JPH0562189A - Rewritable recording medium and its recording method - Google Patents
Rewritable recording medium and its recording methodInfo
- Publication number
- JPH0562189A JPH0562189A JP3219537A JP21953791A JPH0562189A JP H0562189 A JPH0562189 A JP H0562189A JP 3219537 A JP3219537 A JP 3219537A JP 21953791 A JP21953791 A JP 21953791A JP H0562189 A JPH0562189 A JP H0562189A
- Authority
- JP
- Japan
- Prior art keywords
- recording
- recording medium
- colored particles
- layer
- crystalline organic
- 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.)
- Granted
Links
Landscapes
- Optical Record Carriers And Manufacture Thereof (AREA)
- Optical Recording Or Reproduction (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、光あるいは熱により可
逆的に記録、消去が可能な記録媒体に関するもので、カ
ラー記録も可能とするものであり、特に光記録媒体とし
ての応用に利点がある。本発明は、定期券、切符、回数
券などプリペイドカードとして用いられる書換え可能な
表示機能付きメモリーカードや,ICカード、カラー複
写機,ファクシミリ用記録紙および光ディスクなどに広
く利用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium capable of reversibly recording and erasing by light or heat, which enables color recording, and is particularly advantageous for application as an optical recording medium. is there. INDUSTRIAL APPLICABILITY The present invention is widely used for a rewritable memory card with a display function, which is used as a prepaid card such as a commuter ticket, a ticket, and a coupon ticket, an IC card, a color copying machine, a recording paper for facsimile, and an optical disk.
【0002】[0002]
【従来の技術】従来、書換え可能な記録媒体に用いる記
録材料には、ヒートモードの材料とフォトンモードの材
料とがある。2. Description of the Related Art Conventionally, recording materials used for rewritable recording media include heat mode materials and photon mode materials.
【0003】ヒートモードの材料は、光吸収特性を有す
る可逆感熱記録材料によって可能であり、相変化形記録
材料や光磁気記録材料等がある。有機系の可逆感熱記録
材料としては、ロイコ染料と顕色剤および消色剤との組
合せにより可逆的に発色・消色させる感熱染料系の記録
材料と、マトリクスポリマ中の有機結晶粒子の融解・凝
固挙動を利用して、その凝固条件によって粒子の透明性
の変化を利用する相変化形の可逆感熱記録材料、および
例えばコレステリック液晶等の液晶ポリマによりその分
子配列の熱的挙動を利用して透明性を変える方法等があ
る。The heat mode material can be a reversible thermosensitive recording material having a light absorption property, such as a phase change type recording material and a magneto-optical recording material. Organic reversible thermosensitive recording materials include thermosensitive dye recording materials that reversibly develop and decolor by a combination of a leuco dye and a color developer and a decoloring agent, and melting of organic crystal particles in a matrix polymer. A phase-change type reversible thermosensitive recording material that utilizes the change in transparency of particles depending on its coagulation conditions, and a liquid crystal polymer such as cholesteric liquid crystal that is transparent by utilizing the thermal behavior of its molecular arrangement. There is a method of changing sex.
【0004】本発明は、マトリクスポリマ中の有機結晶
分子の融解・凝固挙動を利用して、その凝固条件によっ
て透明性が変化することを利用する相変化形感熱記録原
理を応用した書換え可能な記録材料に関するもので、光
の熱によってマトリクスポリマ中の結晶微粒子を融解さ
せ再び固化し、その条件によって例えば多結晶状態、単
結晶状態、あるいは無定形状態などの凝固形態に起因す
る透明性に違いを生じさせ記録するものである。この感
熱記録材料は、例えば特開昭54−119377に開示
されているように、マトリクスポリマと次のような溶融
性有機分子との組合せにより構成され、きわめて多様な
記録材料を構成できる。ここに開示された溶融性有機分
子としては、脂肪族、芳香族のアルコール、カルボン
酸、アミン、アミドおよび、これらのハロゲン化物、硫
化物などがある。また一方、マトリクスポリマとして
は、ポリエステル、ポリアミド、ポリアクリル酸、スチ
ロール、シリコーン、ポリ塩化ビニル、ポリ塩化ビニリ
デン、ポリアクリロニトリル等の一般的なポリマが開示
されている。また、これを改良して光熱変換にためにカ
ーボンブラックをさらに加えた記録材料や酸化防止剤を
加えたものが、例えば特開昭57−82087および特
開昭57−82088に開示されている。The present invention utilizes the melting and solidification behavior of organic crystal molecules in a matrix polymer to change the transparency depending on the solidification conditions of the matrix polymer. Regarding materials, the crystalline fine particles in the matrix polymer are melted and solidified again by the heat of light, and depending on the conditions, there is a difference in the transparency caused by the solidification morphology such as a polycrystalline state, a single crystal state, or an amorphous state. It is generated and recorded. This heat-sensitive recording material is composed of a combination of a matrix polymer and the following fusible organic molecules, as disclosed in, for example, Japanese Patent Laid-Open No. 54-119377, and can constitute a wide variety of recording materials. The fusible organic molecules disclosed herein include aliphatic and aromatic alcohols, carboxylic acids, amines, amides and their halides, sulfides, and the like. On the other hand, as the matrix polymer, general polymers such as polyester, polyamide, polyacrylic acid, styrene, silicone, polyvinyl chloride, polyvinylidene chloride and polyacrylonitrile are disclosed. Further, a recording material obtained by improving this and further adding carbon black for light-heat conversion and adding an antioxidant are disclosed in, for example, JP-A-57-82087 and 57-82088.
【0005】[0005]
【発明が解決しようとする課題】しかし、上記何れの従
来例には溶融性有機分子やマトリクスポリマやカーボン
ブラックが開示されているものの、それらお互いの相溶
性・分散性並びに光吸収体効果等の詳細は何等述べられ
ておらず、記録の画質、解像度などに優れ濃度が高い記
録が得られないという課題があった。また、カラー記録
ができないという課題もあった。However, although any of the above-mentioned conventional examples discloses a fusible organic molecule, a matrix polymer and carbon black, their mutual compatibility / dispersibility and light absorber effect, etc. No details are given, and there is a problem in that it is not possible to obtain a high-density recording that is excellent in recording image quality and resolution. There is also a problem that color recording cannot be performed.
【0006】そこで、本発明は新規な構成の可逆感熱記
録層を用いることによって、新規で品質の優れた書換え
可能な記録媒体を提供することを第1の目的としてい
る。Therefore, a first object of the present invention is to provide a rewritable recording medium which is new and excellent in quality by using a reversible thermosensitive recording layer having a novel structure.
【0007】第2の目的は,この記録媒体を用いて例え
ば表示機能付きカード、ファクシミリ用紙、光メモリな
どに広く応用する場合の書換え可能な記録方法を提供す
ることにある。A second object of the present invention is to provide a rewritable recording method in which the recording medium is widely applied to, for example, cards with a display function, facsimile sheets, optical memories and the like.
