JP4470468B2 - Reversible multicolor recording medium and method for producing the same - Google Patents
Reversible multicolor recording medium and method for producing the same Download PDFInfo
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/34—Multicolour thermography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/305—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers with reversible electron-donor electron-acceptor compositions
Description
本発明は、繰り返し画像またはデータを記録するための可逆性多色記録媒体、及びその製造方法に関わる。 The present invention relates to a reversible multicolor recording medium for repeatedly recording images or data, and a method for manufacturing the same.
近年、地球環境的な見地から、リライタブル記録技術の必要性が強く認識されている。コンピューターのネットワーク技術、通信技術、ＯＡ機器、記録メディア、記憶メディア等の進歩を背景としてオフィスや家庭でのペーパーレス化が進んでいる。 In recent years, the necessity of rewritable recording technology has been strongly recognized from the viewpoint of the global environment. With the progress of computer network technology, communication technology, OA equipment, recording media, storage media, etc., paperless is progressing in offices and homes.
印刷物に替わる表示媒体の一例として、熱により可逆的に情報の記録や消去が可能な記録媒体、いわゆる可逆性感熱記録媒体が、各種プリペイドカード、ポイントカード、クレジットカード、ＩＣカード等の普及に伴い、残額やその他の記録情報等の可視化、可読化の用途において実用化されており、さらには複写機及びプリンター用途においても実用化されつつある。 As an example of a display medium that replaces printed matter, a recording medium capable of reversibly recording and erasing information by heat, a so-called reversible thermosensitive recording medium, has been widely used for various types of prepaid cards, point cards, credit cards, IC cards, etc. In addition, it has been put into practical use in applications such as visualization and readability of the balance and other recorded information, and is also being put into practical use in copying machines and printers.
上記のような可逆性感熱記録媒体、及びこれを用いた記録方法に関しては、従来においても各種提案がなされている（例えば、特許文献１〜４参照。）。これらは、いわゆる低分子分散タイプ、すなわち樹脂母材中に有機低分子物質を分散させた記録媒体であり、熱履歴により光の散乱を変化させ、記録層を白濁あるいは透明状態に変化させるものであるため、画像形成部と画像未形成部のコントラストが不充分であるという欠点を有しているため、記録層の下に反射層を設けることによりコントラストを向上させた媒体のみが実用化されている。 Various proposals have been made regarding the reversible thermosensitive recording medium and the recording method using the same (see, for example, Patent Documents 1 to 4). These are so-called low-molecular dispersion types, that is, recording media in which organic low-molecular substances are dispersed in a resin base material, which changes the scattering of light by the thermal history and changes the recording layer to cloudy or transparent. Therefore, since the contrast between the image forming portion and the image non-forming portion is insufficient, only a medium whose contrast is improved by providing a reflective layer under the recording layer has been put into practical use. Yes.
一方、ロイコ染料タイプ、すなわち樹脂母材中に電子供与性呈色性化合物であるロイコ染料と、顕・減色剤とが分散された記録層を有する記録媒体、及びこれを用いた記録方法についての開示がなされている（例えば、特許文献５〜９参照。）。これらにおいて、顕・減色剤としては、ロイコ染料を発色させる酸性基と、発色したロイコ染料を消色させる塩基性基を有する両性化合物、または長鎖アルキルをもつフェノール化合物等が用いられている。この記録媒体及び記録方法は、ロイコ染料自体の発色を利用するため、低分子分散タイプに比較してコントラスト、視認性が良好であり、近年広く実用化されつつある。 On the other hand, a leuco dye type, that is, a recording medium having a recording layer in which a leuco dye that is an electron donating color developing compound and a developer / color-reducing agent are dispersed in a resin base material, and a recording method using the same Disclosure has been made (see, for example, Patent Documents 5 to 9). In these, as the developer / color-reducing agent, an amphoteric compound having an acidic group for developing a leuco dye and a basic group for decoloring the developed leuco dye, a phenol compound having a long-chain alkyl, or the like is used. Since this recording medium and recording method utilize the color developed by the leuco dye itself, the recording medium and the recording method have better contrast and visibility than the low molecular dispersion type, and have been widely put into practical use in recent years.
上記各特許文献により開示されている従来技術においては、母材の材料の色すなわち地肌の色と、熱により変色した色の２種類の色のみしか表現することができない。しかし近年では、視認性やファッション性向上のために、多色画像の表示や各種データを色識別して記録したりすることへの要求が非常に高まっている。
これに対し、上記従来方法を応用し、かつ多色画像の表示を行う記録方法が種々提案されている。
In the prior art disclosed in each of the above patent documents, only two types of colors, that is, the color of the base material, that is, the background color, and the color changed by heat can be expressed. However, in recent years, in order to improve visibility and fashionability, there has been a great demand for displaying multicolor images and recording various data by color identification.
On the other hand, various recording methods that apply the above-described conventional method and display a multicolor image have been proposed.
例えば、多色に塗り分けられた層や粒子を、低分子分散タイプの記録層で可視化あるいは隠蔽することで、多色表示を行う記録媒体、及びこれを用いた記録方法が開示されている（特許文献１０〜１２参照。）。しかしこのような構成の記録媒体においては、記録層が下層の色を完全に隠蔽することはできず、母材の色が透けてしまい、高いコントラストが得られなかった。 For example, a recording medium that performs multicolor display by visualizing or concealing layers and particles separately coated in multiple colors with a low molecular dispersion type recording layer, and a recording method using the same are disclosed ( (See Patent Documents 10 to 12.) However, in the recording medium having such a configuration, the recording layer cannot completely hide the color of the lower layer, the color of the base material is transparent, and high contrast cannot be obtained.
また、ロイコ染料を用いた可逆性感熱多色記録媒体について、その他の開示もなされているが（例えば、特許文献１３、１４参照。）、これらは面内に色相の異なる繰り返し単位を有するものであるため、各色相が実際に記録される面積比が小さいため、記録した画像は非常に暗い、または薄い画像しか得ることはできないという問題がある。 Although other disclosures have been made on reversible thermosensitive multicolor recording media using leuco dyes (see, for example, Patent Documents 13 and 14), these have repeating units having different hues in the plane. Therefore, since the area ratio in which each hue is actually recorded is small, there is a problem that a recorded image can be obtained only in a very dark or thin image.
また、発色温度、消色温度、冷却速度等が異なるロイコ染料を用いた記録層を分離、独立した状態で形成された構成の可逆性感熱多色記録媒体に関する開示もなされている（例えば、特許文献１５〜２３参照。）。
しかし、サーマルヘッド等の記録熱源による温度コントロールが困難な上、良好なコントラストが得られず、色のかぶりを避けられないという問題を有している。さらには、三色以上の多色化をサーマルヘッド等による加熱温度及び／または加熱後の冷却速度の違いのみでコントロールするのは非常に困難である。
Also disclosed is a reversible thermosensitive multicolor recording medium having a structure in which recording layers using leuco dyes having different color development temperature, decoloring temperature, cooling rate, etc. are separated and formed independently (for example, patents). Reference 15-23).
However, there are problems that it is difficult to control the temperature with a recording heat source such as a thermal head, a good contrast cannot be obtained, and color fog cannot be avoided. Furthermore, it is very difficult to control the increase of three or more colors only by the difference in heating temperature and / or cooling rate after heating with a thermal head or the like.
また、ロイコ染料を用いた記録層を、分離、独立した状態で形成した構成の可逆性感熱多色記録媒体において、レーザー光の照射による光−熱変換により任意の記録層のみを加熱し、発色させる記録方法に関する開示もなされている（例えば、特許文献２４参照。）。この方法によれば、光−熱変換層の波長選択性の効果により、任意の記録層のみを発色させることができ、従来の可逆性多色記録媒体で問題であった、色のかぶりの問題が解決できる可能性がある。
しかしながら、この技術においては、記録層中に含有されている成分間相互の作用関係や、光−熱変換材料（赤外線吸収剤）の光吸収特性とレーザー光の波長との関係、さらには記録層の積層順等については検討されていない。よって実用上充分に所望の色のみを発色させることは困難であり、色かぶりの問題についても解決できない。
さらには、色の三原色として、レッド、グリーン、ブルーを用いているため、中間色は暗く色再現性が悪いので、フルカラー表示は不可能である。
またさらに、記録媒体を構成する光−熱変換層（レーザー光の吸収層）について、バインダーを含有せずに有機溶剤に溶解した光吸収材料を被着させることにより形成することを好適としているため、極めて広い波長領域においてレーザー光の吸収を有するようになってしまい、表示精度が劣化するという欠点を有している。また、かかる方法において成膜されたレーザー光の吸収層は、可視域においても光吸収を有しているため、消去状態において記録層の透明性が劣化し、記録精度が悪化を招来するという問題も有している。
In addition, in a reversible thermosensitive multicolor recording medium having a structure in which a recording layer using a leuco dye is separated and formed independently, only an arbitrary recording layer is heated by light-to-heat conversion by laser light irradiation, and color development The recording method to be performed is also disclosed (for example, refer to Patent Document 24). According to this method, due to the wavelength selectivity effect of the light-to-heat conversion layer, only an arbitrary recording layer can be colored, and the problem of color fog, which has been a problem with conventional reversible multicolor recording media. May be resolved.
