込１丁目３番６号 株 式会社リコー内 (72)発明者 丸山 勝次 東京都大田区中馬込１丁目３番６号 株 式会社リコー内 (56)参考文献 特開 平９−39394（ＪＰ，Ａ) 特開 昭63−35587（ＪＰ，Ａ) 特開 昭63−81165（ＪＰ，Ａ) 特開 昭58−101093（ＪＰ，Ａ) 特開 平５−193263（ＪＰ，Ａ) 特開 平８−99467（ＪＰ，Ａ) 特開 平２−305832（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B41M 5/26 G11B 7/24 516 ＣＡＰＬＵＳ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noboru Sasa 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd. (72) Katsuji Maruyama 1-3-6 Nakamagome, Ota-ku, Tokyo (56) References JP-A-9-39394 (JP, A) JP-A-63-35587 (JP, A) JP-A-63-81165 (JP, A) JP-A-58-101093 (JP, A) JP-A-5-193263 (JP, A) JP-A-8-99467 (JP, A) JP-A-2-305832 (JP, A) (58) Fields investigated (Int. Cl. 7) , DB name) B41M 5/26 G11B 7/24 516 CAPLUS (STN) REGISTRY (STN)

Claims (6)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 基板上に少なくとも記録層を設けてなる
光記録媒体において、前記記録層中に下記一般式（Ｉ）
で示されるアゾ系錯体化合物の少なくとも１種を含有し
てなることを特徴とする光記録媒体。 【化１】 〔式中、Ｍ、Ｘ、Ｒ1〜Ｒ16及びＹはそれぞれ以下のも
のを表す。 Ｍ：２価の金属原子又は３価の金属原子、 Ｘ：水素原子又はメチル基、 Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、
Ｒ10、Ｒ11、Ｒ12、Ｒ13、Ｒ14、Ｒ15、Ｒ16：それぞれ
独立に水素原子、ニトロ基、ハロゲン原子、アミノ基、
モノアルキルアミノ基、ジアルキルアミノ基、水酸基、
又はアルコキシ基、 Ｙ：水素原子、金属イオン、アンモニウムイオン、置換
若しくは未置換の脂肪族アンモニウムイオン、又は下記
一般式（II）で表わされる四級ピリジニウム誘導体、 【化２】 Ｒ17、Ｒ18：それぞれ独立に水素原子、置換若しくは未
置換のアルキル基、置換若しくは未置換のビニル基、置
換若しくは未置換のアルコキシ基、又はハロゲン原子、 Ｒ19：置換若しくは未置換のアルキル基。〕1. An optical recording medium in which at least a recording layer is provided on a substrate, wherein the recording layer has the following general formula (I):
An optical recording medium comprising at least one kind of an azo complex compound represented by [Chemical 1] [In the formula, M, X, R 1 to R 16 and Y each represent the following. M: divalent metal atom or trivalent metal atom, X: hydrogen atom or methyl group, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 ,
R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a hydrogen atom, a nitro group, a halogen atom, an amino group,
Monoalkylamino group, dialkylamino group, hydroxyl group,
Or an alkoxy group, Y: a hydrogen atom, a metal ion, an ammonium ion, a substituted or unsubstituted aliphatic ammonium ion, or a quaternary pyridinium derivative represented by the following general formula (II): R 17 and R 18 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted alkoxy group, or a halogen atom, R 19 : a substituted or unsubstituted alkyl group . ] 【請求項２】 前記記録層上に更に反射層と保護層とを
その順に設けてなり、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
特徴とする請求項１に記載の光記録媒体。2. A write-once compact disk type recording medium for recording a CD format signal, comprising a reflective layer and a protective layer further provided in this order on the recording layer. Optical recording medium. 【請求項３】 前記記録層が前記一般式（Ｉ）で示され
る化合物の少なくとも１種と６８０ｎｍ〜７５０ｎｍに
最大吸収波長を有する有機色素とを含有してなることを
特徴とする請求項１又は２に記載の光記録媒体。3. The recording layer containing at least one compound represented by the general formula (I) and an organic dye having a maximum absorption wavelength at 680 nm to 750 nm. 2. The optical recording medium according to 2. 【請求項４】 前記６８０ｎｍ〜７５０ｎｍに最大吸収
波長を有する有機色素がシアニン色素、フタロシアニン
色素及びアゾ金属キレート色素の少なくとも１種である
請求項３に記載の光記録媒体。4. The optical recording medium according to claim 3, wherein the organic dye having the maximum absorption wavelength at 680 nm to 750 nm is at least one of a cyanine dye, a phthalocyanine dye and an azo metal chelate dye. 【請求項５】 前記記録層が波長６３０〜７２０ｎｍの
レーザ光によって記録されるものである請求項１〜４の
いずれかに記載の光記録媒体。5. The optical recording medium according to claim 1, wherein the recording layer is recorded by laser light having a wavelength of 630 to 720 nm. 【請求項６】 前記記録層が波長７７０〜８３０ｎｍの
レーザ光によって記録されるものである請求項３又４に
記載の光記録媒体。6. The optical recording medium according to claim 3, wherein the recording layer is recorded by laser light having a wavelength of 770 to 830 nm.
JP18160596A 1996-06-21 1996-06-21 Optical recording medium Expired - Fee Related JP3412078B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP18160596A JP3412078B2 (en) 1996-06-21 1996-06-21 Optical recording medium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP18160596A JP3412078B2 (en) 1996-06-21 1996-06-21 Optical recording medium

