JPS62193885A - Optical information-recording medium - Google Patents

Optical information-recording medium

Info

Publication number
JPS62193885A
JPS62193885A JP61035488A JP3548886A JPS62193885A JP S62193885 A JPS62193885 A JP S62193885A JP 61035488 A JP61035488 A JP 61035488A JP 3548886 A JP3548886 A JP 3548886A JP S62193885 A JPS62193885 A JP S62193885A
Authority
JP
Japan
Prior art keywords
tables
formulas
recording layer
recording medium
recording
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.)
Pending
Application number
JP61035488A
Other languages
Japanese (ja)
Inventor
Toshiyuki Kanno
敏之 管野
Hitoshi Watanabe
均 渡辺
Kohei Hamanishi
浜西　広平
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.)
Olympus Corp
Original Assignee
Olympus Optical 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 Olympus Optical Co Ltd filed Critical Olympus Optical Co Ltd
Priority to JP61035488A priority Critical patent/JPS62193885A/en
Publication of JPS62193885A publication Critical patent/JPS62193885A/en
Pending 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
    • G11B7/246—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
    • 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
    • G11B7/245—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 a polymeric component

Landscapes

  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Abstract

PURPOSE:To contrive higher sensitivity and stability of an optical information- recording medium used for writing and reproducing information by laser light, by providing a recording layer comprising a specified organic coloring matter. CONSTITUTION:A recording layer is provided which comprises an organic coloring matter of formula I, wherein R1 is a 1-6C alkyl, aralkyl or phenyl, A is formula II or the like, X is an anion such as a perchlorate ion and a fluoroborate ion, Y is a 1-18C alkyl, phenyl, -R4OR5 or the like, Z is a benzene ring added to the benzene ring constituting indole. Since the coloring matter has an alicyclic ring of formula II or the like introduced into a methine chain, it has excellent preservation stability and characteristics of deterioration on reproduction. In addition, the coloring matter has excellent moisture resistance, since the benzene ring as Z is added to the benzene ring constituting indole. Further, the coloring matter has the substituent group Y introduced into indole, and when an alkyl, aralkyl or the like is introduced as Y, moisture resistance and heat resistance are relatively enhanced.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明はレーデ、特に半導体レーザによる書き込み、再
生記録がなされる光情報記録媒体に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an optical information recording medium on which writing, reproduction and recording are performed using a radar, particularly a semiconductor laser.

〔従来技術および問題点〕[Prior art and problems]

一般に光ディスクは、基板上に設けた薄膜記録層に形成
された光学的に検出可能な小さな（例えば約１μｍ）ピ
ットをらせん状又は円形のトラック形態圧して高密度情
報を記憶することができる。この様なディスクに情報を
書込むには、レーザ感応層の表面に集束したレーザを走
査し、とのレーザ光線が照射された表面のみにピントを
形成し、このピットをらせん状又は円形トラック等の形
態で形成する。この感応層はレーザエネルギーを吸収し
て光学的に検出可能なピットを形成できる。例えばヒー
トモード記録方式では記録層がレーザエネルギーを吸収
してその照射部分が局部的に加熱され融解蒸発あるいは
凝集等の物理的変化を起こし非照射部分との間に光学的
差異（例えば反射率、吸収室等）を生じさせて読み取る
ことによって検出される。In general, optical disks can store high-density information by forming optically detectable small (for example, about 1 μm) pits in a spiral or circular track shape formed in a thin film recording layer provided on a substrate. To write information on such a disk, a focused laser is scanned over the surface of the laser-sensitive layer, and a focus is formed only on the surface irradiated with the laser beam, and the pits are formed into a spiral or circular track. Formed in the form of. This sensitive layer can absorb laser energy to form optically detectable pits. For example, in the heat mode recording method, the recording layer absorbs laser energy and the irradiated area is locally heated, causing physical changes such as melting, evaporation, or aggregation, resulting in optical differences (e.g. reflectance, etc.) between the recording layer and the non-irradiated area. absorption chambers, etc.) and read them.

この様な光記録媒体としてこれまでアルミニウム蒸着膜
などの金属薄膜、ビスマス薄膜、テルル系薄膜やカルコ
グナイド系非晶質ガラス膜など゛の無機物質が提案され
ている。As such optical recording media, inorganic materials such as metal thin films such as aluminum vapor-deposited films, bismuth thin films, tellurium-based thin films, and chalcoglide-based amorphous glass films have been proposed.