【0008】[0008]
【課題を解決するための手段】上記第1の目的を達成す
るために、本発明の書換え可能な記録媒体は、基板上
に、結晶性有機分子と透明マトリクスポリマと結晶核形
成能を表面に有する着色粒子とを含む記録層を具備す
る。上記第2の目的の、本発明の記録媒体の記録方法
は、低温モードの溶融・冷却過程によって記録層内の着
色粒子の表面近傍の結晶性有機分子を透明化した後、例
えば着色粒子の吸収波長光を照射し、この吸収波長を着
色粒子が吸収することによって高温モードの溶融・冷却
過程をおこない、記録層内の着色粒子の表面近傍の結晶
性有機分子の層を白濁させ、着色粒子を隠ぺいして記録
する方法である。In order to achieve the above-mentioned first object, a rewritable recording medium of the present invention has a crystalline organic molecule, a transparent matrix polymer and a crystal nucleating ability on the surface of a substrate. And a recording layer containing the colored particles. The second object of the present invention is to record a recording medium according to the present invention, in which crystalline organic molecules near the surface of the colored particles in the recording layer are made transparent by a melting / cooling process in a low temperature mode, and then, for example, absorption of colored particles Wavelength light is irradiated, and the colored particles absorb the absorption wavelength to carry out a melting / cooling process in a high temperature mode to cloud the crystalline organic molecule layer near the surface of the colored particles in the recording layer to It is a method of hiding and recording.
【0009】[0009]
【作用】本発明の書換え可能な記録媒体は、記録層に含
まれる結晶性有機分子が、加熱温度によって加熱溶融後
の冷却の際、透明状態と白濁状態とになる現象を利用し
ている。特に表面に結晶核形成能を有する着色粒子の表
面では、透明状態と白濁状態の二状態が双安定な挙動を
する。結晶性有機分子の融点近傍の温度で加熱溶融した
場合は、固化した結晶性有機分子は透明状態であり、さ
らに高い温度で溶融後冷却すると、固化した結晶性有機
分子は白濁状態になる。本発明では、溶融後冷却固化し
て透明状態になる加熱を低温モ−ドと呼び、白濁状態に
なる加熱を高温モ−ドと呼ぶ。この現象の理由は定かで
はないが、高温モ−ドによる加熱後冷却すると、降温速
度が速く結晶性有機分子が過冷却状態で融点以下まで冷
却されるため、一気に結晶化して微結晶となり白濁する
が、低温モ−ドによる加熱後冷却すると、ゆっくりと固
化するため、単結晶が大きく成長し透明状態になると想
定される。The rewritable recording medium of the present invention utilizes the phenomenon that the crystalline organic molecules contained in the recording layer become transparent and cloudy upon cooling after heating and melting depending on the heating temperature. In particular, on the surface of colored particles having the ability to form crystal nuclei on the surface, the two states of the transparent state and the cloudy state behave bistable. When heated and melted at a temperature near the melting point of the crystalline organic molecule, the solidified crystalline organic molecule is in a transparent state, and when it is melted at a higher temperature and then cooled, the solidified crystalline organic molecule becomes cloudy. In the present invention, heating to be melted and then cooled and solidified to be transparent is called a low temperature mode, and heating to be cloudy is called a high temperature mode. The reason for this phenomenon is not clear, but when cooled after being heated in a high temperature mode, the cooling rate is fast and the crystalline organic molecules are cooled to below the melting point in a supercooled state, so they crystallize at once and become fine crystals and become cloudy. However, when heated and cooled in a low temperature mode, it slowly solidifies, and it is assumed that the single crystal grows large and becomes transparent.
【0010】本発明の書換え可能な記録媒体はこのよう
な原理に基づき、表面に結晶核形成能を有する着色粒子
によって記録表示色をだし、この着色粒子を取り囲む結
晶性有機分子の2つの加熱温度モ−ド後の固化したとき
の2状態、即ち隠ぺい(白濁)と可視(透明)とにより
記録を行う。本発明の書換え可能な記録媒体の透明部分
は着色粒子が見えるため、着色粒子の色を示す。単色の
場合には着色粒子の色と白の記録が行え、着色粒子が複
数色に着色した場合には複数色と白の記録が行える。す
なわち、光記録の場合、吸収光が着色粒子に照射される
と、着色粒子は高温モードの温度上昇し冷却の後その表
面近傍は白濁する。一方、着色粒子の透過光が着色粒子
に照射された場合は、記録層の下の光吸収層が昇温し着
色粒子の下側が高温モードの温度上昇し冷却後にその表
面近傍は白濁して上部の着色粒子の色を浮き上がる。ま
た、着色粒子間の隙間では、光が直接に光吸収層に照射
吸収されて記録層の下側部分が高温モードの温度上昇し
て冷却後、白濁して白色を呈する。Based on such a principle, the rewritable recording medium of the present invention emits a recording and displaying color by colored particles having a crystal nucleus forming ability on the surface, and two heating temperatures of crystalline organic molecules surrounding the colored particles. Recording is carried out in two states when solidified after the mode, namely, hiding (white turbidity) and visible (transparent). Since the colored particles are visible in the transparent portion of the rewritable recording medium of the present invention, the color of the colored particles is shown. In the case of a single color, the color of the colored particles and white can be recorded, and when the colored particles are colored in a plurality of colors, the recording of a plurality of colors and white can be performed. That is, in the case of optical recording, when the colored particles are irradiated with the absorbed light, the temperature of the colored particles rises in the high temperature mode, and after cooling, the vicinity of the surface becomes cloudy. On the other hand, when the transmitted light of the colored particles is irradiated to the colored particles, the temperature of the light absorbing layer below the recording layer rises, the lower side of the colored particles rises in the high temperature mode, and after cooling, the vicinity of the surface becomes cloudy and becomes upper. Emboss the color of colored particles. Further, in the gaps between the colored particles, light is directly radiated and absorbed by the light absorbing layer, and the lower portion of the recording layer rises in temperature in the high temperature mode and is cooled, and then becomes cloudy and white.
【0011】[0011]
【実施例】本発明の着色粒子を用いた書換え可能な記録
媒体の代表的な一実施例を図1に示す。図1は、反射膜
2を形成した基板1上に、本発明の記録層3を形成して
いる。その記録層3の上にさらに表面保護層6が形成さ
れている。記録層3は図1に示したように、着色粒子
4、結晶性有機分子並びにマトリクスポリマを含み、例
えば着色粒子4の吸収波長の光を吸収する高温モ−ドに
よって着色粒子4の外殻層5が白濁する。記録層3のマ
トリクスポリマ中の結晶性有機分子が、着色粒子4の表
面近傍にこの外殻層5を形成する様子を拡大すると図2
のようになる。この外殻層5は、低い温度での加熱・放
冷過程(低温モード)によって透明な外殻層5Aと、例
えば着色粒子4が吸収する波長の光照射による高温の加
熱・冷却過程(高温モ−ド)によって白濁して光散乱す
る不透明な外殻層5Bとの2状態をとる。単色着色粒子
による記録の場合はこれがそれぞれ消去・記録に相当す
る。EXAMPLE FIG. 1 shows a typical example of a rewritable recording medium using the colored particles of the present invention. In FIG. 1, a recording layer 3 of the present invention is formed on a substrate 1 on which a reflective film 2 is formed. A surface protective layer 6 is further formed on the recording layer 3. As shown in FIG. 1, the recording layer 3 contains colored particles 4, crystalline organic molecules and a matrix polymer. For example, the outer layer of the colored particles 4 is formed by a high temperature mode that absorbs light having an absorption wavelength of the colored particles 4. 5 becomes cloudy. FIG. 2 is an enlarged view of the crystalline organic molecules in the matrix polymer of the recording layer 3 forming the outer shell layer 5 near the surface of the colored particles 4.
become that way. The outer shell layer 5 is a transparent outer shell layer 5A by a heating / cooling process (low temperature mode) at a low temperature, and a high temperature heating / cooling process (high temperature module) by irradiation with light having a wavelength absorbed by the colored particles 4, for example. -D), it takes two states with the opaque outer shell layer 5B that becomes cloudy and scatters light. In the case of recording with single color particles, this corresponds to erasing / recording.
