JPH0367251B2 - - Google Patents
Info
- Publication number
- JPH0367251B2 JPH0367251B2 JP60231517A JP23151785A JPH0367251B2 JP H0367251 B2 JPH0367251 B2 JP H0367251B2 JP 60231517 A JP60231517 A JP 60231517A JP 23151785 A JP23151785 A JP 23151785A JP H0367251 B2 JPH0367251 B2 JP H0367251B2
- Authority
- JP
- Japan
- Prior art keywords
- recording medium
- optical recording
- dye
- spiropyran
- recording method
- 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 - Lifetime
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
- G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
-
- 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
- G11B7/004—Recording, reproducing or erasing methods; Read, write or erase circuits therefor
- G11B7/0045—Recording
- G11B7/00455—Recording involving reflectivity, absorption or colour changes
-
- 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
-
- 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
- G11B7/2475—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 merocyanine
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
- Optical Recording Or Reproduction (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、光学的記録媒体のうち、特に書き換
え可能な光学記録媒体の記録方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a recording method for an optical recording medium, particularly a rewritable optical recording medium.
従来の技術
従来、書き換え可能な光学記録媒体としてホト
クロミツク色素を用いるものが知られている（例
えば、光デイスクメモリ用材料に関する調査報告
書（昭和57年３月、日本電子工業振興協会）第82
頁）。Conventional technology Conventionally, rewritable optical recording media that use photochromic dyes have been known (for example, Research Report on Materials for Optical Disk Memory (March 1982, Japan Electronic Industry Promotion Association) No. 82).
page).
この動作を以下簡単に説明する。 This operation will be briefly explained below.
ホトクロミツク色素を含む記録層を表面に被覆
した基板に波長λAのレーザー光を集光させる。
このときレーザー光の当たつたスポツト部分でホ
トクロミツク色素が光反応を起こし色が無色から
波長λBに最大吸収を持つ有色に変化して情報が記
録される。情報の書き込みを終えた記録媒体は、
波長λBで光反応を起こさない程度の弱いレーザー
光によつて情報読み出しが行われる。また、波長
λBの強いレーザー光の照射により記録する前の状
態に戻り、情報の再度書き込みが可能となるもの
である。 A laser beam of wavelength λ A is focused on a substrate whose surface is coated with a recording layer containing a photochromic dye.
At this time, the photochromic dye at the spot hit by the laser light undergoes a photoreaction, changing its color from colorless to colored with maximum absorption at wavelength λ B , and information is recorded. The recording medium on which information has been written is
Information is read out using a laser beam of wavelength λ B that is weak enough not to cause a photoreaction. In addition, by irradiating with a strong laser beam of wavelength λ B , the state before recording is returned, and information can be written again.
発明が解決しようとする問題点
ホトクロミツク色素の有色異性体は、一般にき
わめて不安定であり、暗中で自然に退色する性質
がある。このため、ホトクロミツク色素を用いた
光学記録媒体は記録寿命が短いという欠点を有し
ていた。Problems to be Solved by the Invention Colored isomers of photochromic dyes are generally extremely unstable and have the property of spontaneously fading in the dark. For this reason, optical recording media using photochromic dyes have had the disadvantage of short recording life.
問題点を解決するための手段
上記問題点を克服するため、本発明では有機ホ
トクロミツク色素からなる光学記録媒体に、紫外
線などの光の照射と、室温以上でかつ前記色素の
分解または熱転位など熱による分子構造の変化が
おきる温度以下での加熱処理とを組み合わせ、前
記色素の会合体を形成させる工程を含む光学記録
媒体の記録方法を提供する。Means for Solving the Problems In order to overcome the above problems, in the present invention, an optical recording medium made of an organic photochromic dye is irradiated with light such as ultraviolet rays, and subjected to heat such as decomposition or thermal rearrangement of the dye at room temperature or above. Provided is a recording method for an optical recording medium, which includes a step of forming an aggregate of the dye by combining heat treatment at a temperature below the temperature at which a change in the molecular structure occurs.
作 用
上記発明の記録方法を用いることにより、従来
暗中で自然に退色する性質のあつた有機ホトクロ
ミツク色素に対する記録において、分子構造の変
化をおこさずかつ安定な記録状態を実現すること
が可能になる。Effect: By using the recording method of the above invention, it becomes possible to realize a stable recording state without causing any change in the molecular structure when recording with organic photochromic dyes, which conventionally had the property of naturally fading in the dark. .