これらは、蒸着法、ス・ぐツタ法などにより薄膜が得ら
れ、近赤外域でも光吸収を有するため半導体レーデが使
用できるという長所があるが、反面反射率が大きく、し
かも熱伝導率が大きく比熱も大きい等の欠点がある。特
に反射率が大きいということは、レーザ光のエネルギー
を有効に利用できないので記録に要する光エネルギーが
大きくなり、大出力レーザ光源を必要とする。その結果
、記録装置が大型かつ高価になると云う欠点がある。ま
た、テルル、ビスマス、セレン等の薄膜では毒性を有す
るという欠点がある。このような事から、近年吸収性の
選択ができ、吸収率が大きく、さらに熱伝導が小さく、
加えて生産性が良く、且つ毒性が低いことから色素薄膜
を記録層として適用した光学メモリ媒体の研究提案がな
されて来ている。代表的色素としてはシアニン系色素（
特開昭５８−１１２７９０）、アントラキノン系色素（
特開昭５８−２２４４４８）、ナフトキノン系色素（特
開昭５８−’２２４７９３　）及びフタロシアニン系色
素（特開昭６Ｏ−４８３９６）等があシ、これらケ単独
又は自己酸化性樹脂との併用から成る化合物をスピンナ
ー塗布、ディッピング法、プラズマ法又は真空蒸着法等
により、基板上に形成した光記録媒体である。この色素
薄膜系は上記長所を有し、特にシアニン系色素は構造的
に近赤外に吸収波長をもたせることが可能であり、しか
も溶剤に対する溶解性及び融点が低い等の長所を有する
ことから多く検討がなされている。反面、光劣化、熱く
対して不安定及び湿度劣化等があり、長期保存性及び再
生安定性（読み出し光に対する安定性）等に問題がある
と従来言われており、これらの問題について種々の改良
案が出されている。具体的には、記録層上に保饅膜を設
けること（特開昭５５−２２９６１．５７−６６５４１
　）、陵素による退色防止物質を混合すること（特開昭
５９−５５７９５）、長波長域に光吸収を有する金属錯
体な添加すること（特開昭５９−２１５８９２）等が提
案されている。しかしながら、これらの提案によっても
問題を十分に解決しておらず、史に添加剤による成膜性
や反射率、吸収率の低下という問題が生じる。These have the advantage that thin films can be obtained by vapor deposition methods, suction methods, etc., and semiconductor radars can be used because they absorb light even in the near-infrared region, but on the other hand, they have high reflectance and high thermal conductivity. It has drawbacks such as high specific heat. In particular, if the reflectance is high, the energy of the laser beam cannot be used effectively, so the optical energy required for recording increases, and a high-output laser light source is required. As a result, the disadvantage is that the recording apparatus becomes large and expensive. Furthermore, thin films of tellurium, bismuth, selenium, etc. have the disadvantage of being toxic. For this reason, in recent years it has become possible to select absorbency, with high absorption rate and low heat conduction.
In addition, research proposals have been made on optical memory media using dye thin films as recording layers because of their high productivity and low toxicity. Typical pigments include cyanine pigments (
JP-A-58-112790), anthraquinone pigments (
JP-A-58-224448), naphthoquinone dyes (JP-A-58-224793), and phthalocyanine dyes (JP-A-6O-48396), which can be used alone or in combination with self-oxidizing resins. This is an optical recording medium in which a compound is formed on a substrate by spinner coating, dipping, plasma, vacuum evaporation, or the like. This dye thin film system has the above-mentioned advantages, and in particular, cyanine dyes are structurally capable of having an absorption wavelength in the near infrared region, and also have advantages such as low solubility in solvents and low melting point, so they are often used. It is being considered. On the other hand, it has been said that there are problems with long-term storage and playback stability (stability against readout light), etc. due to light deterioration, instability against heat, and humidity deterioration. Various improvements have been made to address these problems. A proposal has been proposed. Specifically, a protective film is provided on the recording layer (Japanese Patent Application Laid-Open No. 55-22961.57-66541).
), mixing an anti-fading substance based on phosphorus (Japanese Patent Laid-Open No. 59-55795), and adding a metal complex having light absorption in a long wavelength region (Japanese Patent Laid-Open No. 59-215892) have been proposed. However, even these proposals have not sufficiently solved the problem, and problems have arisen in which additives cause a decrease in film formability, reflectance, and absorption.

こうしたことから、記録密度及び反射性の点より下記一
般式に示すシアニン系色素を用いた塗布型記録媒体が注
目されている。For these reasons, a coating type recording medium using a cyanine dye represented by the following general formula is attracting attention from the viewpoint of recording density and reflectivity.

（但し、式中のＣはＯ、Ｓ　ｓ　Ｓｏ　ｅ　Ｃ，Ｘは／
”１０ｒン陰イオン、　ＢＦ４−、　Ｃ４Ｏ４″″、Ｒ
はアルキルを示す） しかしながら、上記一般式で表わされるシアニン系色素
についても成膜性、熱光安定性に欠けるという本質的な
間＠を有する。成膜性については、メチン連鎖数（ｎ）
の増加により浴剤溶解性が低下すること、両端の複素環
の種類及び置換基の種類によシ溶解性が変わることが知
られている。熱光安定性については、メチン連鎖数が増
加する程、熱、光に対して不安定になり、酸化劣化も起
こり易くなること、複素環の種類により熱、光に対する
安定性が異なることが知られている。(However, C in the formula is O, S s So e C, X is /
"10rn anion, BF4-, C4O4"", R
(indicates alkyl) However, the cyanine dye represented by the above general formula also has an inherent drawback of lacking film-forming properties and heat-light stability. Regarding film formability, the number of methine chains (n)
It is known that the solubility in bath agents decreases due to an increase in the number of compounds, and that the solubility changes depending on the types of heterocycles at both ends and the types of substituents. Regarding thermophotostability, it is known that as the number of methine chains increases, it becomes more unstable to heat and light, and oxidative degradation is more likely to occur, and that the stability to heat and light differs depending on the type of heterocycle. It is being

本発明は、上記事情に鑑みなされたもので、高い反射率
と高い記録感度を有し、光学的信号の書き込み、再生を
安定して行なうことが可能で、かつ再生時の光や日光、
湿度に対する安定性の高い無公害の光情報記録媒体を提
供しようとするものである。The present invention was developed in view of the above circumstances, and has high reflectance and high recording sensitivity, enables stable writing and reproduction of optical signals, and is capable of handling light and sunlight during reproduction.
The present invention aims to provide a pollution-free optical information recording medium that is highly stable against humidity.