【0012】本発明の書換え可能な記録媒体をカラー記
録化するには、例えば図3に示したような構成でおこな
われる。着色粒子をそれぞれ赤(R)、緑(G)、青(B)の
三原色の光透過性着色粒子より構成し、これを含む記録
層3を図3のように三原色の着色粒子4R,4G,4B
が一層に並ぶように構成し、記録層3の下に結晶性有機
分子と透明マトリクスポリマとよりなる第二の記録層7
を介して光吸収層8を設ける。この光吸収層8は、上の
各着色粒子の透過光を吸収し昇温する。ここではコント
ラストを良くするために新たに第二の記録層7を設けた
が、記録層3中の各着色粒子4R,4G,4Bの下側部
分が同様の働きをするため、図4のようにこの第二の記
録層7は必ずしも必要でない構成もある。図3の記録層
3中の各着色粒子4R、4Gおよび4Bのまわりには、
図1と同様結晶性有機分子とマトリクスポリマとを有
し、さらに記録層3上に表面保護層6が設けられてい
る。まず、低温モードの溶融・冷却過程によって記録層
3および第二の記録層7を透明化する。これによって透
明な着色粒子4R、4Gおよび4Bは各色に顕色する
が、その下にある光吸収層8のためにその各粒子の透過
光は吸収され、表面保護層6側から見ると黒色を呈す
る。これが記録前の初期状態である。これに、カラー画
像の光を図3のように照射すると、それぞれのR,G,
Bに着色された粒子4R、4Gおよび4Bは自分の透過
光以外の光を吸収し温度上昇する。その温度上昇した粒
子の近傍の結晶性有機分子が融解し、この高温モードの
溶融・冷却過程によって白濁し、着色粒子の色を隠ぺい
する。即ち、白色光の照射された部分では三原色の全て
の着色粒子は自分の透過光以外の光を吸収するため温度
上昇し、全ての着色粒子が粒子外殻に白濁層を形成して
白色を呈する。カラー部分の記録については、例えば緑
色光を照射した場合は緑着色粒子4Gだけが光を吸収し
ないため、緑着色粒子4Gのまわりは透明のまま保持さ
れるが、その緑色の透過光が光吸収層8で吸収され昇温
し高温モ−ドの溶融・冷却過程により粒子4Gの下に設
けた第二の記録層7を白濁化し、表面保護層6側から見
ると着色粒子4Gの色すなわち緑を呈する。緑色光の照
射された赤着色粒子4Rおよび青着色粒子4Bは、いず
れも光を吸収して温度上昇し、各々の表面近傍で白濁化
し白色を呈する。それ故、緑色の光を照射した箇所は緑
色を呈する。赤色光を照射した場合も同様の機構で、赤
色の記録が形成できる。一方、光の照射されない黒色部
では、全ての着色粒子はそのままで白濁化されず赤着色
粒子4R,緑着色粒子4Gおよび青着色粒子4Bはそれ
ぞれ光が透過し、各粒子直下の光吸収層8に各透過光が
吸収され結果として黒色を呈する。Color recording of the rewritable recording medium of the present invention is performed, for example, by the structure shown in FIG. The colored particles are composed of light-transmissive colored particles of the three primary colors of red (R), green (G), and blue (B), respectively, and the recording layer 3 including these is colored particles 4R, 4G of the three primary colors as shown in FIG. 4B
Second recording layer 7 composed of crystalline organic molecules and a transparent matrix polymer under the recording layer 3.
The light absorption layer 8 is provided via the. The light absorption layer 8 absorbs the transmitted light of the above colored particles and raises the temperature. Here, the second recording layer 7 is newly provided in order to improve the contrast, but since the lower parts of the respective colored particles 4R, 4G, 4B in the recording layer 3 have the same function, as shown in FIG. In some cases, the second recording layer 7 is not always necessary. Around each colored particle 4R, 4G and 4B in the recording layer 3 of FIG.
Similar to FIG. 1, it has a crystalline organic molecule and a matrix polymer, and further, a surface protective layer 6 is provided on the recording layer 3. First, the recording layer 3 and the second recording layer 7 are made transparent by a melting / cooling process in a low temperature mode. As a result, the transparent colored particles 4R, 4G, and 4B develop respective colors, but the transmitted light of each particle is absorbed by the light absorbing layer 8 therebelow, and when viewed from the surface protective layer 6 side, black is obtained. Present. This is the initial state before recording. When the light of the color image is applied to this as shown in FIG. 3, the R, G, and
The particles 4R, 4G, and 4B colored B absorb light other than their own transmitted light and rise in temperature. The crystalline organic molecules in the vicinity of the particles whose temperature has risen are melted, and due to the melting / cooling process in this high temperature mode, they become cloudy and hide the color of the colored particles. That is, in the portion irradiated with white light, the temperature of all the colored particles of the three primary colors absorbs light other than the transmitted light, and the temperature rises, and all colored particles form a white turbid layer on the outer shell of the particle and thus appear white. .. Regarding the recording of the color portion, for example, when green light is irradiated, only the green colored particles 4G do not absorb the light, so that the surroundings of the green colored particles 4G remain transparent, but the green transmitted light absorbs the light. The second recording layer 7 provided below the particles 4G is made cloudy by being absorbed in the layer 8 and being heated and melted / cooled in a high temperature mode, and when viewed from the surface protective layer 6 side, the color of the colored particles 4G, that is, green. Present. The red colored particles 4R and the blue colored particles 4B irradiated with green light both absorb light and rise in temperature, and become turbid and white in the vicinity of their surfaces. Therefore, the portion irradiated with green light exhibits a green color. A red recording can be formed by the same mechanism when red light is irradiated. On the other hand, in the black portion not irradiated with light, all the colored particles are not turbid and the red colored particles 4R, the green colored particles 4G and the blue colored particles 4B respectively transmit light, and the light absorbing layer 8 immediately below each particle. Each of the transmitted light is absorbed by and the resulting black color appears.
【0013】図4における第二の記録層7を用いない構
成も同様の原理で、この場合は記録層3の下側部分がこ
の第二の記録層7の機能をする。The structure in which the second recording layer 7 is not used in FIG. 4 has the same principle. In this case, the lower part of the recording layer 3 functions as the second recording layer 7.
【0014】なお、図3および図4では着色粒子に4
R、4Gおよび4Bの3種を用いた形態を示したが、単
色もしくは複数色(多色)記録であっても同様な作用で記
録できること勿論である。また、単色記録の場合には、
図3および図4に示した光吸収層8は光を吸収する機能
を有する必要はなく、例えば図1に示したような反射膜
2であってもよく、直接基板1上に記録層3を設けても
よい。さらに、単色記録の場合の着色粒子4は必ずしも
光に透明である必要はなく、黒色を再現しない場合には
不透明であってもよい。また、黒色を再現しない場合に
は、光吸収層8やその上の第二の記録層7も不必要であ
る。It should be noted that in FIGS.
Although the form using three kinds of R, 4G and 4B is shown, it is needless to say that the same operation can be performed even in the case of single color or plural color (multicolor) recording. In the case of single color recording,
The light absorption layer 8 shown in FIGS. 3 and 4 does not need to have a function of absorbing light, and may be the reflection film 2 shown in FIG. 1, for example, and the recording layer 3 may be directly formed on the substrate 1. It may be provided. Furthermore, the colored particles 4 in the case of monochromatic recording do not necessarily have to be transparent to light, and may be opaque when black is not reproduced. Further, when the black color is not reproduced, the light absorption layer 8 and the second recording layer 7 thereon are unnecessary.