However, in this technique, the interaction between the components contained in the recording layer, the relationship between the light absorption characteristics of the light-heat conversion material (infrared absorber) and the wavelength of the laser beam, and further the recording layer The order of stacking has not been studied. Therefore, it is difficult to develop only a desired color practically, and the problem of color cast cannot be solved.
Furthermore, since red, green, and blue are used as the three primary colors, the intermediate color is dark and has poor color reproducibility, so that full color display is impossible.
Furthermore, the light-heat conversion layer (laser light absorption layer) constituting the recording medium is preferably formed by depositing a light absorption material dissolved in an organic solvent without containing a binder. However, there is a disadvantage that the laser beam is absorbed in an extremely wide wavelength region, and the display accuracy is deteriorated. In addition, the laser light absorption layer formed by such a method has light absorption even in the visible region, so that the transparency of the recording layer is deteriorated in the erased state, and the recording accuracy is deteriorated. Also have.
上述したように、多色感熱記録を行うことができる記録媒体について、明瞭で鮮やかな色調による記録を実現することへの要望は大きくなりつつあるが、特に、多数回繰り返して記録及び消去を行った場合における記録特性の劣化を極力低減化したり、あるいは長期間保存後においても初期と同等の記録特性を維持したりすることへの検討は未だ充分になされていない。 As described above, there is an increasing demand for recording with clear and vivid color tone on a recording medium capable of performing multicolor thermal recording. In particular, recording and erasing are repeatedly performed many times. However, no study has been made yet to minimize the deterioration of the recording characteristics in the case of recording, or to maintain the recording characteristics equivalent to the initial values even after long-term storage.
そこで、本発明においては、このような従来技術の問題に鑑みて、安定な発消色、コントラストを有し、かつ日常生活においても実用上優れた画像安定性を実現でき、かつ多数回繰り返して記録及び消去を行った後においても優れた記録特性を維持可能な、信頼性の高い可逆性多色記録媒体、及びその製造方法を提供することとした。 Therefore, in the present invention, in view of such problems of the prior art, it is possible to realize stable color development, contrast, and practically excellent image stability in daily life, and it is repeated many times. A highly reliable reversible multicolor recording medium capable of maintaining excellent recording characteristics even after recording and erasing, and a method for manufacturing the same.
本発明の可逆性多色記録媒体は、支持基板の面方向に、可逆的に異なる色調に発色する複数の記録層が、前記支持基板側から、第１の記録層、第２の記録層、・・・、第ｎの記録層となるように、分離・積層形成されてなり、各々の記録層には、少なくとも、電子供与性を有する呈色性化合物と、電子受容性を有する顕・減色剤とが、樹脂中に含有されている粒子径が３μｍ以下の微粒子状の発色組成物と、少なくとも、それぞれ異なる波長域の赤外線を吸収する光−熱変換材料を含有する光−熱変換組成物とが、互いに分離・独立した状態で混合されてなり、前記複数の記録層に含有されている光−熱変換組成物それぞれの吸収波長（λmaxn）が、λmax1＞λmax2＞・・・＞λmaxnの関係にあって、前記光−熱変換組成物が、それぞれ異なる波長域の赤外線を吸収し、発熱することにより、前記呈色性化合物と前記顕・減色剤との間の可逆的反応を起こさせるようになされており、前記発色組成物を構成する樹脂が、その周囲に存する記録層中の樹脂と相溶せず、前記発色組成物が、前記記録層中において分離・独立した状態で存在するものとする。
In the reversible multicolor recording medium of the present invention, a plurality of recording layers that reversibly develop different color tones in the surface direction of the support substrate from the support substrate side, the first recording layer, the second recording layer, ... Separated and laminated so as to form the nth recording layer. Each recording layer has at least a color-forming compound having an electron donating property and a visible / subtractive color having an electron accepting property. A light-heat conversion composition containing a fine particle color-forming composition having a particle diameter of 3 μm or less contained in a resin and a light-heat conversion material that absorbs at least infrared rays in different wavelength ranges. Are mixed in a state of being separated and independent from each other, and the absorption wavelength (λmaxn) of each of the light-heat conversion compositions contained in the plurality of recording layers is λmax1>λmax2>. Each of the light-to-heat conversion compositions has different wavelength ranges. Absorb infrared radiation, by heating, the have been made so as to cause a reversible reaction between the coloring compound and the developing-color reduction agent, the resin constituting the color forming composition comprises at its periphery It is assumed that the coloring composition is incompatible with the resin in the existing recording layer and is present in a separated and independent state in the recording layer .
また、本発明の可逆性多色記録媒体の製造方法においては、上述したような構成の可逆性多色記録媒体を作製する際、電子供与性を有する呈色性化合物と、電子受容性を有する顕・減色剤とを、樹脂中に含有させて発色組成物を作製する工程と、この発色組成物と、光−熱変換組成物とを混合し、前記記録層を成膜する工程とを有し、前記発色組成物を構成する樹脂として、前記発色組成物が、前記記録層中において分離・独立した状態で存在するように当該発色組成物の周囲に存する記録層中の成分と相溶しないものを選定するものとする。
Further, in the method for producing a reversible multicolor recording medium of the present invention, when producing a reversible multicolor recording medium having the above-described configuration, a colorable compound having an electron donating property and an electron accepting property are provided. A step of preparing a coloring composition by adding a developer / color-reducing agent in the resin, and a step of forming the recording layer by mixing the coloring composition and the light-heat conversion composition. In addition, as the resin constituting the coloring composition, the coloring composition is incompatible with the components in the recording layer existing around the coloring composition so that the coloring composition exists in a separated and independent state in the recording layer. A thing shall be selected.
本発明によれば、発色組成物と光−熱変換材料とを分離・独立させた状態で記録層に含有させたので、これらの干渉による特性劣化が回避される。 According to the present invention, since the coloring composition and the light-to-heat conversion material are contained in the recording layer in a separated and independent state, characteristic deterioration due to these interferences is avoided.
本発明によれば、安定な発消色、コントラストを有し、かつ日常生活においても実用上優れた画像安定性を実現でき、かつ優れた繰り返し特性、及び保存特性を有する信頼性の高い可逆性多色記録媒体が得られた。
また、本発明方法によれば、上記のような繰り返し特性及び保存特性に優れた信頼性の高い可逆性多色記録媒体を極めて簡易なプロセスにより製造することができた。
According to the present invention, it has stable color development / contrast, contrast, can realize practically excellent image stability even in daily life, and has excellent repetitive characteristics and storage characteristics, and is highly reliable and reversible. A multicolor recording medium was obtained.
Further, according to the method of the present invention, a highly reliable reversible multicolor recording medium having excellent repeatability and storage characteristics as described above can be produced by a very simple process.
以下、本発明の実施の形態について図面を参照して具体的に説明するが、本発明は、以下に示す例に限定されるものではない。
図１に本発明の可逆性多色記録媒体の一例の概略断面図を示す。
可逆性多色記録媒体１０は、支持基板１上に、第１の記録層１１、第２の記録層１２及び第３の記録層１３が、それぞれ断熱層１４、１５を介して積層されており、最上層に保護層１６が形成された構成を有している。以下、各層について詳細に説明する。
Hereinafter, embodiments of the present invention will be specifically described with reference to the drawings. However, the present invention is not limited to the following examples.
FIG. 1 shows a schematic sectional view of an example of the reversible multicolor recording medium of the present invention.