〔問題点を解決するだめの手段及び作用〕本発明は、下
記一般式にて表わされる有機色素を含む記録Ｒを有する
ことを特徴とする光情報記録媒体ｚ”ｈｓ。[Means and effects for solving the problems] The present invention provides an optical information recording medium z''hs characterized by having a recording R containing an organic dye represented by the following general formula.

但し、式中のＲ１は炭素数１〜６のアルキル基、アラル
キル基又はフェニル基、 （Ｒ２；水膜原子又は炭素数１〜６のアルキル基）、 Ｘは、／千−クロレート、フルオロ？レート、アイオダ
イド、クロライド、ブロマイド、ｐ−トルエンスルフォ
ネートから選ばれる陰イオン、Ｙは、炭素数１〜１８の
アルキル基、フェニル基、−Ｒ４０Ｒ，５、−Ｒ４ＣＯ
Ｒ５、−Ｒ４ＣＯＯＲ５、基、Ｒ５；炭素数１〜１８の
アルキル基又はフェニル基）、 ２は、インドールを構成するベンゼン環に付加されるベ
ンゼン環、 を示す。However, R1 in the formula is an alkyl group having 1 to 6 carbon atoms, an aralkyl group, or a phenyl group, (R2; a water film atom or an alkyl group having 1 to 6 carbon atoms), and X is /1,000-chlorate, fluoro? Anion selected from ester, iodide, chloride, bromide, p-toluenesulfonate, Y is an alkyl group having 1 to 18 carbon atoms, phenyl group, -R40R,5, -R4CO
R5, -R4COOR5, group, R5; alkyl group having 1 to 18 carbon atoms or phenyl group), 2 represents a benzene ring added to the benzene ring constituting indole.

本発明に用いる有機色素は、メチン連鎖中に四環等を導
入することにより、特開昭５９−８５７９１号に開示さ
れた のようなメチン連鎖のみから構成されたシアニン色素に
比べて耐熱性、耐光性が向上し、より耐保存性、再生劣
化特性に優れた記録層を形成できる。前記シクロ環等に
導入されるＲ２は、既述のとおりであるが、特にハロゲ
ン原子を用いた場合、ＣＬ　、　Ｂｒ又はアルキル基を
用いた場合、炭素数１〜３のものが好ましい。By introducing a tetracycle or the like into the methine chain, the organic dye used in the present invention has higher heat resistance and better heat resistance than the cyanine dye composed only of methine chains as disclosed in JP-A-59-85791. It is possible to form a recording layer with improved light resistance and better storage resistance and playback deterioration characteristics. R2 introduced into the cyclo ring and the like is as described above, but particularly when a halogen atom, CL, Br, or an alkyl group is used, R2 preferably has 1 to 3 carbon atoms.

また、本発明に用いる有機色素は、インドールを構成す
るベンゼン環に２としてのベンゼン環を付加させること
により、特開昭５９−１５０７９５号、特開昭５８−１
９４５９５号に開示された、例えば のようなインドールを構成するベンゼン環が未置換もし
くはアルキル基で置換された有機色素に比べて疎水性が
高められ、耐環境性の要素の１つである耐湿性を向上で
き、又耐光退色性が向上する事から媒体特性の１つであ
る再生劣化について良くなる。Furthermore, the organic dye used in the present invention can be prepared by adding a benzene ring as 2 to the benzene ring constituting the indole.
94595, in which the benzene ring constituting the indole is unsubstituted or substituted with an alkyl group, has improved hydrophobicity and moisture resistance, which is one of the elements of environmental resistance. Furthermore, since the light fading resistance is improved, reproduction deterioration, which is one of the characteristics of the medium, is improved.

更に、本発明に用いる有機色素はインドールに既述した
置換基Ｙが導入された構造であるが、Ｙとしてアルキル
基、アラルキル基等を導入すると比較的耐湿性、耐熱性
の向上がなされ、Ｙとして−Ｒ４ＣＯＲ５，−Ｒ４０Ｒ
５，−Ｒ４ＣＯＯＲ５基等を導入すると溶剤溶解性、成
膜性の向上がなされる。Furthermore, the organic dye used in the present invention has a structure in which the above-mentioned substituent Y is introduced into indole, but if an alkyl group, aralkyl group, etc. are introduced as Y, the moisture resistance and heat resistance are relatively improved; as -R4COR5, -R40R
When a 5,-R4COOR5 group or the like is introduced, solvent solubility and film forming properties are improved.