【0015】このように、本発明の記録方法によれば、
何れも書換え可能記録ができ、しかも高温モ−ドの加熱
温度の程度によって白濁化の程度を制御でき隠ぺい力が
異なる記録ができるため、ハーフトーン記録も可能であ
り、簡単な構成によって書換え可能な記録を可能とし、
多色記録やカラー記録にも対応できる。As described above, according to the recording method of the present invention,
Rewritable recording is possible in each case, and the degree of clouding can be controlled depending on the heating temperature of the high-temperature mode, and recording can be performed with different hiding power, so halftone recording is also possible and rewriting is possible with a simple configuration. Enables recording,
It can also be used for multicolor recording and color recording.
【0016】本発明に供される基板1としては、例えば
ガラス、金属、高分子フィルム等が挙げられ、本発明の
記録媒体の用途により適当な材質を選択することができ
る。ただ、基板1として例えばアルミニウム、ステンレ
ススティール等の反射率の高い金属材料単独、例えば金
属蒸着フィルムまたは金属箔をラミネートした複合材料
等を用いると、本発明の記録媒体に図1に示したような
反射膜2が形成できる。また、本発明に供される反射膜
2には上記のような金属製の材料の他にも、例えば白濁
化処理を施した高分子フィルム等によっても対応でき、
何れの反射膜2を用いても反射光で記録表示でき、記録
画像のコントラストを高め、色純度を向上させるため好
ましい。The substrate 1 used in the present invention includes, for example, glass, metal, polymer film and the like, and an appropriate material can be selected depending on the use of the recording medium of the present invention. However, when the substrate 1 is made of a metal material having a high reflectance such as aluminum or stainless steel alone, for example, a metal vapor-deposited film or a composite material laminated with a metal foil, the recording medium of the present invention is as shown in FIG. The reflective film 2 can be formed. Further, the reflection film 2 used in the present invention can be supported by, for example, a polymer film that has been subjected to an opaque treatment, in addition to the above-mentioned metallic materials,
It is preferable that any of the reflection films 2 can be used for recording and display by reflected light, the contrast of a recorded image can be increased, and the color purity can be improved.
【0017】本発明の着色粒子4に供される材料として
は、着色顔料、染料もしくは顔料で着色された熱可塑性
樹脂または熱硬化性樹脂の高分子、ガラス、等の有機あ
るいは無機物質が挙げられ、着色粒子4は少なくとも表
面に結晶核を形成する機能を有する。これらの着色粒子
4の材料の中でも、高分子またはガラスは自由に粒子の
大きさを調整でき易いため好ましい。また、本発明の着
色粒子4は透明不透明何れでも良い。但し、着色粒子4
に透明な粒子を用い例えばカラー記録等のような多色記
録を行う場合だけには、図3に示したように着色粒子4
は記録層3中に1層並べる必要がある。着色粒子4の結
晶核を形成する機能としては、例えば着色粒子4の材料
に結晶性有機分子を結合させる、あるいは結晶成長を促
す例えば極性基等を結合させる等により達成できる。そ
の中でも、例えば水酸基、カルボキシル基、アミノ基も
しくはアミド基等の水素結合性基を着色粒子4の少なく
とも表面に結合させると、結晶性有機分子材料の選択が
広くなるため好ましい。Materials used for the colored particles 4 of the present invention include organic or inorganic substances such as coloring pigments, dyes or polymers of thermosetting resins colored with dyes or pigments, and glass. The colored particles 4 have a function of forming crystal nuclei on at least the surface. Among these materials for the colored particles 4, polymer or glass is preferable because the particle size can be easily adjusted freely. The colored particles 4 of the present invention may be transparent or opaque. However, colored particles 4
Only when multicolor recording such as color recording is performed by using transparent particles for the colored particles 4 as shown in FIG.
It is necessary to arrange one layer in the recording layer 3. The function of forming crystal nuclei of the colored particles 4 can be achieved by, for example, binding a crystalline organic molecule to the material of the colored particles 4 or binding a polar group or the like that promotes crystal growth. Among them, it is preferable to bond a hydrogen-bonding group such as a hydroxyl group, a carboxyl group, an amino group or an amide group to at least the surface of the colored particles 4 because the selection of the crystalline organic molecular material is widened.
【0018】着色粒子4の形状は、例えば球形粒子、円
盤状粒子、六角板状粒子あるいは立方体形状粒子等の何
れであってもよく、最密充填されると画質及び記録濃度
が向上するため望ましい。特に球形粒子は製法が比較的
容易で、粒子の充填率も向上させ易いため好ましい。着
色粒子4の大きさは、記録画像の解像力に直接影響を及
ぼすため小さい方が好ましいが、着色粒子4の歩留まり
を考慮すると1〜100μm程度が適当である。また、
着色粒子4の粒度分布は作製した記録層3の表面形状、
記録画像の解像力及び着色粒子4の記録層3中の充填率
等に影響を及ぼし、粒度分布が広い方が充填率及び記録
層3の表面形状には好ましいが、高温モ−ドでの加熱・
冷却の結果着色粒子4表面の白濁の濃度は着色粒子4の
光吸収割合に比例するため、着色粒子4の粒度分布はで
きるだけ均一の方が好ましい。したがって、着色粒子4
の粒度分布は記録層3の表面形状および記録画像の再現
性に応じて決定される。また、記録層3を構成する結晶
性有機分子およびマトリクスポリマと着色粒子4とを混
合し、例えば印刷もしくはキャスト法等の通常の手法を
適用して記録層3を形成でき、多色記録に適応するため
の着色粒子4を1層並べる手段としては、例えばリソグ
ラフィ、精密印刷、電子写真法等種々の方法が可能であ
り、容易にこの記録層3を構成できる。The shape of the colored particles 4 may be any of, for example, spherical particles, disk-shaped particles, hexagonal plate-shaped particles, cubic particles, and the like, and the most closely packed state improves the image quality and the recording density, which is desirable. .. In particular, spherical particles are preferable because the production method is relatively easy and the packing rate of particles is easily improved. The size of the colored particles 4 is preferably small because it directly affects the resolving power of the recorded image, but considering the yield of the colored particles 4, 1 to 100 μm is suitable. Also,
The particle size distribution of the colored particles 4 depends on the surface shape of the recording layer 3 produced,
The resolution of the recorded image and the filling rate of the colored particles 4 in the recording layer 3 are affected, and a wider particle size distribution is preferable for the filling rate and the surface shape of the recording layer 3, but heating in a high temperature mode
As a result of cooling, the concentration of white turbidity on the surface of the colored particles 4 is proportional to the light absorption ratio of the colored particles 4. Therefore, it is preferable that the particle size distribution of the colored particles 4 is as uniform as possible. Therefore, the colored particles 4
The particle size distribution of is determined according to the surface shape of the recording layer 3 and the reproducibility of the recorded image. In addition, the crystalline organic molecules and the matrix polymer forming the recording layer 3 are mixed with the colored particles 4, and the recording layer 3 can be formed by applying a usual method such as a printing or casting method, which is suitable for multicolor recording. As a means for arranging one layer of colored particles 4 for this purpose, various methods such as lithography, precision printing and electrophotography can be used, and the recording layer 3 can be easily constructed.