In the reversible multicolor recording medium 10, a first recording layer 11, a second recording layer 12, and a third recording layer 13 are laminated on a support substrate 1 via heat insulating layers 14 and 15, respectively. The protective layer 16 is formed as the uppermost layer. Hereinafter, each layer will be described in detail.
支持基板１は、耐熱性に優れ、かつ平面方向の寸法安定性の高い材料であれば従来公知の材料を適宜使用することができる。例えばポリエステル、硬質塩化ビニル等の高分子材料の他、ガラス材料、ステンレス等の金属材料、あるいは紙等の材料から適宜選択できる。但し、オーバーヘッドプロジェクター等の透過用途以外では、支持基板１は最終的に得られる可逆性多色記録媒体１０に対して情報の記録を行った際の視認性の向上を図るため、白色、あるいは金属色を有する可視光に対する反射率の高い材料によって形成することが好ましい。 As the support substrate 1, a conventionally known material can be appropriately used as long as the material has excellent heat resistance and high dimensional stability in the planar direction. For example, it can be appropriately selected from polymer materials such as polyester and hard vinyl chloride, glass materials, metal materials such as stainless steel, and materials such as paper. However, for purposes other than transmission applications such as overhead projectors, the support substrate 1 is white or metallic in order to improve the visibility when information is recorded on the finally obtained reversible multicolor recording medium 10. It is preferably formed of a material having a high reflectance with respect to visible light having a color.
次に、第１〜第３の記録層１１〜１３について説明する。図２に示すように記録層１１〜１３には、発色組成物２１と光−熱変換組成物２２とが含有されている。 Next, the first to third recording layers 11 to 13 will be described. As shown in FIG. 2, the recording layers 11 to 13 contain a coloring composition 21 and a light-heat conversion composition 22.
発色組成物２１は、電子供与性を有する呈色性化合物、例えばロイコ染料、電子受容性を有する顕・減色剤、樹脂、及び各種添加剤等により構成されてなる。
一方、光−熱変換組成物２２は、近赤外線吸収色素よりなる光−熱変換材料、樹脂、及び各種添加剤等により構成されている。
発色組成物２１と光−熱変換組成物２２とは、記録層１１〜１３中において互いに分離・独立した状態で混合されている。
The coloring composition 21 is composed of a color-forming compound having an electron donating property, such as a leuco dye, a color developing / color-reducing agent having an electron accepting property, a resin, and various additives.
On the other hand, the light-heat conversion composition 22 is composed of a light-heat conversion material, a resin, various additives, and the like made of a near-infrared absorbing dye.
The coloring composition 21 and the light-heat conversion composition 22 are mixed in the recording layers 11 to 13 in a separated and independent state.
発色組成物２１を構成する呈色性化合物としては、第１〜第３の記録層１１〜１３が、それぞれ発色する所望の色に応じて所定の呈色性化合物、例えばロイコ染料を用いる。
例えば第１〜第３の記録層１１〜１３においてイエロー、マゼンダ、シアンの三原色を発色するようにすれば、この可逆性多色記録媒体１０全体としてフルカラー画像の形成が可能になる。ロイコ染料としては、既存の感圧紙、感熱紙用染料等を適用することができる。
また、顕・減色剤としては、従来これらに用いられている長鎖アルキル基を有する有機酸（特開平５−１２４３６０号公報、特開平７−１０８７６１号公報、特開平７−１８８２９４号公報、特開２００１−１０５７３３号公報、特開２００１−１１３８２９号公報等に記載）等を適用することができる。
As the color forming compound constituting the color forming composition 21, a predetermined color forming compound, for example, a leuco dye, is used according to a desired color that the first to third recording layers 11 to 13 respectively develop.
For example, if the three primary colors of yellow, magenta, and cyan are developed in the first to third recording layers 11 to 13, a full color image can be formed as the entire reversible multicolor recording medium 10. As the leuco dye, existing pressure-sensitive paper, thermal paper dye, and the like can be applied.
Further, as the developer / color-reducing agent, organic acids having a long-chain alkyl group conventionally used in these (JP-A-5-124360, JP-A-7-108761, JP-A-7-188294, JP 2001-105733 A, JP 2001-113829 A, etc.) can be applied.
発色組成物２１を形成する樹脂としては、例えばポリ塩化ビニル、ポリ酢酸ビニル、塩化ビニル−酢酸ビニル共重合体、エチルセルロース、ポリスチレン、スチレン系共重合体、フェノキシ樹脂、ポリエステル、芳香族ポリエステル、ポリウレタン、ポリカーボネート、ポリアクリル酸エステル、ポリメタクリル酸エステル、アクリル酸系共重合体、マレイン酸系重合体、ポリビニルアルコール、変性ポリビニルアルコール、ヒドロキシエチルセルロース、カルボキシメチルセルロース、デンプン等が挙げられる。これらの樹脂に必要に応じて紫外線吸収剤、酸化防止剤、光安定剤等の各種添加剤を併用してもよい。 Examples of the resin forming the color forming composition 21 include polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrene copolymer, phenoxy resin, polyester, aromatic polyester, polyurethane, Examples include polycarbonate, polyacrylic acid ester, polymethacrylic acid ester, acrylic acid copolymer, maleic acid polymer, polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, and starch. If necessary, these resins may be used in combination with various additives such as an ultraviolet absorber, an antioxidant, and a light stabilizer.
光−熱変換組成物２２は、第１〜第３の記録層１１〜１３の各層において、それぞれ異なる波長域に吸収をもつ光−熱変換材料、樹脂ポリマー、及び各種添加剤等により構成されている。例えば、第１〜第３の記録層１１〜１３において、異なる波長の赤外線（図１中λ1、λ2、λ3）を吸収して発熱する光−熱変換材料が含有されているものとする。 The light-to-heat conversion composition 22 is composed of a light-to-heat conversion material, a resin polymer, and various additives having absorption in different wavelength ranges in each of the first to third recording layers 11 to 13. Yes. For example, the first to third recording layers 11 to 13 contain light-to-heat conversion materials that generate heat by absorbing infrared rays having different wavelengths (λ 1 , λ 2 , λ 3 in FIG. 1). To do.
光−熱変換組成物２２を構成する光−熱変換材料としては、例えば、可視波長域にほとんど吸収がない近赤外線吸収色素として一般的に用いられる、金属錯体系色素、ジイモニウム塩系色素、アミニウム塩系色素、イミニウム塩系色素、ポリメチン系色素等を適用できる。
さらに、任意の記録層のみを発熱させるために、これら色素は光吸収帯が狭く、互いに重なり合わない材料の組み合わせを選択するのが好ましく、この理由から支持基板に最も近い第１の記録層１１を除いては、シアニン、スクアリリウム、クロコニウム系等のポリメチン系色素、またはフタロシアニン、ナフタロシアニン系色素を主成分として用いることにより色かぶりを効果的に防止できる。
Examples of the light-heat conversion material constituting the light-heat conversion composition 22 include metal complex dyes, diimonium salt dyes, and aminiums that are generally used as near-infrared absorbing dyes that hardly absorb in the visible wavelength range. A salt dye, an iminium salt dye, a polymethine dye, or the like can be applied.
Further, in order to generate heat only in an arbitrary recording layer, it is preferable to select a combination of materials having a narrow light absorption band for these dyes and not overlapping each other. For this reason, the first recording layer 11 closest to the support substrate is selected. Except for, a color cast can be effectively prevented by using a polymethine dye such as cyanine, squarylium, croconium or the like, or a phthalocyanine or naphthalocyanine dye as a main component.
また、上記光−熱変換材料として、ポリメチン系色素を用いる場合には、特にこれら色素の劣化を防ぐための添加剤を含有させることが好ましい。添加剤としては、一般的に使用されている、金属錯体系色素、ジイモニウム塩系色素、アミニウム塩系色素、イミニウム塩系色素等を適用できる。さらには、任意の光−熱変換材料のみを発熱させるために、光吸収帯が狭く、互いに重なり合わない材料の組み合わせを選択することが好ましい。 Moreover, when using a polymethine pigment | dye as said light-heat conversion material, it is preferable to contain the additive for preventing deterioration of these pigment | dyes especially. As the additive, generally used metal complex dyes, diimonium salt dyes, aminium salt dyes, iminium salt dyes and the like can be applied. Furthermore, in order to generate heat only in an arbitrary light-heat conversion material, it is preferable to select a combination of materials having a narrow light absorption band and not overlapping each other.