こうしたことから、置換基Ｙは記録媒体の構成、目的に
より適宜選択すればよい。For this reason, the substituent Y may be appropriately selected depending on the configuration and purpose of the recording medium.

上記一般式にて表わされる色素を具体的に例示すると、
下記構造式（１）〜αυに示すもの等が挙げられる。Specific examples of the dye represented by the above general formula include:
Examples include those shown in the following structural formulas (1) to αυ.

上記一般式で表わされる色素を含む記録層は、該色素を
酢酸エチル、トルエン、アセトン、メチルエチルケトン
、メチルイソブチルケトン、塩化メチレン、アルコール
等の溶剤に溶解してスピンナー法、ディッピング法、ド
クターブレード法、ロールコータ法等により基板上に薄
膜を形成することにより得られる。この記録層の厚さは
、薄い程、記鎌感度が高くなるが、反射率が膜厚に依存
するために、１０　ｎｍ〜１ｏ００ｎｍ、好ましくば３
０　ｎｍ〜５００　ｎｍの範囲にすることが適切である
。また、基板としてはガラス、グラスチック、金属等の
一般に用いられるものが使用可能であるが、アクリル樹
脂、ポリカーぜネート、ポリオレフィン、ポリエステル
、？リイミドのフィルム又は成型板でもよい。A recording layer containing a dye represented by the above general formula can be prepared by dissolving the dye in a solvent such as ethyl acetate, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methylene chloride, alcohol, etc., using a spinner method, dipping method, doctor blade method, etc. It is obtained by forming a thin film on a substrate using a roll coater method or the like. The thinner the recording layer is, the higher the recording sensitivity becomes. However, since the reflectance depends on the film thickness, the thickness is 10 nm to 1000 nm, preferably 30 nm to 1000 nm.
A range of 0 nm to 500 nm is appropriate. In addition, commonly used substrates such as glass, plastic, and metal can be used, but acrylic resin, polycarbonate, polyolefin, polyester, etc. It may also be a liimide film or molded plate.

記録層は上述した方法により形成される。更に色素にバ
インダ樹脂を１〜４０重敗係、好ましくは３〜２０１ｉ
ｉ係添加することにより、膜形成することができ、成膜
性、耐熱性、耐湿性を向上させることができる。ここに
用いるバインダ樹脂としては、例えばアクリル、エステ
ル、ニトロセルロース、エチレン、フロピレン、カーゴ
ネート、エチレンテレフタレート、エポキシ、ブチラー
ル、塩化ビニル、酢酸ビニル、スチレン等の単独重合体
、これらの共重合体等を挙げることができる。The recording layer is formed by the method described above. Furthermore, a binder resin is added to the dye at a rate of 1 to 40 times, preferably 3 to 201 times.
By adding i, it is possible to form a film, and film formability, heat resistance, and moisture resistance can be improved. Examples of the binder resin used here include homopolymers of acrylic, ester, nitrocellulose, ethylene, fluoropylene, carbonate, ethylene terephthalate, epoxy, butyral, vinyl chloride, vinyl acetate, styrene, and copolymers thereof. be able to.

また、上記バインダ樹脂の代りに他の色素を混入させる
か、又は色素層を重ねた多層構造にすることによって成
膜性の向上や耐熱、耐湿、耐光性を向上させることがで
き、ひいては高密度、高感度で再生劣化等のない耐久性
の優れた光情報記録媒体を得ることができる。この場合
、他の色素を積層して耐熱性、耐湿性、耐光性を向上さ
せることも可能である。ここに用いる色素としては、例
えばシアニン色素、メロシアニン色素、アントラキノン
色素、トリフェニルメタン色素、キサンチン系色素、フ
タロシアニン系色素等を挙げることができる。In addition, by mixing other dyes in place of the binder resin or creating a multilayer structure in which dye layers are stacked, film formability, heat resistance, moisture resistance, and light resistance can be improved, resulting in higher density. Therefore, it is possible to obtain an optical information recording medium with high sensitivity and excellent durability without reproduction deterioration. In this case, it is also possible to layer other dyes to improve heat resistance, moisture resistance, and light resistance. Examples of the dyes used here include cyanine dyes, merocyanine dyes, anthraquinone dyes, triphenylmethane dyes, xanthine dyes, and phthalocyanine dyes.

例えば下記一般式（Ａ）　、　（Ｂ）にて表わされるア
ミン化合物や下記一般式（Ｃ）にて表わされるジチオレ
ート金属錯体を添加し、光、酸素、水分による記録層の
光学特性の劣化を防止することも可能である。For example, amine compounds represented by the following general formulas (A) and (B) or dithiolate metal complexes represented by the following general formula (C) are added to prevent deterioration of the optical properties of the recording layer due to light, oxygen, and moisture. It is also possible to do so.

Ｒえ 但し１式中のＲ，、Ｒ２，Ｒ４，Ｒ５は炭素数１〜で、
Ｒは炭素数１〜６のアルキル基を示す。R, however, R,, R2, R4, R5 in formula 1 have 1 or more carbon atoms,
R represents an alkyl group having 1 to 6 carbon atoms.