【0019】光吸収層8は、上層に設けた着色粒子4の
透過光を吸収する色相を有すればよいが、一般的には黒
色層とすればよい。The light absorbing layer 8 may have a hue that absorbs the transmitted light of the colored particles 4 provided in the upper layer, but it is generally a black layer.
【0020】本発明の記録層3および第二の記録層7に
用いる結晶性有機分子は、無色な低分子が供されるが、
易結晶性を考慮すると水素結合基を有する分子が好まし
い。水素結合基の中でも、カルボキシル基、ヒドロキシ
キシル基、アミノ基、アミド基のうちの少なくとも一つ
をもつ有機分子であると、結晶成長性が高いため好まし
く、しかも60〜120℃に融点を有する分子を用いる
と記録または消去に必要な熱エネルギーまたは光強度が
低く済むため望ましい。また、これらの分子の融点調整
のため、これら結晶性有機分子をさらに別個の例えば高
級アルコール、脂肪酸、アルキルアミン、オキシカルボ
ン酸、ジカルボン酸、ジアミン、アルキレングリコール
などと共晶あるいは錯体を形成させて、所望の融点を有
する結晶性有機分子を形成させることもできる。The crystalline organic molecule used in the recording layer 3 and the second recording layer 7 of the present invention is a colorless low molecule,
A molecule having a hydrogen bonding group is preferable in view of easy crystallinity. Among hydrogen bonding groups, an organic molecule having at least one of a carboxyl group, a hydroxyxyl group, an amino group, and an amide group is preferable because of high crystal growth property, and a molecule having a melting point of 60 to 120 ° C. It is desirable to use since the heat energy or light intensity required for recording or erasing can be reduced. Further, in order to adjust the melting point of these molecules, these crystalline organic molecules may be further formed into a eutectic or complex with a separate alcohol such as higher alcohol, fatty acid, alkylamine, oxycarboxylic acid, dicarboxylic acid, diamine, alkylene glycol. It is also possible to form crystalline organic molecules having a desired melting point.
【0021】本発明に用いるマトリクスポリマは、結晶
性有機分子と相互作用し結晶化挙動に大きな影響を与え
る。具体的にはポリエステル、ポリアクリル酸エステ
ル、ポリ塩化ビニル、塩化ビニルー酢酸ビニル共重合
体、酢酸セルロース、ポリビニルブチラール、ポリスチ
レン、スチレンーブタジエン共重合体などの透明な高分
子が挙げられるが、水素結合基を一部含有する透明マト
リクスポリマが相溶性を制御する意味で適している。具
体的な例として、接着性(OH基含有)ポリエステル、部
分ケン化酢酸ビニルー塩化ビニル共重合体、ポリアミ
ド、ポリウレタン、熱可塑性フェノール樹脂、ビニルア
ルコール共重合体、アクリル酸共重合体、アクリルアミ
ド共重合体、マレイン酸共重合体等がある。また、これ
に可塑剤を適時併用することも当然である。The matrix polymer used in the present invention interacts with the crystalline organic molecule and exerts a great influence on the crystallization behavior. Specific examples thereof include transparent polymers such as polyester, polyacrylic acid ester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, cellulose acetate, polyvinyl butyral, polystyrene, and styrene-butadiene copolymer, but hydrogen bond A transparent matrix polymer partially containing a group is suitable for controlling the compatibility. Specific examples include adhesive (OH group-containing) polyester, partially saponified vinyl acetate-vinyl chloride copolymer, polyamide, polyurethane, thermoplastic phenol resin, vinyl alcohol copolymer, acrylic acid copolymer, acrylamide copolymer. Examples include coalesced and maleic acid copolymers. In addition, it is natural to use a plasticizer in combination with this at appropriate times.
【0022】また、本発明の記録層には、例えば酸化防
止剤、紫外線吸収剤あるいは可塑剤等の添加剤を常法に
従い添加しても良いこと勿論である。Of course, additives such as an antioxidant, an ultraviolet absorber or a plasticizer may be added to the recording layer of the present invention by a conventional method.
【0023】なお、記録層3または第二の記録層7を構
成する結晶性有機分子のマトリクスポリマに対する添加
量は、5〜50%の範囲で加えることができるが、15
〜40%の添加が望ましい。結晶性有機分子の比率がこ
れ以上になると、結着力が弱まり記録層として均質なコ
ーティングも困難になる。逆に、マトリクスポリマの比
率が高くなると、結晶性有機分子の量が少なくなるた
め、不透明化が困難になり、記録のコントラストが悪く
なる。The addition amount of the crystalline organic molecules constituting the recording layer 3 or the second recording layer 7 to the matrix polymer can be added in the range of 5 to 50%.
Addition of ~ 40% is desirable. When the ratio of the crystalline organic molecules is higher than this, the binding force is weakened and it becomes difficult to uniformly coat the recording layer. On the other hand, when the ratio of the matrix polymer is high, the amount of crystalline organic molecules is small, which makes opacity difficult and deteriorates the contrast of recording.
【0024】本発明の書換え可能な記録媒体は、各種光
源およびレーザーにより記録・消去が可能であり、低コ
ストの光ディスクやプリンター、ファクシミリ用の記録
としても利用できるが、特にカラー記録において複写機
に用いるカラー画像再現の方法としても利用できる。こ
のように、光を用いる場合、その焦点深度によって記録
層3と第二の記録層7の昇温速度比の調整が可能であ
る。The rewritable recording medium of the present invention can be recorded / erased by various light sources and lasers, and can be used as recording for low-cost optical disks, printers, and facsimiles. It can also be used as a method of reproducing a color image to be used. As described above, when light is used, the temperature increase rate ratio between the recording layer 3 and the second recording layer 7 can be adjusted by the depth of focus.
【0025】本発明はレーザや一般光源のみならず例え
ば感熱ヘッド等の熱的手段によっても記録・消去が可能
である。但し、熱的手段で記録する場合は、一般的に単
色記録に応用されるが、高精度の記録ピッチで着色部分
の色相と対応できれば熱的手段でも多色記録は可能であ
ること勿論である。また、初期状態または消去状態にす
る加熱には、例えば熱ローラ等を用いる場合もある。In the present invention, recording / erasing can be performed not only by a laser or a general light source but also by a thermal means such as a thermal head. However, when recording by thermal means, it is generally applied to single-color recording, but it goes without saying that multi-color recording is also possible by thermal means if it can correspond to the hue of the colored portion with a highly accurate recording pitch. .. In addition, a heating roller or the like may be used for heating in the initial state or the erased state.
【0026】本発明における表面保護層6は、必ずしも
必要はないが、一般的に記録層3の傷やほこり等を防止
する目的で常法により形成される場合が多く、表面保護
層6を設けた形態が実用的である。また、耐摩耗性の表
面保護層6を付与すれば、例えば感熱ヘッドの接触に対
しても経時劣化が小さく繰り返し耐久性の高い記録媒体
を構成することができる。The surface protective layer 6 in the present invention is not always necessary, but in general, it is often formed by a conventional method for the purpose of preventing scratches and dust on the recording layer 3, and the surface protective layer 6 is provided. The form is practical. Further, by providing the abrasion-resistant surface protective layer 6, for example, it is possible to construct a recording medium which has little deterioration over time and has high durability against repeated contact with a thermal head.