更に、本発明の可逆性多色記録媒体において、支持基板１側からの積層順として、第１の記録層、第２の記録層、・・・、第ｎの記録層とするとき、光−熱変換組成物２２の吸収波長（λmaxn）は、λmax1＞λmax2＞・・・＞λmaxnの関係を有しているものとする。
これは、一般的にフタロシアニン系色素、ナフタロシアニン系色素、シアニン系色素、スクアリリウム系色素、クロコニウム系色素等は、吸収ピークより長波長側の吸収帯は非常に狭いため、本発明のような積層構造を有する可逆性多色記録媒体においては、記録層の下層ほど長波長に吸収ピークを有するように層構成を設定することにより、上層でのレーザー光の吸収及び下層へのレーザー光の透過等を低減できるからである。その結果、記録感度の向上が図られ、色かぶりを効果的に低減化できる。
Furthermore, in the reversible multicolor recording medium of the present invention, when the first recording layer, the second recording layer,. The absorption wavelength (λmaxn) of the heat conversion composition 22 is assumed to have a relationship of λmax1>λmax2>.
In general, phthalocyanine dyes, naphthalocyanine dyes, cyanine dyes, squarylium dyes, croconium dyes, and the like have a very narrow absorption band on the long wavelength side from the absorption peak, and thus are laminated as in the present invention. In a reversible multicolor recording medium having a structure, by setting the layer structure so that the lower layer of the recording layer has an absorption peak at a longer wavelength, absorption of the laser beam in the upper layer and transmission of the laser beam to the lower layer, etc. It is because it can reduce. As a result, the recording sensitivity can be improved and the color cast can be effectively reduced.
光−熱変換組成物２２を構成する樹脂としては、例えばポリ塩化ビニル、ポリ酢酸ビニル、塩化ビニル−酢酸ビニル共重合体、エチルセルロース、ポリスチレン、スチレン系共重合体、フェノキシ樹脂、ポリエステル、芳香族ポリエステル、ポリウレタン、ポリカーボネート、ポリアクリル酸エステル、ポリメタクリル酸エステル、アクリル酸系共重合体、マレイン酸系重合体、ポリビニルアルコール、変性ポリビニルアルコール、ヒドロキシエチルセルロース、カルボキシメチルセルロース、デンプン等が挙げられる。 Examples of the resin constituting the light-heat conversion composition 22 include polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrene copolymer, phenoxy resin, polyester, and aromatic polyester. , Polyurethane, polycarbonate, polyacrylic acid ester, polymethacrylic acid ester, acrylic acid copolymer, maleic acid polymer, polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, starch and the like.
次に、記録層１１〜１３を構成する発色組成物２１と光−熱変換組成物２２との、記録層中における状態について説明する。
図２に示すように、発色組成物２１と光−熱変換組成物２２とは記録層中において互いに分離・独立した状態で混合されている。
このようにするためには、例えば、発色組成物２１形成用の樹脂として水溶性ポリマーを使用する場合に、光−熱変換組成物２２形成用の樹脂として非水溶性ポリマーを使用したり、あるいは、発色組成物２１形成用の樹脂として非水溶性ポリマーを使用する場合に、光−熱変換組成物２２形成用の樹脂として水溶性ポリマーや熱硬化あるいは紫外線硬化等の処理を施した非水溶性ポリマーを使用したりすることにより、双方の樹脂が相溶し合わないようにする方法が挙げられる。
その他としては、光−熱変換組成物２２形成用の樹脂を溶解させるために使用する溶剤として、発色組成物２１形成用の樹脂を溶解しない材料を選定する方法も挙げられる。
Next, the state in the recording layer of the coloring composition 21 and the light-heat conversion composition 22 constituting the recording layers 11 to 13 will be described.
As shown in FIG. 2, the color forming composition 21 and the light-heat conversion composition 22 are mixed and separated from each other in the recording layer.
In order to do this, for example, when a water-soluble polymer is used as the resin for forming the coloring composition 21, a water-insoluble polymer is used as the resin for forming the light-heat conversion composition 22, or When a water-insoluble polymer is used as the resin for forming the color forming composition 21, a water-insoluble polymer subjected to a treatment such as a water-soluble polymer or heat curing or ultraviolet curing as the resin for forming the light-heat conversion composition 22 is used. For example, a method of preventing both resins from being compatible with each other by using a polymer may be used.
Other examples include a method of selecting a material that does not dissolve the resin for forming the coloring composition 21 as a solvent used for dissolving the resin for forming the light-heat conversion composition 22.
また、上述したような方法に限定されず、発色組成物２１を、周囲の光−熱変換組成物２２形成用の樹脂と相溶しない材料よりなるバリア層（図示せず）により被覆し、発色組成物２１が、記録層１１〜１３中において分離・独立した状態で存在するようにしてもよい。 Further, the present invention is not limited to the above-described method, and the coloring composition 21 is covered with a barrier layer (not shown) made of a material that is incompatible with the surrounding resin for forming the light-to-heat conversion composition 22, and coloring is performed. The composition 21 may exist in the recording layers 11 to 13 in a separated and independent state.
記録層１１〜１３中において、発色組成物２１と光−熱変換組成物２２をそれぞれ構成する樹脂が相溶しあう場合、記録層作製プロセスにおいて、両組成物が均一に混合してしまい、顕・減色剤及びロイコ染料が光−熱変換材料の劣化を加速させたり、光−熱変換材料がロイコ染料の劣化を加速させたりし、繰り返し特性あるいは保存特性などの信頼性に影響を及ぼす。このことから、本発明においては、発色組成物２１と光−熱変換組成物２２とは、互いに分離させた状態で記録層１１〜１３中に混合されるものとした。 In the recording layers 11 to 13, when the resins constituting the color forming composition 21 and the light-heat conversion composition 22 are compatible with each other, both compositions are uniformly mixed in the recording layer manufacturing process. The color-reducing agent and the leuco dye accelerate the deterioration of the light-heat conversion material, and the light-heat conversion material accelerates the deterioration of the leuco dye, thereby affecting the reliability such as repetition characteristics or storage characteristics. Therefore, in the present invention, the coloring composition 21 and the light-heat conversion composition 22 are mixed in the recording layers 11 to 13 while being separated from each other.
さらにまた、記録層１１〜１３中で、発色組成物２１を、光−熱変換組成物２２が存する領域から分離・独立した状態で存在させるようにするためには、発色組成物２１は、記録層１１〜１３の層厚を考慮しつつ充分に微細化する必要がある。
この微細化方法としては、粉砕機、ボールミルによる方法やスプレー乾燥法等が挙げられ、何ら制限はなく、記録感度の向上、あるいは記録画像の高精彩化のためには粒子径が８μｍ以下であることが好ましく、更には３μｍ以下であることが望ましい。
Furthermore, in order to allow the coloring composition 21 to exist in the recording layers 11 to 13 in a state separated and independent from the region where the light-heat conversion composition 22 exists, the coloring composition 21 is recorded on the recording layers 11 to 13. It is necessary to reduce the thickness sufficiently while considering the layer thicknesses of the layers 11 to 13.
Examples of the miniaturization method include a pulverizer, a ball mill method, a spray drying method, and the like. There is no limitation, and the particle diameter is 8 μm or less for improving the recording sensitivity or enhancing the recording image. It is preferable that it is 3 μm or less.
次に、本発明の可逆性多色記録媒体１０の製造方法について、その要部である記録層１１〜１３の成膜方法に関し説明する。
先ず、呈色性化合物、例えばロイコ染料、顕・減色剤、及び各種添加剤等を、任意の溶剤を用いて樹脂ポリマー中に溶解させ、その後溶剤を揮発させ、上述したような微細化処理を行い、微細粒子状の発色組成物２１を作製する。
続いて、光−熱変換材料、及び各種添加剤等を任意の溶剤を用いて樹脂ポリマー中に溶解させた塗料状の光−熱変換組成物２２を作製する。
そして、発色組成物２１と光−熱変換組成物２２とを、所定の溶剤を用いて混合して記録層形成用塗料とし、これを所望の位置に塗布することによって記録層１１〜１３を成膜する。
なお、このとき、発色組成物２１を構成する樹脂ポリマーとして、発色組成物２１の周囲に存する記録層１１〜１３中の成分と相溶しないものを選定することが望ましいが、上述したように、発色組成物２１を、周囲の光−熱変換組成物２２形成用の樹脂と相溶しない材料よりなるバリア層（図示せず）により被覆された構成とする場合には、任意の材料を選定することができる。
Next, the manufacturing method of the reversible multicolor recording medium 10 of the present invention will be described with respect to the film forming method of the recording layers 11 to 13 as the main part.