本発明に用いるホトクロミツク色素としては、
スピロピランが好ましい。特に下記の一般式で示
されるスピロピランは会合対の形成が容易である
ため最も好ましい。また、このような作用を実現
するために、光学記録媒体はスピンコート法な
ど、基板面に水平な力を加える方法かあるいは
LB（ラングミユア・ブロジエツト）膜法により作
成された場合が特に効果的である。 Photochromic dyes used in the present invention include:
Spiropyran is preferred. In particular, spiropyran represented by the general formula below is most preferred because it facilitates the formation of association pairs. In addition, in order to achieve this effect, optical recording media can be manufactured using methods that apply horizontal force to the substrate surface, such as spin coating, or
It is particularly effective when produced by the LB (Langmiur-Blodget) film method.
（ただし、A1〜A9はＨ、CH3、NO2、OCH3、
CN、ハロゲン、NH2、COOHまたはCONH2で
あり、B1，B2はＸがＣのときのみ存在するＨま
たはアルキル基であり、R1，R2はＨまたはアル
キル基であり、ＸはＣ、ＮまたはＳ、ＹはＣまた
はＮである。）
実施例 １
式
で表わされるスピロピランの２％クロロホルム溶
液を、トリメチルクロルシラン処理したガラス基
板表面に塗布した後、500rpmで30秒、1500rpm
で100秒それぞれスピンを加えて乾燥した。この
基板は最初無色であるが、波長350nｍ付近の光
を含む紫外線を15分間照射することによりホトク
ロミツク反応をして図の曲線Ａの吸収スペクトル
を持つホトメロシアニンが生成した。さらに10分
間38℃に加熱すると図の曲線Ｂの吸収スペクトル
を有するホトメロシアニンのＪ−会合体を生じ
た。加熱する前の通常のホトメロシアニンは常温
暗中で約20時間で退色したのに対し、本実施例で
生じたＪ−会合体は１年を経過しても退色せず非
常に安定であつた。 (However, A 1 to A 9 are H, CH 3 , NO 2 , OCH 3 ,
CN, halogen, NH 2 , COOH or CONH 2 , B 1 and B 2 are H or an alkyl group that exists only when X is C, R 1 and R 2 are H or an alkyl group, and X is C, N or S, Y is C or N. ) Example 1 Formula After applying a 2% chloroform solution of spiropyran represented by to the surface of a glass substrate treated with trimethylchlorosilane, it was heated at 500 rpm for 30 seconds, then at 1500 rpm.
Spin for 100 seconds each to dry. This substrate was initially colorless, but by irradiating it with ultraviolet light containing light with a wavelength of around 350 nm for 15 minutes, a photochromic reaction occurred, producing photomerocyanine with an absorption spectrum shown by curve A in the figure. Further heating at 38° C. for 10 minutes produced a J-aggregate of photomerocyanine having an absorption spectrum of curve B in the figure. While ordinary photomerocyanine before heating discolored in about 20 hours in the dark at room temperature, the J-aggregate produced in this example did not discolor even after one year and remained very stable.
なお、このようにして生じたＪ−会合体に、波
長：620nｍ、エネルギー：20ｍＪ／cm2のレーザ
光を照射することによつて、元の無色状態に戻つ
た。また、この状態から再度記録、消去の繰り返
し操作を行なうことができた。 By irradiating the J-aggregate thus produced with a laser beam having a wavelength of 620 nm and an energy of 20 mJ/cm 2 , it returned to its original colorless state. Further, from this state, it was possible to repeat recording and erasing operations again.
このような紫外線照射と加熱操作による不安定
種の安定化は、本実施例で行なつた構造以外の場
所に置換基を有するスピロピランでも同様に観測
された。またほかのホトクロミツク化合物、たと
えばフルギド、チオインジゴ、ジアリールエテ
ン、アゾベンゼンでも同様に観測された。 Such stabilization of unstable species by ultraviolet irradiation and heating operations was similarly observed in spiropyrans having substituents at positions other than those in the structure performed in this example. Similar observations were also made with other photochromic compounds, such as fulgide, thioindigo, diarylethene, and azobenzene.
実施例 ２
実施例１と同じスピロピランの１ｍＭベンゼン
溶液をPH7.0、18℃のLB膜装置の水面に適下した
後、圧縮し、表面圧20dyne／cmでトリメチルク
ロルシラン処理したガラス基板上に12層累積した
LB膜を得た。実施例１と同じく紫外線照射、加
熱の操作を行い同様のＪ−会合体を得た。Example 2 A 1mM benzene solution of spiropyran, the same as in Example 1, was dropped onto the water surface of an LB membrane device at pH 7.0 and 18°C, compressed, and placed on a glass substrate treated with trimethylchlorosilane at a surface pressure of 20 dyne/cm. 12 layers accumulated
An LB film was obtained. The same J-aggregates were obtained by performing ultraviolet irradiation and heating in the same manner as in Example 1.