【0027】次に、具体的実施例を用いて本発明を説明
する。 (実施例1)記録材料の結晶性有機分子としてヒドロキ
システアリン酸4gと、添加剤としてフェノール系酸化
防止剤0.1gと、透明マトリクスポリマとして部分ケ
ン化した水酸基をもつ塩化ビニルー酢酸ビニル共重合体
10gとを、テトラヒドロフラン100mlに溶解し、
さらに着色粒子4として平均粒径15μmの赤色のガラ
スビーズを7g分散し、図1に示す反射層2を有する基
板1としてアルミ蒸着した0.2mmのポリエステル高
分子シート基板上に、13μmの厚さで記録層3をグラ
ビア塗布法で形成した。その記録層3の上にさらに耐摩
耗性の表面保護層6として紫外線硬化形アクリル樹脂の
プレポリマをバー塗布法で20μmコーティング後、紫
外線照射して硬化させた。こうしてできた書換え可能な
記録媒体に半導体レーザによって、書き込み・消去をお
こなった。この記録媒体の透明化温度領域は約70〜9
0℃であった。この条件から半導体レーザによってエネ
ルギーを与え100℃で書き込み80℃で消去した。書
き込まれた不透明化域と消去された透明化域をそれぞれ
X線回折により解析したところ、いずれにも回折ピーク
が観測され微結晶であることがわかった。これらはそれ
ぞれ着色粒子4の粒子周辺の結晶性有機分子層の外殻層
5が多結晶状態で白濁し光散乱状態となった不透明な外
殻層5Bと、単結晶状態で透明な外殻層5Aとに相当し
ていることがわかった。また、ガラスビーズによる赤色
の記録は鮮明な画質を示した。耐久試験では、600回
の繰り返しが可能であった。Next, the present invention will be described with reference to specific examples. (Example 1) 4 g of hydroxystearic acid as a crystalline organic molecule of a recording material, 0.1 g of a phenolic antioxidant as an additive, and a vinyl chloride-vinyl acetate copolymer having a partially saponified hydroxyl group as a transparent matrix polymer. 10 g and is dissolved in 100 ml of tetrahydrofuran,
Further, 7 g of red glass beads having an average particle diameter of 15 μm were dispersed as the coloring particles 4, and the substrate 1 having the reflective layer 2 shown in FIG. The recording layer 3 was formed by the gravure coating method. On the recording layer 3, a prepolymer of an ultraviolet curable acrylic resin was further coated as a wear-resistant surface protective layer 6 by a bar coating method to a thickness of 20 μm and then cured by irradiation with ultraviolet rays. The rewritable recording medium thus formed was written / erased by a semiconductor laser. The transparentization temperature range of this recording medium is about 70-9.
It was 0 ° C. Under this condition, energy was applied by a semiconductor laser to write at 100 ° C. and erase at 80 ° C. When the written opaque region and the erased transparent region were analyzed by X-ray diffraction, diffraction peaks were observed in both and it was found that they were fine crystals. These are respectively an opaque outer shell layer 5B in which the outer shell layer 5 of the crystalline organic molecule layer around the particles of the colored particles 4 is in a polycrystalline state and becomes opaque and in a light scattering state, and a transparent outer shell layer in a single crystal state. It was found to correspond to 5A. Further, the red recording by the glass beads showed a clear image quality. In the durability test, it could be repeated 600 times.
【0028】(実施例2)記録材料の結晶性有機分子と
してベヘン酸3gと、添加剤としてフェノール系酸化防
止剤0.1gと、透明マトリクスポリマとして接着性ポ
リエステル(東洋紡(株)バイロン)2gとポリウレタン
5gとを、テトラヒドロフラン100mlに溶解し、さ
らに着色粒子として平均粒径20μmの黒色で導電性の
マグネタイト粒子4を7g分散し、図1に示す0.2m
mのポリエステル高分子シート基板1の一方の面を白濁
させた白色の反射層2上に、記録層3として20μmの
厚さでロール塗布法で形成した。その記録層3の上にさ
らに耐摩耗性の表面保護層6として紫外線硬化形アクリ
ル樹脂のプレポリマをバー塗布法で25μmコーティン
グ後、紫外線照射して硬化させた。こうしてできた書換
え可能な記録媒体に半導体レーザを照射し、書き込み・
消去をおこなった。このシートの透明化温度領域は約9
0〜110℃であった。この条件から半導体レーザによ
ってエネルギーを与え120℃で書き込み100℃で消
去したところ、黒色の鮮明な記録が得られた。さらに繰
り返して寿命特性を測定したところ480回の繰り返し
に耐えた。(Example 2) 3 g of behenic acid as a crystalline organic molecule of a recording material, 0.1 g of a phenolic antioxidant as an additive, and 2 g of an adhesive polyester (Byron Co., Ltd.) as a transparent matrix polymer. Polyurethane (5 g) was dissolved in tetrahydrofuran (100 ml), and black conductive black magnetite particles (4 g) having an average particle size of 20 μm were dispersed as colored particles to give 0.2 m shown in FIG.
A polyester polymer sheet substrate 1 of m having a thickness of 20 μm was formed as a recording layer 3 on a white reflective layer 2 having a white turbidity by a roll coating method. On the recording layer 3, a prepolymer of an ultraviolet-curable acrylic resin was further coated as a wear-resistant surface protective layer 6 by a bar coating method to a thickness of 25 μm and then irradiated with ultraviolet rays to be cured. The rewritable recording medium thus created is irradiated with a semiconductor laser to write / write.
It was erased. The transparency temperature range of this sheet is about 9
It was 0-110 degreeC. Under this condition, when energy was applied by a semiconductor laser and writing was performed at 120 ° C. and erasing was performed at 100 ° C., clear black recording was obtained. Further, the life characteristics were measured repeatedly, and it was able to withstand 480 repetitions.
【0029】(実施例3)記録材料の結晶性有機分子と
してヒドロキシステアリン酸4gと、添加剤としてヒン
ダードフェノール系酸化防止剤0.1gと、透明マトリ
クスポリマとして塩化ビニルー酢酸ビニルーアクリルア
ミド共重合体6gとをテトラヒドロフラン100mlに
溶解し記録材料溶液とした。この記録材料溶液を用い、
図3に示したように、カーボンブラックを含有した厚さ
15μmの黒色の光吸収層8を有した基板1の0.2m
m厚のポリエステルシート上に、厚さ10μmの第二の
記録層7をブレード塗布法で形成した。一方、この記録
材料溶液にさらに着色粒子4としてR,G,Bにそれぞ
れ着色された平均粒径20μmのメラミン樹脂粒子を4
g分散し、記録層3として25μmの厚さで、上記の基
板1の第二の記録層7の上にブレード塗布法で形成し
た。その記録層3の上にさらに耐摩耗性の表面保護層6
として紫外線硬化形アクリル樹脂のプレポリマをバー塗
布法で20μmコーティング後、紫外線照射して硬化さ
せた。こうしてできた書換え可能な記録媒体にカラー画
像の光を照射し、書き込みをおこなったところ、鮮明な
カラー画像が得られた。さらに、消去をおこなったの
ち、再度カラー画像の光を照射し、繰り返しカラー画像
を形成させた。この記録媒体の透明化温度領域は約70
〜90℃であった。さらに繰り返して寿命特性を測定し
たところ150回の繰り返しに耐えた。Example 3 4 g of hydroxystearic acid as a crystalline organic molecule of a recording material, 0.1 g of a hindered phenolic antioxidant as an additive, and a vinyl chloride-vinyl acetate-acrylamide copolymer as a transparent matrix polymer. 6 g was dissolved in 100 ml of tetrahydrofuran to obtain a recording material solution. Using this recording material solution,
As shown in FIG. 3, 0.2 m of the substrate 1 having the black light absorbing layer 8 containing carbon black and having a thickness of 15 μm
A 10 μm-thick second recording layer 7 was formed on a m-thick polyester sheet by a blade coating method. On the other hand, 4 melamine resin particles each having an average particle size of 20 μm and colored with R, G and B were further added as colored particles 4 to the recording material solution.
g was dispersed, and a recording layer 3 having a thickness of 25 μm was formed on the second recording layer 7 of the substrate 1 by a blade coating method. An abrasion-resistant surface protective layer 6 is further formed on the recording layer 3.