Publications (2)

Publication Number Publication Date
JPH106651A JPH106651A (en) 1998-01-13
JP3412078B2 true JP3412078B2 (en) 2003-06-03

Family

ID=16103738

Family Applications (1)

Application Number Title Priority Date Filing Date
JP18160596A Expired - Fee Related JP3412078B2 (en) 1996-06-21 1996-06-21 Optical recording medium

Country Status (1)

Country Link
JP (1) JP3412078B2 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4702730B2 (en) 1999-12-02 2011-06-15 株式会社林原生物化学研究所 Styryl dye
EP1429324A1 (en) 1999-12-17 2004-06-16 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Monomethine cyanine dyes suitable for the use in optical recording media
AU4692801A (en) * 2000-04-17 2001-10-30 Mitsubishi Chemical Corporation Optical recording medium
US6737143B2 (en) 2001-06-14 2004-05-18 Ricoh Company Ltd. Optical recording medium, optical recording method and optical recording device
JP2003063139A (en) * 2001-08-27 2003-03-05 Ricoh Co Ltd Optical recording medium
WO2004088649A2 (en) * 2003-04-04 2004-10-14 Ciba Specialty Chemicals Holding Inc. High-capacity optical storage media
JP4137691B2 (en) 2003-04-30 2008-08-20 株式会社リコー Optical recording medium

Also Published As

Publication number Publication date
JPH106651A (en) 1998-01-13

Similar Documents

Publication Publication Date Title
JP3486709B2 (en) Optical recording medium
JPH1139707A (en) Optical recording medium
JP3412078B2 (en) Optical recording medium
JPH10181206A (en) Optical recording medium
JPH1120317A (en) Light information recording medium
JPH1086519A (en) Optical recording medium
JP3482481B2 (en) Optical information recording medium
JP3456621B2 (en) Optical recording medium
JP3776201B2 (en) Optical recording medium
JP2002264521A (en) Optical recording medium
JP3624989B2 (en) Optical recording medium
JPH08282107A (en) Optical recording medium
JP3409101B2 (en) Optical information recording medium
JP3681030B2 (en) Optical recording medium
JP3477501B2 (en) Optical information recording medium
JP3412077B2 (en) Optical recording medium
JP3632095B2 (en) Optical recording medium
JP3623039B2 (en) Optical recording medium
JPH091934A (en) Optical information recording medium
JPH09147413A (en) Optical information recording medium and recording/ reproducing method
JP3525270B2 (en) Optical recording medium
JPH0776169A (en) Optical information record medium
JPH07156550A (en) Optical data recording medium
JP3776209B2 (en) Optical recording medium
JPH1142857A (en) Optical recording medium and method for optically recording and reproducing using the medium

Legal Events

Date Code Title Description
FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20090328

Year of fee payment: 6

LAPS Cancellation because of no payment of annual fees