・・・・・・　ＣＢ） 但し、式中のＲは水素原子又は炭素数１〜６のアルキル
基、Ｘは過塩素酸イオン、弗化硼素酸イオン、ヘキサフ
ルオロ酸イオン等の陰イオン、ｍはＯ又は１，２の整数
、Ａは前記ｍ＝ｏ、１としては、例えば市販されている
ＩＲＱ−００２゜ＩＲＱ−００３（いずれも日本化薬（
株）裂開品名）等がある。...... CB) However, R in the formula is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X is an anion such as a perchlorate ion, a fluoroborate ion, a hexafluoroate ion, m is O or an integer of 1 or 2, A is m=o, and 1 is, for example, commercially available IRQ-002゜IRQ-003 (both Nippon Kayaku (Nippon Kayaku)
Co., Ltd.) and others.

・・・・・・　（Ｃ） 但し、式中のＲ１−Ｒ４はアルキル基又はフェニル基、
Ｘ、Ｙは水素、アルキル基、ハロゲン基、ＭはＮｌ　ｅ
　Ｃｏ　ｙ　Ｆｅ　ＨＣｒ等の金属を示すものである。...... (C) However, R1-R4 in the formula are an alkyl group or a phenyl group,
X, Y are hydrogen, alkyl group, halogen group, M is Nl e
It shows metals such as Co y Fe HCr.

かかる金属錯体としては１例えばＰＡ１００１〜１００
６　（いずれも三井東圧ファイン■展商品名〕、Ｎｌ−
ビス（０−キシレ／−４，５・ジオール）テトラ（ｔ−
ジチル）アンモニム塩等がある。Such metal complexes include 1, for example PA1001-100.
6 (Both are Mitsui Toatsu Fine Exhibition product names), Nl-
Bis(0-xylene/-4,5-diol)tetra(t-
(dityl) ammonium salts, etc.

々お、上記一般式の色素を含む記録層の他に必要に応じ
て中間層、保護層を設けることかできる。中間層は、接
着性の向上と共に酸素、水分からの保護の目的で設けら
れ、主に樹脂又は無機化合物から形成される。樹脂とし
ては、例、ｔ［ｊＪ［化ヒニル、酢酸ビニル、アクリル
、エステル、ニトロセルロース、カーカネート、工Ｉキ
シ、エチレン、グロピレン、ブチラール等の単独もしく
は共重合体等を用いることができ、必要に応じて酸化防
止剤、紫外光吸収剤、レベリング剤や撥水剤等を含有さ
せることが可能である。これらは、スピンナー法、ディ
ッピング法、ドクターブレード法により形成される。無
機化合物としては、例えばｓｉｏ　　ｅ　ｓｉｏ　ｅ　
ｈｔ２ｏ、。In addition to the recording layer containing the dye of the above general formula, an intermediate layer and a protective layer may be provided as necessary. The intermediate layer is provided for the purpose of improving adhesion and protecting from oxygen and moisture, and is mainly formed from a resin or an inorganic compound. As the resin, for example, single or copolymers of t[jJ], vinyl acetate, acrylic, ester, nitrocellulose, carcanate, ethylene, glopyrene, butyral, etc. can be used, and if necessary, Depending on the situation, it is possible to contain antioxidants, ultraviolet light absorbers, leveling agents, water repellents, etc. These are formed by a spinner method, a dipping method, or a doctor blade method. Examples of inorganic compounds include sio e sio e
ht2o,.

５ｎ０２　ｔ　ＭｇＦ２等が用いられ、イオンビーム、
電子ビーム、ス・９ツタ法により薄膜が形成される。5n02t MgF2 etc. are used, and the ion beam,
A thin film is formed using an electron beam and the S9 method.

前記保護層も中間層と同様の構成をとり、光、酸素、水
分からの記録層の保護、傷、ホコリ等からの保護のため
て用いられる。The protective layer also has the same structure as the intermediate layer, and is used to protect the recording layer from light, oxygen, and moisture, and from scratches, dust, and the like.

次に、本発明の光情報記録媒体の構成例について図面を
参照して説明する。Next, a configuration example of the optical information recording medium of the present invention will be described with reference to the drawings.

＠１図は、光情報記録媒体の基本構成を示すもので、基
板１上に一般式の色素！含む記録層２を設けた構造であ
る。記録、再生はレーデ光３ヶ集光レンズにより記録層
２上に０．８〜１．５μｍの大きさのスＩウドに集光し
て行なわれる。Figure @1 shows the basic structure of an optical information recording medium, with a dye of the general formula on a substrate 1! This is a structure in which a recording layer 2 including a recording layer 2 is provided. Recording and reproduction are performed by condensing Radhe beams into a square having a size of 0.8 to 1.5 μm on the recording layer 2 using three condenser lenses.

記録再生のレーデ光３は、記録層２から照射してもよい
が、基板１が透明な材料からなる場合には基板１側から
照射する方が一般的に汚れやゴミの影響を少なくできる
。The radar light 3 for recording and reproduction may be irradiated from the recording layer 2, but when the substrate 1 is made of a transparent material, it is generally better to irradiate from the substrate 1 side to reduce the influence of dirt and dust.