As a prepolymer of an ultraviolet-curable acrylic resin was coated by a bar coating method to a thickness of 20 μm, the resin was irradiated with ultraviolet rays to be cured. When the rewritable recording medium thus formed was irradiated with light of a color image to perform writing, a clear color image was obtained. Further, after erasing, color image light was irradiated again to repeatedly form a color image. The transparentization temperature range of this recording medium is about 70.
Was ~ 90 ° C. Further, the life characteristics were measured repeatedly, and it was able to withstand 150 times of repetition.
【0030】(実施例4)黒色光吸収層8として厚さ1
5μmのカーボンブラック含有塗料を吹き付けた0.2
mm厚のポリエステルシートを基板1として用い、この
光吸収層8上に、図4のように実施例3と同じ記録材料
を用いて記録層3を実施例3と同様な手法で35μmの
厚みで形成し、さらに表面保護層6として紫外線硬化形
アクリル樹脂のプレポリマをバー塗布法で20μmコー
ティング後、紫外線照射して硬化させた。こうしてでき
た書換え可能な記録媒体に実施例3と同様にカラー画像
の光を照射し、書き込みをおこなったところ、鮮明なカ
ラー画像が得られた。さらに、消去をおこなったのち、
再度カラー画像の光を照射し、繰り返しカラー画像を形
成させた。この記録媒体の透明化温度領域は約70〜9
0℃であった。さらに繰り返して寿命特性を測定したと
ころ270回の繰り返しに耐えた。(Example 4) Black light absorbing layer 8 having a thickness of 1
0.2 sprayed with 5 μm carbon black containing paint
A mm-thick polyester sheet is used as the substrate 1, and the same recording material as in Example 3 is used to form a recording layer 3 on the light absorption layer 8 in the same manner as in Example 3 with a thickness of 35 μm. Further, a prepolymer of an ultraviolet curable acrylic resin was coated as the surface protective layer 6 by a bar coating method to a thickness of 20 μm, and was then irradiated with ultraviolet rays to be cured. When the rewritable recording medium thus formed was irradiated with light of a color image in the same manner as in Example 3 to perform writing, a clear color image was obtained. Furthermore, after erasing,
The color image light was irradiated again to repeatedly form a color image. The transparentization temperature range of this recording medium is about 70-9.
It was 0 ° C. Further, the life characteristics were measured repeatedly, and it was possible to endure the repetition of 270 times.
【0031】なお、上記実施例は何れも光記録の例を示
したが、例えば感熱ヘッド等による熱記録も可能であっ
た。特に上記実施例に示したように表面保護層6の効果
で、感熱ヘッドによる損傷もなく、良好な記録ができ
た。In each of the above embodiments, an example of optical recording was shown, but thermal recording with a thermal head or the like was also possible. In particular, as shown in the above-mentioned examples, the effect of the surface protective layer 6 did not damage the thermal head, and good recording was possible.
【0032】また、上記実施例では単色記録とカラー記
録の場合を例示したが、多色記録であっても同様に記録
できること勿論である。Further, in the above embodiment, the case of monochromatic recording and color recording was illustrated, but it is needless to say that the same recording can be performed even in multicolor recording.
【0033】[0033]
【発明の効果】以上のように本発明は、基板上に、結晶
性有機分子と透明マトリクスポリマと結晶核形成表面を
有する着色粒子とを含む記録層を形成した記録媒体であ
るため、優れた書換え可能な記録媒体を提供するもので
ある。As described above, the present invention is an excellent recording medium in which a recording layer containing crystalline organic molecules, a transparent matrix polymer, and colored particles having a crystal nucleation surface is formed on a substrate. A rewritable recording medium is provided.
【0034】また、本発明の書換え可能な記録媒体は、
着色粒子を多色化すると、カラー記録表示をおこなうこ
とができる。このように本発明は、簡単な構成によって
書換え可能なカラーの記録を可能とするものである。The rewritable recording medium of the present invention is
When the colored particles are multicolored, color recording display can be performed. As described above, the present invention enables rewritable color recording with a simple configuration.
【図1】本発明の書換え可能な記録媒体の一実施例の構
成を示す要部拡大断面図FIG. 1 is an enlarged sectional view of an essential part showing the configuration of an embodiment of a rewritable recording medium of the present invention.
【図2】(a)は本発明の書換え可能な記録媒体の一実
施例の着色粒子表面近傍の透明状態の結晶性有機分子層
を説明する要部拡大断面図 (b)は本発明の書換え可能な記録媒体の一実施例の着
色粒子表面近傍の不透明状態の結晶性有機分子層を説明
する要部拡大断面図FIG. 2 (a) is an enlarged cross-sectional view of an essential part for explaining a crystalline organic molecular layer in a transparent state in the vicinity of a surface of a colored particle of an embodiment of a rewritable recording medium of the present invention. An enlarged cross-sectional view of an essential part for explaining an opaque crystalline organic molecular layer in the vicinity of the surface of the colored particles in one example of a possible recording medium
【図3】本発明の書換え可能な記録媒体の別の実施例の
構成をを示す要部拡大断面図FIG. 3 is an enlarged sectional view of an essential part showing the configuration of another embodiment of the rewritable recording medium of the present invention.
【図4】本発明の書換え可能な記録媒体の他の実施例の
構成をを示す要部拡大断面図FIG. 4 is an enlarged sectional view of an essential part showing the configuration of another embodiment of the rewritable recording medium of the present invention.
1 基板 2 反射膜 3 記録層 4 着色粒子 4R 赤着色粒子 4G 緑着色粒子 4B 青着色粒子 5 外殻層 5A 透明な外殻層 5B 不透明な外殻層 6 表面保護層 7 第二の記録層 8 光吸収層 1 substrate 2 reflective film 3 recording layer 4 colored particles 4R red colored particles 4G green colored particles 4B blue colored particles 5 outer shell layer 5A transparent outer shell layer 5B opaque outer shell layer 6 surface protective layer 7 second recording layer 8 Light absorption layer
Claims (9)
クスポリマと、前記結晶性有機分子の結晶核形成能を少
なくとも表面に有する着色粒子とを含む記録層を設けた
ことを特徴とする書換え可能な記録媒体。1. A recording layer comprising a crystalline organic molecule, a transparent matrix polymer, and colored particles having at least the surface capable of forming crystal nuclei of the crystalline organic molecule on a substrate. Rewritable recording medium.
る平均粒径が1〜100μmの球状粒子であることを特
徴とする、請求項1記載の書換え可能な記録媒体。2. The rewritable recording medium according to claim 1, wherein the colored particles are spherical particles made of glass or polymer and having an average particle diameter of 1 to 100 μm.