First, a color developing compound such as a leuco dye, a developer / color-reducing agent, and various additives are dissolved in a resin polymer using an arbitrary solvent, and then the solvent is volatilized, and the above-described refinement treatment is performed. The fine color coloring composition 21 is produced.
Subsequently, a paint-like light-heat conversion composition 22 in which a light-heat conversion material, various additives, and the like are dissolved in a resin polymer using an arbitrary solvent is prepared.
Then, the coloring layer 21 and the light-heat conversion composition 22 are mixed using a predetermined solvent to form a recording layer-forming coating material, which is applied to a desired position, thereby forming the recording layers 11 to 13. Film.
At this time, it is desirable to select a resin polymer constituting the coloring composition 21 that is incompatible with the components in the recording layers 11 to 13 existing around the coloring composition 21, as described above. When the coloring composition 21 is covered with a barrier layer (not shown) made of a material that is incompatible with the surrounding resin for forming the light-to-heat conversion composition 22, an arbitrary material is selected. be able to.
なお、発色組成物２１は、記録層形成用塗料の溶剤には溶解せず、光−熱変換組成物２２を構成する材料と共に同時混合可能であり、図２に示したような構成の他、例えば、特開２００１−１６４５号公報に記載されているように、発色組成物２１と光−熱変換組成物２２とをそれぞれ独立に積層させた多層構成の記録層とすることもできる。 The coloring composition 21 does not dissolve in the solvent for the recording layer forming paint, and can be mixed simultaneously with the material constituting the light-heat conversion composition 22. In addition to the configuration shown in FIG. For example, as described in Japanese Patent Application Laid-Open No. 2001-1645, a recording layer having a multilayer structure in which the coloring composition 21 and the light-heat conversion composition 22 are laminated independently can be used.
記録層１１〜１３は、それぞれ膜厚１〜２０μｍ程度に形成することが望ましく、更には２〜１０μｍ程度が望ましい。これらの膜厚が１μｍ未満であると充分な発色濃度が得られず、１５μｍを超えた膜厚になると記録層１１〜１３の熱容量が大きくなり、発色性や消色性が劣化するためである。 The recording layers 11 to 13 are preferably formed to a thickness of about 1 to 20 μm, and more preferably about 2 to 10 μm. If these film thicknesses are less than 1 μm, a sufficient color density cannot be obtained, and if the film thickness exceeds 15 μm, the heat capacity of the recording layers 11 to 13 increases, and the color developability and decoloring properties deteriorate. .
第１の記録層１１と第２の記録層１２との間、第２の記録層１２と第３の記録層１３との間には、それぞれ透光性の断熱層１４、１５を形成することが望ましい。これによって隣接する記録層からの熱伝導が回避され、いわゆる色かぶりの発生を防止することができる。 Translucent heat insulating layers 14 and 15 are formed between the first recording layer 11 and the second recording layer 12 and between the second recording layer 12 and the third recording layer 13, respectively. Is desirable. As a result, heat conduction from the adjacent recording layer is avoided, and so-called color fogging can be prevented.
断熱層１４、１５は、従来公知の透光性のポリマーを用いて形成することができる。例えば、ポリ塩化ビニル、ポリ酢酸ビニル、塩化ビニル−酢酸ビニル共重合体、エチルセルロース、ポリスチレン、スチレン系共重合体、フェノキシ樹脂、ポリエステル、芳香族ポリエステル、ポリウレタン、ポリカーボネート、ポリアクリル酸エステル、ポリメタクリル酸エステル、アクリル酸系共重合体、マレイン酸系重合体、ポリビニルアルコール、変性ポリビニルアルコール、ヒドロキシエチルセルロース、カルボキシメチルセルロース、デンプン等が挙げられる。
また、断熱層１４、１５は透光性の無機膜を用いて形成することもできる。例えば、多孔質のシリカ、アルミナ、チタニア、カーボン、またはこれらの複合体等を用いると、熱伝導率が低くなり断熱効果が高く好ましい。これらは液層から膜形成できるゾル−ゲル法によって形成することができる。
断熱層１４、１５は、膜厚３〜１００μｍ程度に形成することが望ましく、さらには５〜５０μｍ程度に形成することが好ましい。これらの膜厚が薄すぎると充分な断熱効果が得られず、膜厚が厚すぎると、後述する記録方法において記録媒体全体を均一加熱する際に熱伝導性が劣化したり、透光性が低下したりするためである。
The heat insulation layers 14 and 15 can be formed using a conventionally known translucent polymer. For example, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrene copolymer, phenoxy resin, polyester, aromatic polyester, polyurethane, polycarbonate, polyacrylic acid ester, polymethacrylic acid Examples include esters, acrylic acid copolymers, maleic acid polymers, polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, and starch.
Moreover, the heat insulation layers 14 and 15 can also be formed using a translucent inorganic film. For example, when porous silica, alumina, titania, carbon, or a composite thereof is used, the thermal conductivity is lowered and the heat insulating effect is high, which is preferable. These can be formed by a sol-gel method capable of forming a film from a liquid layer.
The heat insulating layers 14 and 15 are preferably formed to a thickness of about 3 to 100 μm, and more preferably about 5 to 50 μm. If these film thicknesses are too thin, a sufficient heat insulating effect cannot be obtained, and if the film thickness is too thick, the thermal conductivity deteriorates when the entire recording medium is uniformly heated in the recording method to be described later, or the translucency is low. It is because it falls.
保護層１６は、従来公知の紫外線硬化性樹脂や熱硬化性樹脂を用いて形成することができ、膜厚は０．１〜２０μｍ、さらには０．５〜５μｍ程度とすることが望ましい。
保護層１６の膜厚が０．１μｍ未満であると充分な保護効果が得られず、一方、２０μｍを超えた膜厚にすると熱伝導性が悪化するという不都合を生じるためである。
The protective layer 16 can be formed using a conventionally known ultraviolet curable resin or thermosetting resin, and the film thickness is preferably about 0.1 to 20 μm, more preferably about 0.5 to 5 μm.
This is because if the film thickness of the protective layer 16 is less than 0.1 μm, a sufficient protective effect cannot be obtained, whereas if the film thickness exceeds 20 μm, there is a disadvantage that the thermal conductivity deteriorates.
次に、可逆性多色記録媒体１０を用いた多色記録を行う原理について説明する。
先ず、多色記録の第１の原理を説明する。
図１に示した可逆性多色記録媒体１０を、各記録層が消色する程度の温度、例えば１２０℃程度の温度で全面加熱し、次に冷却し、第１〜第３の記録層１１〜１３を予め消色状態にしておく。すなわちこの状態においては、支持基板１の色が露出している状態となっているものとする。
次に、可逆性多色記録媒体１０の任意の部分に、波長及び出力を任意に選択した赤外線を半導体レーザー等により照射する。
例えば第１の記録層１１を発色させる場合には、波長λ1の赤外線を第１の記録層１１が発色温度に達する程度のエネルギーで照射し、光−熱変換材料を発熱させて、呈色化合物と顕・減色剤との間の反応を起こさせ、照射部分を発色させる。
同様に、第２の記録層１２及び第３の記録層１３についても、それぞれ波長λ2、λ3の赤外線を発色温度に達する程度のエネルギーを照射してそれぞれの光−熱変換材料を発熱させて照射部分を発色させる。
上述したように、記録媒体１０の任意の部分を発色させることができ、フルカラー画像形成や種々の情報の記録が可能となる。
Next, the principle of performing multicolor recording using the reversible multicolor recording medium 10 will be described.
First, the first principle of multicolor recording will be described.
The reversible multicolor recording medium 10 shown in FIG. 1 is entirely heated at a temperature at which each recording layer is decolored, for example, at a temperature of about 120 ° C., then cooled, and the first to third recording layers 11. ˜13 are set in a decolored state in advance. That is, in this state, it is assumed that the color of the support substrate 1 is exposed.
Next, an arbitrary part of the reversible multicolor recording medium 10 is irradiated with infrared light having an arbitrarily selected wavelength and output by a semiconductor laser or the like.
For example, when the first recording layer 11 is colored, an infrared ray having a wavelength λ 1 is irradiated with energy that the first recording layer 11 reaches the coloring temperature, and the light-to-heat conversion material is heated so that the color is generated. A reaction between the compound and the developer / color-reducing agent is caused, and the irradiated portion is colored.