第２図は、基板１と記録層２の間に中間層４を、記録層
２上に保護層５を夫々設けた構造のものである。FIG. 2 shows a structure in which an intermediate layer 4 is provided between the substrate 1 and the recording layer 2, and a protective layer 5 is provided on the recording layer 2.

＠３図は、同一構成の２枚の媒体を記録層２が互に対向
するようにス（−サ６を介して配置させたものである。In Figure 3, two media having the same configuration are arranged with a spacer 6 in between so that the recording layers 2 face each other.

なお、第３図中の７はエアーギャップ、８はスピンドル
穴である。かかる構成によれば、特性的に良好であり、
更に記録層２への汚れやゴミの影響を抑制できる利点を
有する。In addition, 7 in FIG. 3 is an air gap, and 8 is a spindle hole. According to this configuration, the characteristics are good,
Furthermore, it has the advantage that the influence of dirt and dust on the recording layer 2 can be suppressed.

更に、前述した第１図〜第３図の構成において、Ａ／、
　、　Ａｇ等及びその他の反射膜を基板と記録層の間に
設けてもよい。Furthermore, in the configurations of FIGS. 1 to 3 described above, A/,
, Ag, or other reflective films may be provided between the substrate and the recording layer.

〔発明の実施例〕[Embodiments of the invention]

以下、本発明の実施例を詳細に説明する。 Examples of the present invention will be described in detail below.

実施例１ 上述した構造式（１）の色素をメチルエチルケトンで溶
解し、２悌溶液とした後、これをスピンナーコータで厚
さ１．２ｍのガラス基板上に塗布、乾燥して厚さ７５　
ｎｍの記録層を形成して記録媒体を製造した。Example 1 The above-mentioned dye of structural formula (1) was dissolved in methyl ethyl ketone to form a 2-hour solution, which was coated onto a 1.2 m thick glass substrate using a spinner coater and dried to a thickness of 75 m.
A recording medium was manufactured by forming a recording layer with a thickness of 100 nm.

実施例２ 上述した構造式（６）の色素を塩化メチレンで溶値１　
　０　ｅｔ　′ＪＮ儒しｌ　４ａ　　、ｌ−ｙＭ　ｂ　
−２ｕ−／−）−−コータで厚さ１．２　ｍのガラス基
板上に塗布、乾燥して厚さ７０　ｎｍの記録層全形成し
て記録媒体を製造した。Example 2 The dye of structural formula (6) described above was dissolved in methylene chloride at a solubility value of 1.
0 et 'JN Confucianism 4a, lyM b
-2u-/-)--It was coated on a glass substrate with a thickness of 1.2 m using a coater and dried to form a recording layer with a thickness of 70 nm to produce a recording medium.

実施例３ 上述した構造式（８）の色素をメチルエチルケトンで溶
解して２１ｇ液とした後、これをスピンナーコータで厚
さ１．２１のガラス基板上に塗布、乾燥して厚さ７５　
ｎｍの記録層を形成して記録媒体を製造した。Example 3 The above-mentioned dye of structural formula (8) was dissolved in methyl ethyl ketone to obtain a 21 g solution, which was then applied onto a glass substrate with a thickness of 1.21 mm using a spinner coater and dried to a thickness of 75 mm.
A recording medium was manufactured by forming a recording layer with a thickness of 100 nm.

実施例４ 上述した構造式（２）の色素を塩化メチレンで溶解し、
２チ溶液とした後、これをスピンナーコータで厚さ１．
２−のガラス基板上に塗布、乾燥して厚さ８０　ｎｍの
記録層を形成し、記録媒体を製造した〇 実施例５ 上述した構造式（２）の色素に、バインダ樹脂としての
アクリル樹脂（三菱レーヨン社製：ダイヤナールＢＲ−
６０）を１０重ｉ％添加し、これをメチルエチルケトン
で溶解して３幅溶液とした後、この溶液をスピンナーコ
ータで厚さ１．２−のガラス基板上に塗布、乾燥して厚
さ９０　ｎｍの記録層を形成して記録媒体を製造し九。Example 4 The dye of structural formula (2) described above was dissolved in methylene chloride,
After making a 2-inch solution, this was coated with a spinner coater to a thickness of 1.
A recording layer was formed with a thickness of 80 nm by coating and drying on the glass substrate of 2-, and a recording medium was manufactured. Manufactured by Mitsubishi Rayon Co., Ltd.: Dianal BR-
60) was added at 10% by weight and dissolved in methyl ethyl ketone to obtain a 3-width solution. This solution was applied onto a 1.2-thick glass substrate using a spinner coater and dried to a thickness of 90 nm. (9) manufacturing a recording medium by forming a recording layer;

実施例６ 上述した構造式αＱの色素と赤外線吸収剤（日本化薬社
製商品名：　ＩＲＧ−ｏｏ：３　）とを重量比で３：１
の割合にて混合し、これを塩化メチレンで溶解して２チ
容液とした後、この溶液をスピンナーコータで厚さ１．
２　ｗのガラス基板上に塗布、乾燥して厚さ７０　ｎｍ
の記録層を形成して記録媒体を製造した。Example 6 The dye having the structural formula αQ described above and the infrared absorber (trade name: IRG-oo:3, manufactured by Nippon Kayaku Co., Ltd.) were mixed in a weight ratio of 3:1.
This was mixed with methylene chloride to make a 2-inch volume solution, and this solution was coated with a spinner coater to a thickness of 1.
Coated on a 2W glass substrate and dried to a thickness of 70 nm.
A recording medium was manufactured by forming a recording layer.