の光透過性粒子であり、前記着色粒子を記録層中に1層
並べ、前記記録層の下に前記着色粒子の透過光を吸収す
る光吸収層を設けたことを特徴とする、請求項1または
2何れかに記載の書換え可能な記録媒体。3. The colored particles are a plurality of light transmissive particles each having a plurality of hues, one layer of the colored particles is arranged in a recording layer, and the transmitted light of the colored particles is absorbed under the recording layer. 3. The rewritable recording medium according to claim 1, further comprising a light absorbing layer.
れ色分解した着色粒子よりなることを特徴とする、請求
項3記載の書換え可能な記録媒体。4. The rewritable recording medium according to claim 3, wherein the colored particles are colored particles which are color-separated into three primary colors of red, green and blue.
透明マトリクスポリマとを含む第二の記録層を設けてな
ることを特徴とする、請求項1、3または4何れかに記
載の書換え可能な記録媒体。5. A second recording layer containing crystalline organic molecules and a transparent matrix polymer is provided between the substrate and the light absorbing layer, according to claim 1, 3 or 4. Rewritable recording medium described.
粒子の表面が水素結合基を有することを特徴とする、請
求項1または2何れかに記載の書換え可能な記録媒体。6. The rewritable recording medium according to claim 1, wherein the crystalline organic molecule has a hydrogen bonding group, and the surface of the colored particle has a hydrogen bonding group.
ロキシキシル基の少なくとも一つを持ち、60〜120
℃に融点を有する分子よりなることを特徴とする、請求
項6記載の書換え可能な記録媒体。7. The crystalline organic molecule has at least one of a carboxyl group and a hydroxyxyl group, and has 60 to 120.
7. The rewritable recording medium according to claim 6, wherein the rewritable recording medium comprises a molecule having a melting point at ° C.
なることを特徴とする請求項1記載の書換え可能な記録
媒体。8. A rewritable recording medium according to claim 1, further comprising a light reflection film provided between the substrate and the recording layer.
透明マトリクスポリマと、少なくとも表面に前記結晶性
有機分子の結晶核形成能を有する着色粒子とを含む記録
層を、低温モードでの溶融後冷却過程によって前記記録
層内の前記着色粒子の表面近傍の前記結晶性有機分子を
透明化した後、前記着色粒子の吸収波長光を照射し前記
着色粒子が前記吸収光の吸収を伴う高温モードでの溶融
後冷却過程をおこない、前記記録層内の前記着色粒子の
表面近傍の前記結晶性有機分子を白濁化し、前記着色粒
子の色を隠ぺいして記録することを特徴とする書換え可
能な記録媒体の記録方法。9. A crystalline organic molecule provided on a substrate,
A recording layer containing a transparent matrix polymer and a colored particle having at least a surface capable of forming crystal nuclei of the crystalline organic molecule, in the vicinity of the surface of the colored particle in the recording layer by a cooling process after melting in a low temperature mode. After making the crystalline organic molecule transparent, the colored particles are irradiated with light having an absorption wavelength, and the colored particles undergo a cooling process after melting in a high temperature mode accompanied by absorption of the absorbed light, and the coloring in the recording layer. A method for recording on a rewritable recording medium, characterized in that the crystalline organic molecule in the vicinity of the surface of a particle is made cloudy and the color of the colored particle is hidden and recorded.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3219537A JP2993203B2 (en) | 1991-08-30 | 1991-08-30 | Rewritable recording medium and recording method thereof |
US07/936,413 US5364829A (en) | 1991-08-30 | 1992-08-27 | Rewritable recording medium and a method of recording in the same |
DE69202940T DE69202940T2 (en) | 1991-08-30 | 1992-08-28 | Rewritable recording material and recording method using this material. |
EP92114731A EP0530699B1 (en) | 1991-08-30 | 1992-08-28 | A rewritable recording medium and a method of recording in the same |
US08/222,778 US5543381A (en) | 1991-08-30 | 1994-04-04 | Rewritable recording medium and a method of recording in the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3219537A JP2993203B2 (en) | 1991-08-30 | 1991-08-30 | Rewritable recording medium and recording method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0562189A true JPH0562189A (en) | 1993-03-12 |
JP2993203B2 JP2993203B2 (en) | 1999-12-20 |
Family
ID=16737044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3219537A Expired - Fee Related JP2993203B2 (en) | 1991-08-30 | 1991-08-30 | Rewritable recording medium and recording method thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2993203B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1391315A2 (en) | 2002-08-19 | 2004-02-25 | Sony Corporation | Reversible multicolor recording medium, and recording method using the same |
JP2010027811A (en) * | 2008-07-17 | 2010-02-04 | Glory Science Co Ltd | Light emitting diode and method for controlling intensity of light emitting diode |
JP2014508058A (en) * | 2011-02-28 | 2014-04-03 | ピエール ラザリ、ジャン | Method for forming a color laser image with high reflectivity, and document in which the color laser image is produced by this method |
-
1991
- 1991-08-30 JP JP3219537A patent/JP2993203B2/en not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1391315A2 (en) | 2002-08-19 | 2004-02-25 | Sony Corporation | Reversible multicolor recording medium, and recording method using the same |
US6995116B2 (en) | 2002-08-19 | 2006-02-07 | Sony Corporation | Reversible multicolor recording medium, and recording method using the same |
JP2010027811A (en) * | 2008-07-17 | 2010-02-04 | Glory Science Co Ltd | Light emitting diode and method for controlling intensity of light emitting diode |
JP2014508058A (en) * | 2011-02-28 | 2014-04-03 | ピエール ラザリ、ジャン | Method for forming a color laser image with high reflectivity, and document in which the color laser image is produced by this method |
Also Published As
Publication number | Publication date |
---|---|
JP2993203B2 (en) | 1999-12-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0530699B1 (en) | A rewritable recording medium and a method of recording in the same | |
JP4117080B2 (en) | Reversible recording medium, recording method and reversible recording apparatus using the reversible recording medium | |
JP3635876B2 (en) | Image recording medium and image forming method and erasing method in recording medium | |
JP2004074584A (en) | Reversible multi-color recording medium and recording method using the recording medium | |
CN113771520A (en) | Structural color thermal sensitive paper based on thermochromic photonic crystals and preparation and application thereof | |
JP2993203B2 (en) | Rewritable recording medium and recording method thereof | |
JP2004155010A (en) | Reversible multicolor recording medium and recording method using the same | |
JP3164845B2 (en) | Recording method of rewritable recording medium | |
JP2004168024A (en) | Reversibile multicolor recording medium and recording method using the same | |
JP2005205882A (en) | Thermal recording medium | |
JP2004188827A (en) | Recorder for reversible multi-color recording medium | |
JP2004074583A (en) | Reversible multi-color recording medium and recording method using the recording medium | |
JP2004188829A (en) | Recorder for reversible multi-color recording medium | |
JP2000198275A (en) | Rewritable recording medium and method for recording it | |
JP2701613B2 (en) | Reversible thermosensitive recording medium | |
JP2000079767A (en) | Reversible thermosensitive recording medium | |
JP4287016B2 (en) | Reversible recording medium | |
JPH07314899A (en) | Heat-sensitive recording medium | |
JP2004249540A (en) | Recorder for reversible multicolor recording medium | |
JP4586353B2 (en) | Recording method | |
JP2005153156A (en) | Reversible multicolor recording medium and recording method using the same | |
JP2005131909A (en) | Recording medium and coloring composition | |
JP2004249539A (en) | Recorder for reversible multicolor recording medium | |
JP2002103825A (en) | Reversible heat sensitive recording medium and method for recording the same | |
US20030160906A1 (en) | Image forming method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
LAPS | Cancellation because of no payment of annual fees |