Similarly, the second recording layer 12 and the third recording layer 13 are also irradiated with energy having a wavelength of λ 2 and λ 3 to reach the coloring temperature, respectively, so that each light-heat conversion material generates heat. To color the irradiated area.
As described above, an arbitrary portion of the recording medium 10 can be colored, and a full-color image can be formed and various information can be recorded.
また、上記のようにして発色させた所定の記録層において、さらに任意の波長の赤外線を、各記録層１１〜１３が消色温度に達する程度のエネルギーで照射し、光−熱変換材料を発熱させて、呈色化合物と顕・減色剤との間で消色反応を起こさせることによって、記録の消去を行うことができる。 Further, in the predetermined recording layer colored as described above, an infrared ray having an arbitrary wavelength is further irradiated with energy at which each recording layer 11 to 13 reaches the decoloring temperature, and the light-heat conversion material generates heat. Thus, the recording can be erased by causing a decoloring reaction between the coloring compound and the developer / color-reducing agent.
また、上述のようにして一部を着色化させた可逆性多色記録媒体１０の全体を、全ての記録層が消色する程度の温度、例えば１２０℃で一様に加熱することによって、記録情報や画像を消去することができ、その後上述したような操作を行うことにより繰り返し記録が可能である。 Further, the entire reversible multicolor recording medium 10 partially colored as described above is uniformly heated at a temperature at which all the recording layers are decolored, for example, 120 ° C. Information and images can be erased, and recording can be repeated by performing the operations described above.
次に、多色記録の第２の原理を説明する。
先ず、図１に示した可逆性多色記録媒体１０を、各記録層１１〜１３が発色する程度の温度、例えば２００℃程度の高温で全面加熱し、次に冷却し、第１〜第３の記録層１１〜１３を全て予め発色状態にしておく。
次に、可逆性多色記録媒体１０の任意の部分に、波長及び出力を任意に選択した赤外線を半導体レーザー等により照射する。
例えば第１の記録層１１を消色させる場合には、波長λ1の赤外線を第１の記録層１１が消色する程度のエネルギーで照射し、光−熱変換材料を発熱させて記録層１１を消色状態とする。
同様に、第２の記録層１２及び第３の記録層１３についても、それぞれ波長λ2、λ3の赤外線を、消色温度に達する程度のエネルギーで照射してそれぞれの光−熱変換材料を発熱させて照射部分を消色させることができる。
上述のようにすることによって、可逆性多色記録媒体１０の任意の部分を消色させることができ、フルカラー画像形成や種々の情報の記録が可能となる。
Next, the second principle of multicolor recording will be described.
First, the reversible multicolor recording medium 10 shown in FIG. 1 is heated on the entire surface at a temperature at which each of the recording layers 11 to 13 develops color, for example, at a high temperature of about 200 ° C., and then cooled. All of the recording layers 11 to 13 are colored in advance.
Next, an arbitrary part of the reversible multicolor recording medium 10 is irradiated with infrared light having an arbitrarily selected wavelength and output by a semiconductor laser or the like.
For example, when the first recording layer 11 is decolored, the recording layer 11 is irradiated with infrared light having a wavelength λ 1 with such energy that the first recording layer 11 is decolored to generate heat. Is decolored.
Similarly, the second recording layer 12 and the third recording layer 13 are each irradiated with infrared rays having wavelengths λ 2 and λ 3 with energy to reach the decoloring temperature, and the respective light-to-heat conversion materials are applied. The irradiated portion can be decolored by generating heat.
As described above, an arbitrary portion of the reversible multicolor recording medium 10 can be erased, and a full-color image can be formed and various information can be recorded.
上記のようにして消色させた各記録層１１〜１３において、さらに任意の波長の赤外線を、各記録層１１〜１３が発色温度に達する程度のエネルギーで照射し、光−熱変換材料を発熱させて、呈色化合物と顕・減色剤との間の発色反応を起こさせることによって、記録層の任意の部分を発色化させることができる。 In each of the recording layers 11 to 13 decolorized as described above, an infrared ray having an arbitrary wavelength is further irradiated with energy at which the recording layers 11 to 13 reach the coloring temperature, and the light-heat conversion material generates heat. Thus, by causing a color development reaction between the color forming compound and the developer / subtractor, any portion of the recording layer can be colored.
更に、上述のようにして一部を消色化、あるいは発色化させた可逆性多色記録媒体１０の全体を、全ての記録層が着色する程度の温度、例えば２００℃で一様に加熱し、次いで冷却することによって、記録情報や画像を消去することができ、上述した操作を行うことにより、再度繰り返し記録が可能となる。 Further, the entire reversible multicolor recording medium 10 partially erased or developed as described above is uniformly heated at a temperature at which all the recording layers are colored, for example, 200 ° C. Then, the recording information and the image can be erased by cooling, and the recording can be repeated again by performing the operation described above.
本発明の可逆性多色記録媒体１０に対して、上記第１の原理、及び第２の原理に示した記録方法のうち、いずれの方法を適用するかは、記録層の特性、記録光源の性能に合わせて適宜選択する。
例えば、記録層を高温で発色してそれ以下の温度で消色する、いわゆるポジ型の層として形成してもよく、高温で消色してそれ以下の温度で発色する、いわゆるネガ型の層として形成してもよい（例えば特開平８−１９７８５３号公報）。
Which of the recording methods shown in the first principle and the second principle is applied to the reversible multicolor recording medium 10 of the present invention depends on the characteristics of the recording layer and the recording light source. Select appropriately according to the performance.
For example, the recording layer may be formed as a so-called positive type layer that develops color at a high temperature and erases at a temperature lower than that, or a so-called negative type layer that erases at a high temperature and develops color at a temperature below that. (For example, JP-A-8-197853).
次に、本発明の可逆性多色記録媒体について、具体的な実施例及び比較例を挙げて説明するが、本発明は以下に示す例に限定されるものではない。 Next, the reversible multicolor recording medium of the present invention will be described with specific examples and comparative examples, but the present invention is not limited to the examples shown below.
〔実施例１〕
下記においては、図１に示したように、支持基板１上に第１の記録層１１、断熱層１４、第２の記録層１２、断熱層１５、第３の記録層１３、及び保護層１６が順次積層された、三層の記録層を有する可逆性多色記録媒体を作製する。
[Example 1]
In the following, as shown in FIG. 1, the first recording layer 11, the heat insulating layer 14, the second recording layer 12, the heat insulating layer 15, the third recording layer 13, and the protective layer 16 are formed on the support substrate 1. A reversible multicolor recording medium having three recording layers laminated sequentially is manufactured.
支持基板１として、厚さ１ｍｍの白色のポリエチレンテレフタレート基板を用意した。
次に第１の記録層１１を形成した。すなわち支持基板１上に下記材料を含有する塗料をペイントシェイカーを用いて１時間分散させた後、ワイヤーバーで塗布し、１１０℃にて５分間加熱乾燥処理を施し、シアンに発色させることのできる記録層を膜厚８μｍに形成した。
第１の記録層１１に含有する光−熱変換組成物の波長９４０ｎｍの光における吸光度は１．０であった。
A white polyethylene terephthalate substrate having a thickness of 1 mm was prepared as the support substrate 1.
Next, the first recording layer 11 was formed. That is, a paint containing the following materials can be dispersed on the support substrate 1 using a paint shaker for 1 hour, and then applied with a wire bar and heat-dried at 110 ° C. for 5 minutes to develop cyan. The recording layer was formed to a thickness of 8 μm.
The absorbance of the light-heat conversion composition contained in the first recording layer 11 in light having a wavelength of 940 nm was 1.0.