実施例７ 上述した構造式（１）の色素と下記構造式αＱの色素と
を重量比で２：１の割合で混合し、これを実施例１と同
様に溶解し、基板上に塗布、乾燥して厚さ７０　ｎｍの
記録層を形成し、記録媒体を製造した。Example 7 The dye having the structural formula (1) described above and the dye having the following structural formula αQ were mixed at a weight ratio of 2:1, dissolved in the same manner as in Example 1, coated on a substrate, and dried. A recording layer with a thickness of 70 nm was formed in this manner, and a recording medium was manufactured.

実施例８ 実施例１と同様な方法によりプラス基板上に構造式（８
）の色素からなる厚さ６０　ｎｍの記録層を形成した後
、この記録層上に下記構造式αηに示すアルミニウムナ
フタロシアニンを真空度１、ＯＸ　１０　　Ｔｏｒｒ　
　の条件下で真空加熱蒸着して厚さ３０　ｎｍの反射性
保護層を形成し、記録媒体を製造した◇ ・・・・・・　α力 比較例１ 下記構造式（１）の色素な塩化メチレンで溶解して２幅
溶液とした後、この溶液をスピンナーコータで厚さ１．
２１のガラス基板上に塗布し、乾燥して厚さ７０　ｎｍ
の記録層を形成し、記録媒体を製造した。Example 8 Structural formula (8
) After forming a recording layer with a thickness of 60 nm consisting of a dye of
A recording medium was produced by forming a reflective protective layer with a thickness of 30 nm by vacuum heating vapor deposition under the conditions of After dissolving to make a two-width solution, this solution was coated with a spinner coater to a thickness of 1.
21 on a glass substrate and dried to a thickness of 70 nm.
A recording layer was formed to produce a recording medium.

比較例２ 下記構造式（ｎ）の色素を比較例１と同様な方法で洛解
し、ガラス基板上に塗布、乾燥して厚さ７０　ｎｍの記
録層を形成し、記録媒体を製造した。Comparative Example 2 A dye having the following structural formula (n) was dissolved in the same manner as in Comparative Example 1, coated on a glass substrate, and dried to form a recording layer with a thickness of 70 nm to produce a recording medium.

比較例３ 下記構造式（ＩＩＩ）の色撫を比較例１と同様な方法で
溶解し、ガラス基板上に塗布、乾燥して厚さ７０　ｎｍ
の記録層を形成し、記録媒体を製造した。Comparative Example 3 A liquid having the following structural formula (III) was dissolved in the same manner as in Comparative Example 1, applied onto a glass substrate, and dried to a thickness of 70 nm.
A recording layer was formed to produce a recording medium.

比較例４ 下記構造式（ＩＶ）の色素を比較例１と同様な方法で溶
解し、ガラス基板上に酋布、乾燥して厚さ７０　ｎｍの
記録層を形成し、記録媒体を製造した。Comparative Example 4 A dye having the following structural formula (IV) was dissolved in the same manner as in Comparative Example 1, spread on a glass substrate, and dried to form a recording layer with a thickness of 70 nm to produce a recording medium.

しかして、本実施例１〜８及び比較例１〜４の記録媒体
の記録層について、波長８３０　ｎｍの半導体レーザ光
を媒体面出カフ　ｍＷとなるように直径１．２μｍのス
ポットに集光し、この集光レーザ光を各記録媒体の基板
側からその移動速度を９ｇ／ａｅｃの条件下でＩ　ＭＨ
ｚの信号を書き込み、同レーデ光で再生出力０．４ｍＷ
で再生を行なって記録感度（記録エネルギー閾値）及び
再生信号のＣ２へ側を測定した。更に１本実施例１〜８
及び比較例１〜４の記録媒体を５０℃、９５係の雰囲気
下に１５０時間放置し、放置前後の吸光度低下率、反射
率低下率を測定する耐熱湿性試験を行なう九。各記録媒
体に２５℃、６０４の雰囲気でｓｏｏｗタングステン光
を５０１Ｍへだてて１００時間照射し、タングステン光
の照射前後での吸光度低下率、反射率低下率を測定する
射光試験を行なった。これらの結果を下記−に示した。For the recording layers of the recording media of Examples 1 to 8 and Comparative Examples 1 to 4, semiconductor laser light with a wavelength of 830 nm was focused onto a spot with a diameter of 1.2 μm so that the medium surface output was mW. , this focused laser beam was moved from the substrate side of each recording medium at a moving speed of 9 g/aec under the condition of I MH
Write z signal and reproduce output 0.4mW with the same radar light
The recording sensitivity (recording energy threshold) and the C2 side of the reproduced signal were measured. One more example 1-8
The recording media of Comparative Examples 1 to 4 were left for 150 hours at 50 DEG C. in a 95% atmosphere, and a heat-humidity test was conducted to measure the absorbance decrease rate and reflectance decrease rate before and after the exposure. A light emission test was conducted in which each recording medium was irradiated with 501 M soow tungsten light in an atmosphere of 604°C at 25° C. for 100 hours, and the absorbance reduction rate and reflectance reduction rate before and after irradiation with the tungsten light were measured. These results are shown below.