なお、色素膜の形成は他の被覆方法によつても
よく、また記録時の紫外線照射と加熱は同時に行
なつてもさしつかえない。 Note that the dye film may be formed by other coating methods, and ultraviolet irradiation and heating during recording may be performed simultaneously.
さらに、熱線を含む光源を用いて化学的手段で
加熱を行なう方法も当然有効である。 Naturally, a method of heating by chemical means using a light source containing heat rays is also effective.
発明の効果
本発明により、記録の寿命を伸ばすことが可能
となつた。Effects of the Invention The present invention has made it possible to extend the life of recording.
図はホトメロシアニン及びホトメロシアニンＪ
−会合体の可視吸収スペクトルを示す図である。
The figure shows photomerocyanine and photomerocyanine J.
- It is a figure showing the visible absorption spectrum of an aggregate.
Claims (1)
体に、紫外線などの光の照射操作と、室温以上で
かつ前記色素の分解または熱転位など熱による分
子構造の変化がおきる温度以下での可熱処理操作
とを組み合わせ、前記色素の会合体を形成させる
工程を含む光学記録媒体の記録方法。 ２ 有機ホトクロミツク色素がスピロピランであ
る特許請求の範囲第１項に記載の光学記録媒体の
記録方法。 ３ スピロピランが下記の一般式で示させる構造
を有する特許請求の範囲第２項に記載の光学記録
媒体の記録方法。 （ただし、A1〜A9はＨ、CH3、OCH3CN、ハロ
ゲン、NH2、COOHまたはCONH2であり、B1，
B2はＸがＣのときのみ存在するＨまたはアルキ
ル基であり、R1，R2はＨまたはアルキル基であ
り、ＸはＣ、ＮまたはＳ、ＹはＣまたはＮであ
る。）[Scope of Claims] 1. An optical recording medium made of an organic photochromic dye is irradiated with light such as ultraviolet rays and treated at a temperature above room temperature and below a temperature at which a change in the molecular structure due to heat such as decomposition or thermal rearrangement of the dye occurs. A recording method for an optical recording medium, comprising a step of forming an aggregate of the dye in combination with a heat treatment operation. 2. The recording method for an optical recording medium according to claim 1, wherein the organic photochromic dye is spiropyran. 3. The recording method for an optical recording medium according to claim 2, wherein spiropyran has a structure represented by the following general formula. (However, A 1 to A 9 are H, CH 3 , OCH 3 CN, halogen, NH 2 , COOH or CONH 2 , and B 1 ,
B 2 is H or an alkyl group present only when X is C, R 1 and R 2 are H or an alkyl group, X is C, N or S, and Y is C or N. )
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60231517A JPS6290651A (en) | 1985-10-17 | 1985-10-17 | Recording method on optical recording media |
| DE3689891T DE3689891T2 (en) | 1985-03-06 | 1986-03-05 | High density optical recording media, methods of making the same and methods for recording optical information in this medium. |
| US06/836,625 US4737427A (en) | 1985-03-06 | 1986-03-05 | Optical high density recording mediums, method for making same and method for recording optical information in the medium |
| EP86102848A EP0193931B1 (en) | 1985-03-06 | 1986-03-05 | Optical high density recording mediums, method for making same and method for recording optical information in the medium |
| US07/145,686 US4845021A (en) | 1985-03-06 | 1988-01-14 | Method for recording optical information in optical high density recording mediums |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60231517A JPS6290651A (en) | 1985-10-17 | 1985-10-17 | Recording method on optical recording media |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6290651A JPS6290651A (en) | 1987-04-25 |
| JPH0367251B2 true JPH0367251B2 (en) | 1991-10-22 |
Family
ID=16924726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60231517A Granted JPS6290651A (en) | 1985-03-06 | 1985-10-17 | Recording method on optical recording media |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6290651A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2808117B2 (en) * | 1988-06-27 | 1998-10-08 | 津田駒工業株式会社 | Horizontal insertion control method |
| JP2732314B2 (en) * | 1989-03-24 | 1998-03-30 | 富士写真フイルム株式会社 | Optical information recording method and information recording medium |
| JPH0816981B2 (en) * | 1989-07-31 | 1996-02-21 | パイオニア株式会社 | Rewritable photochromic optical disk playback device |
| JP2559400Y2 (en) * | 1991-10-15 | 1998-01-14 | 株式会社パイオラックス | Lid locking device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5127279B2 (en) * | 1972-06-28 | 1976-08-11 |
-
1985
- 1985-10-17 JP JP60231517A patent/JPS6290651A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6290651A (en) | 1987-04-25 |
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