（第１の記録層用の発色組成物）
ロイコ染料（下記化学式（１）に示す物質）：２重量部
(Coloring composition for first recording layer)
Leuco dye (substance shown in chemical formula (1) below): 2 parts by weight
顕・減色剤（下記化学式（２）に示す物質）：４重量部 Developer / color-reducing agent (substance shown in chemical formula (2) below): 4 parts by weight
塩化ビニル−酢酸ビニル−ビニルアルコール共重合体：５重量部
（塩化ビニル９１％、酢酸ビニル３％、ビニルアルコール６％）
イソシアネート化合物：１重量部
（日本ポリウレタン社製、コロネートＬ）
メチルエチルケトン（ＭＥＫ）：９１重量部
上記材料をペイントシェイカーを用いて２４時間分散させ、次に４８時間、８０℃のオーブン中にて保存処理を行い充分に熱硬化させ、これをボールミルにより平均粒径１μｍに粉砕し、微粒子状とした。
Vinyl chloride-vinyl acetate-vinyl alcohol copolymer: 5 parts by weight (91% vinyl chloride, 3% vinyl acetate, 6% vinyl alcohol)
Isocyanate compound: 1 part by weight (manufactured by Nippon Polyurethane, Coronate L)
Methyl ethyl ketone (MEK): 91 parts by weight The above materials were dispersed using a paint shaker for 24 hours, then stored in an oven at 80 ° C. for 48 hours and sufficiently heat-cured. It was pulverized to 1 μm to form fine particles.
（第１の記録層用の光−熱変換組成物）
シアニン系赤外吸収色素：０．１９重量部
（Ｈ．Ｗ．ＳＡＮＤＳ社製、ＳＤＡ７７７５、記録層中での吸収波長ピーク：９３３ｎｍ）
一重項酸素失活剤：０．１０重量部
（林原生物化学研究所製、ＮＫＸ−１１９９）
塩化ビニル−酢酸ビニル共重合体：１０重量部
（塩化ビニル９０％、酢酸ビニル１０％、平均分子量（Ｍ．Ｗ．）１１５０００）
メチルエチルケトン（ＭＥＫ）：９１重量部
(Light-heat conversion composition for the first recording layer)
Cyanine-based infrared absorbing dye: 0.19 parts by weight (manufactured by HW SANDS, SDA7775, absorption wavelength peak in recording layer: 933 nm)
Singlet oxygen quenching agent: 0.10 parts by weight (manufactured by Hayashibara Biochemical Research Institute, NKX-1199)
Vinyl chloride-vinyl acetate copolymer: 10 parts by weight (90% vinyl chloride, 10% vinyl acetate, average molecular weight (M.W.) 115000)
Methyl ethyl ketone (MEK): 91 parts by weight
上述のようにして成膜した第１の記録層１１上に、ポリビニルアルコール水溶液を塗布、乾燥して膜厚２０μｍの断熱層１４を形成した。 On the first recording layer 11 formed as described above, an aqueous polyvinyl alcohol solution was applied and dried to form a heat insulating layer 14 having a thickness of 20 μm.
断熱層１４上に、第２の記録層１２を形成した。すなわち下記材料を含有する塗料をペイントシェイカーを用いて１時間分散させた後、塗料をワイヤーバーで塗布し、１１０℃にて５分間加熱乾燥処理を施し、マゼンダに発色させることのできる記録層を膜厚８μｍに形成した。
第２の記録層１２に含有する光−熱変換組成物の波長８６０ｎｍの光における吸光度は１．０であった。
A second recording layer 12 was formed on the heat insulating layer 14. That is, after a coating material containing the following materials is dispersed for 1 hour using a paint shaker, the coating layer is applied with a wire bar and subjected to a heat drying treatment at 110 ° C. for 5 minutes to form a recording layer capable of coloring magenta. The film thickness was 8 μm.
The absorbance of the light-heat conversion composition contained in the second recording layer 12 in light having a wavelength of 860 nm was 1.0.
（第２の記録層用の発色組成物）
ロイコ染料（下記化学式（３）に示す物質）：１．８重量部
(Coloring composition for second recording layer)
Leuco dye (substance shown in chemical formula (3) below): 1.8 parts by weight
顕・減色剤（下記化学式（２）に示す物質）：４重量部 Developer / color-reducing agent (substance shown in chemical formula (2) below): 4 parts by weight
塩化ビニル−酢酸ビニル−ビニルアルコール重合体：５重量部
（塩化ビニル９１％、酢酸ビニル３％、ビニルアルコール６％）
イソシアネート化合物：１重量部
（日本ポリウレタン社製、コロネートＬ）
メチルエチルケトン（ＭＥＫ）：９１重量部
上記材料をペイントシェイカーを用いて２４時間分散させ、次に４８時間、８０℃のオーブン中にて保存処理を行い充分に熱硬化させ、これをボールミルにより平均粒径１μｍに粉砕し、微粒子状とした。
Vinyl chloride-vinyl acetate-vinyl alcohol polymer: 5 parts by weight (91% vinyl chloride, 3% vinyl acetate, 6% vinyl alcohol)
Isocyanate compound: 1 part by weight (manufactured by Nippon Polyurethane, Coronate L)
Methyl ethyl ketone (MEK): 91 parts by weight The above materials were dispersed using a paint shaker for 24 hours, then stored in an oven at 80 ° C. for 48 hours and sufficiently heat-cured. It was pulverized to 1 μm to form fine particles.
（第２の記録層用の光−熱変換組成物）
シアニン系赤外吸収色素：０．１２重量部
（Ｈ．Ｗ．ＳＡＮＤＳ社製、ＳＤＡ５６８８、記録層中での吸収波長ピーク８６１ｎｍ）
一重項酸素失活剤：０．１０重量部
（住友精化製、ＥＳＴ５−Ｎｉ）
塩化ビニル−酢酸ビニル共重合体：５重量部
（塩化ビニル９０％、酢酸ビニル１０％、平均分子量（Ｍ．Ｗ．）１１５０００）
メチルエチルケトン（ＭＥＫ）：９１重量部
(Light-to-heat conversion composition for second recording layer)
Cyanine-based infrared absorbing dye: 0.12 parts by weight (manufactured by HW SANDS, SDA5688, absorption wavelength peak in recording layer 861 nm)
Singlet oxygen quencher: 0.10 parts by weight (Sumitomo Seika, EST5-Ni)
Vinyl chloride-vinyl acetate copolymer: 5 parts by weight (90% vinyl chloride, 10% vinyl acetate, average molecular weight (M.W.) 115000)
Methyl ethyl ketone (MEK): 91 parts by weight
上述のようにして成膜した第２の記録層１２上に、ポリビニルアルコール水溶液を塗布、乾燥して膜厚２０μｍの断熱層１５を形成した。 On the second recording layer 12 formed as described above, an aqueous polyvinyl alcohol solution was applied and dried to form a heat insulating layer 15 having a thickness of 20 μm.
断熱層１５上に、第３の記録層１３を形成した。
下記材料を含有する塗料をペイントシェイカーを用いて１時間分散させた後、塗料をワイヤーバーで塗布し、１１０℃にて５分間加熱乾燥処理を施し、イエローに発色させることのできる記録層を膜厚８μｍに形成した。
第３の記録層１３に含有する光−熱変換組成物の波長８００ｎｍの光における吸光度は１．０であった。
A third recording layer 13 was formed on the heat insulating layer 15.
After a paint containing the following materials is dispersed for 1 hour using a paint shaker, the paint is applied with a wire bar and heat-dried at 110 ° C. for 5 minutes to form a recording layer capable of developing yellow. The thickness was 8 μm.
The absorbance of the light-heat conversion composition contained in the third recording layer 13 in light having a wavelength of 800 nm was 1.0.
（第３の記録層用の発色組成物）
ロイコ染料（下記化学式（４）に示す物質）：１．３重量部
(Coloring composition for the third recording layer)
Leuco dye (substance shown in chemical formula (4) below): 1.3 parts by weight
顕・減色剤（下記化学式（２）に示す物質）：４重量部 Developer / color-reducing agent (substance shown in chemical formula (2) below): 4 parts by weight
塩化ビニル−酢酸ビニル−ビニルアルコール重合体：５重量部
（塩化ビニル９１％、酢酸ビニル３％、ビニルアルコール６％）
イソシアネート化合物：１重量部
（日本ポリウレタン社製、コロネートＬ）
メチルエチルケトン（ＭＥＫ）：１４０重量部
上記材料をペイントシェイカーを用いて２４時間分散させ、次に４８時間、８０℃のオーブン中にて保存処理を行い充分に熱硬化させ、これをボールミルにより平均粒径２μｍに粉砕し、微粒子状とした。
Vinyl chloride-vinyl acetate-vinyl alcohol polymer: 5 parts by weight (91% vinyl chloride, 3% vinyl acetate, 6% vinyl alcohol)
Isocyanate compound: 1 part by weight (manufactured by Nippon Polyurethane, Coronate L)
Methyl ethyl ketone (MEK): 140 parts by weight The above materials were dispersed using a paint shaker for 24 hours, then stored in an oven at 80 ° C. for 48 hours and sufficiently heat-cured. It was pulverized to 2 μm to form fine particles.