〔発明の効果〕〔Effect of the invention〕

以上詳述した如く、本発明によれば高い反射率と高い記
録感度を有し、光学的信号の書き込み、再生を安定して
行なうことが可能で、かつ再生光や日光、湿度に対する
安定性の高い無公害の光情報記録媒体を提供できる。As detailed above, the present invention has high reflectance and high recording sensitivity, enables stable writing and reproduction of optical signals, and has low stability against reproduction light, sunlight, and humidity. A highly pollution-free optical information recording medium can be provided.

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

第１図〜第３図は、夫々本発明の光情報記録媒体を示す
概略図である。 １・・・基板、２・・・記録層、３・・・レーデ光、４
・・・中間層、５・・・保護層、６・・・スペーサ。 出願人代理人　弁理士　坪　井　　　淳第２図 第３　図1 to 3 are schematic diagrams showing optical information recording media of the present invention, respectively. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Recording layer, 3... Rade light, 4
... Intermediate layer, 5... Protective layer, 6... Spacer. Applicant's representative Patent attorney Atsushi Tsuboi Figure 2 Figure 3

Claims (1)

【特許請求の範囲】 下記一般式にて表わされる有機色素を含む記録層を有す
ることを特徴とする光情報記録媒体。 ▲数式、化学式、表等があります▼ 但し、式中のＲ＿１は炭素数１〜６のアルキル基、アラ
ルキル基又はフェニル基、 Ａは、▲数式、化学式、表等があります▼、▲数式、化
学式、表等があります▼、▲数式、化学式、表等があり
ます▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、▲数式、化学式、表等があります▼
、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼ （Ｒ＿２；水素原子又は炭素数１〜６のアルキル基）、 Ｘは、パークロレート、フルオロボレート、アイオダイ
ド、クロライド、ブロマイド、ｐ−トルエンスルフォネ
ートから選ばれる陰イオン、Ｙは、炭素数１〜１８のア
ルキル基、フェニル基、−Ｒ＿４ＯＲ＿５、−Ｒ＿４Ｃ
ＯＲ＿５、−Ｒ＿４ＣＯＯＲ＿５、▲数式、化学式、表
等があります▼（Ｒ＿４；炭素数１〜２０のアルキル基
、Ｒ＿５；炭素数１〜１８のアルキル基又はフェニル基
）、 Ｚは、インドールを構成するベンゼン環に付加されるベ
ンゼン環、 を示す。[Scope of Claims] An optical information recording medium characterized by having a recording layer containing an organic dye represented by the following general formula. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R_1 in the formula is an alkyl group with 1 to 6 carbon atoms, an aralkyl group, or a phenyl group, and A is ▲ There are ▲ mathematical formulas, chemical formulas, tables, etc. , tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables etc. ▼ (R_2; hydrogen atom or alkyl group having 1 to 6 carbon atoms), X is an anion selected from perchlorate, fluoroborate, iodide, chloride, bromide, p-toluenesulfonate, Y is , C1-C18 alkyl group, phenyl group, -R_4OR_5, -R_4C
OR_5, -R_4COOR_5, ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (R_4: alkyl group with 1 to 20 carbon atoms, R_5: alkyl group with 1 to 18 carbon atoms or phenyl group), Z is benzene constituting indole A benzene ring added to the ring is shown.
JP61035488A 1986-02-20 1986-02-20 Optical information-recording medium Pending JPS62193885A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP61035488A JPS62193885A (en) 1986-02-20 1986-02-20 Optical information-recording medium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP61035488A JPS62193885A (en) 1986-02-20 1986-02-20 Optical information-recording medium

Publications (1)

Publication Number Publication Date
JPS62193885A true JPS62193885A (en) 1987-08-26

Family

ID=12443131

Family Applications (1)

Application Number Title Priority Date Filing Date
JP61035488A Pending JPS62193885A (en) 1986-02-20 1986-02-20 Optical information-recording medium

Country Status (1)

Country Link
JP (1) JPS62193885A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007291348A (en) * 2006-03-09 2007-11-08 Fujifilm Corp Compound having polymethine-chain structure, image forming material using the same, planographic printing original plate, image forming method, and mehod of making planographic printing original plate and planographic printing method
WO2006136543A3 (en) * 2005-06-21 2008-04-10 Agfa Graphics Nv Infrared absorbing dye

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006136543A3 (en) * 2005-06-21 2008-04-10 Agfa Graphics Nv Infrared absorbing dye
US8178282B2 (en) 2005-06-21 2012-05-15 Agfa Graphics Nv Heat-sensitive imaging element
JP2007291348A (en) * 2006-03-09 2007-11-08 Fujifilm Corp Compound having polymethine-chain structure, image forming material using the same, planographic printing original plate, image forming method, and mehod of making planographic printing original plate and planographic printing method

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