（第３の記録層用の光−熱変換組成物）
シアニン系赤外吸収色素：０．１０重量部
（日本化薬製、ＣＹ−１０、記録層中での吸収波長ピーク７９８ｎｍ）
一重項酸素失活剤：０．１０重量部
（住友精化製、ＥＳＴ５−Ｎｉ）
塩化ビニル−酢酸ビニル共重合体：５重量部
（塩化ビニル９０％、酢酸ビニル１０％、平均分子量（Ｍ．Ｗ．）１１５０００）
メチルエチルケトン（ＭＥＫ）：９１重量部
(Light-to-heat conversion composition for the third recording layer)
Cyanine infrared absorbing dye: 0.10 parts by weight (manufactured by Nippon Kayaku Co., Ltd., CY-10, absorption wavelength peak in recording layer 798 nm)
Singlet oxygen quencher: 0.10 parts by weight (Sumitomo Seika, EST5-Ni)
Vinyl chloride-vinyl acetate copolymer: 5 parts by weight (90% vinyl chloride, 10% vinyl acetate, average molecular weight (M.W.) 115000)
Methyl ethyl ketone (MEK): 91 parts by weight
上述のようにして成膜した第３の記録層１３上に、紫外線硬化性樹脂を用いて膜厚約２μｍの保護層１６を形成し、可逆性多色記録媒体１０を得た。 On the third recording layer 13 formed as described above, a protective layer 16 having a thickness of about 2 μm was formed using an ultraviolet curable resin to obtain a reversible multicolor recording medium 10.
この可逆性多色記録媒体１０を、１２０℃に加熱したセラミックスバーを用いて一様に加熱し、第１、第２及び第３の記録層１１〜１３を消色状態にしたものをサンプルとした。 The reversible multicolor recording medium 10 is uniformly heated using a ceramic bar heated to 120 ° C., and the first, second and third recording layers 11 to 13 are in a decolored state as a sample. did.
〔実施例２〕
実施例１における、光−熱変換組成物を構成する樹脂ポリマーを、ポリエステルポリオール（ユニチカ製エリーテルＵＥ−３３００）に変更した。
その他の条件は実施例１と同様として、サンプルとなる可逆性多色記録媒体を作製した。
[Example 2]
In Example 1, the resin polymer constituting the light-heat conversion composition was changed to polyester polyol (Eritel UE-3300 manufactured by Unitika).
Other conditions were the same as in Example 1, and a reversible multicolor recording medium as a sample was produced.
〔実施例３〕
実施例１における光−熱変換組成物を構成する樹脂ポリマーを、アクリルポリオール樹脂（三菱レイヨン社製：ＬＲ５０３）に変更した。
その他の条件は実施例１と同様として、サンプルとなる可逆性多色記録媒体を作製した。
Example 3
The resin polymer constituting the light-heat conversion composition in Example 1 was changed to an acrylic polyol resin (manufactured by Mitsubishi Rayon Co., Ltd .: LR503).
Other conditions were the same as in Example 1, and a reversible multicolor recording medium as a sample was produced.
〔実施例４〕
実施例１における光−熱変換組成物を構成する樹脂ポリマーを、ポリビニルアセタール樹脂（積水化学工業社製：ＢＬ−１）に変更した。
その他の条件は実施例１と同様として、サンプルとなる可逆性多色記録媒体を作製した。
Example 4
The resin polymer constituting the light-heat conversion composition in Example 1 was changed to a polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd .: BL-1).
Other conditions were the same as in Example 1, and a reversible multicolor recording medium as a sample was produced.
〔実施例５〕
実施例１において発色組成物に含有させたイソシアネート化合物を、コロネートＨＬ（日本ポリウレタン社製）に変更した。
その他の条件は実施例１と同様として、サンプルとなる可逆性多色記録媒体を作製した。
Example 5
In Example 1, the isocyanate compound contained in the coloring composition was changed to Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.).
Other conditions were the same as in Example 1, and a reversible multicolor recording medium as a sample was produced.
〔実施例６〕
実施例１における、発色組成物を構成する樹脂ポリマーを、ポリビニルアルコールに変更し、溶媒をメチルエチルケトン（ＭＥＫ）から水に変更した。
その他の条件は実施例１と同様として、サンプルとなる可逆性多色記録媒体を作製した。
Example 6
The resin polymer constituting the color forming composition in Example 1 was changed to polyvinyl alcohol, and the solvent was changed from methyl ethyl ketone (MEK) to water.
Other conditions were the same as in Example 1, and a reversible multicolor recording medium as a sample was produced.
〔実施例７〕
実施例１における発色組成物を、ボールミルを用いて平均粒径０．５μｍに微細化した粒子とした。
その他の条件は実施例１と同様として、サンプルとなる可逆性多色記録媒体を作製した。
Example 7
The coloring composition in Example 1 was made into particles refined to an average particle size of 0.5 μm using a ball mill.
Other conditions were the same as in Example 1, and a reversible multicolor recording medium as a sample was produced.
〔実施例８〕
実施例１における発色組成物を、スプレードライヤーを用いて平均粒径０．５μｍに微細化した粒子とした。
その他の条件は実施例１と同様として、サンプルとなる可逆性多色記録媒体を作製した。
Example 8
The coloring composition in Example 1 was made into particles refined to an average particle size of 0.5 μm using a spray dryer.
Other conditions were the same as in Example 1, and a reversible multicolor recording medium as a sample was produced.
〔比較例１〕
発色組成物（呈色性化合物、顕・減色剤等）を樹脂ポリマーに含有させず、そのまま光−熱変換組成物と混合して記録層を形成した。すなわち、記録層中において分離・独立した状態としなかった。
その他の条件は実施例１と同様として、サンプルとなる可逆性多色記録媒体を作製した。
[Comparative Example 1]
A coloring layer (color developing compound, developing / color-reducing agent, etc.) was not contained in the resin polymer, and was directly mixed with the light-heat conversion composition to form a recording layer. That is, the recording layer was not separated and independent.
Other conditions were the same as in Example 1, and a reversible multicolor recording medium as a sample was produced.
〔比較例２〕
発色組成物にイソシアネート化合物（日本ポリウレタン社製、コロネートＬ）を含有させず、光−熱変換組成物と混合して記録層を形成した。
その他の条件は実施例１と同様として、サンプルとなる可逆性多色記録媒体を作製した。
[Comparative Example 2]
The coloring composition was not mixed with an isocyanate compound (manufactured by Nippon Polyurethane Co., Coronate L), and was mixed with the light-heat conversion composition to form a recording layer.
Other conditions were the same as in Example 1, and a reversible multicolor recording medium as a sample was produced.
〔比較例３〕
発色組成物の平均粒径が６μｍとなるように粉砕した。
その他の条件は実施例１と同様として、サンプルとなる可逆性多色記録媒体を作製した。
[Comparative Example 3]
The coloring composition was pulverized so as to have an average particle size of 6 μm.
Other conditions were the same as in Example 1, and a reversible multicolor recording medium as a sample was produced.
〔比較例４〕
光−熱変換組成物に含有される光−熱変換材料について変更した。
第１の記録層１１中の光−熱変換材料としてシアニン系赤外吸収色素（日本化薬製、ＣＹ−１０、記録層中での吸収波長ピーク７９８ｎｍ）を用い、第２の記録層１２中の光−熱変換材料としてシアニン系赤外吸収色素（Ｈ．Ｗ．ＳＡＮＤＳ社製、ＳＤＡ５６８８、記録層中での吸収波長ピーク８６１ｎｍ）を用い、第３の記録層１３中の光−熱変換材料としてシアニン系赤外吸収色素（Ｈ．Ｗ．ＳＡＮＤＳ社製、ＳＤＡ７７７５、記録層中での吸収波長ピーク：９３３ｎｍ）を用いた。
その他の条件は実施例１と同様として、サンプルとなる可逆性多色記録媒体を作製した。
[Comparative Example 4]
It changed about the light-heat conversion material contained in a light-heat conversion composition.
In the second recording layer 12, a cyanine infrared absorbing dye (Nippon Kayaku Co., Ltd., CY-10, absorption wavelength peak in the recording layer 798 nm) is used as the light-heat conversion material in the first recording layer 11. A light-to-heat conversion material in the third recording layer 13 using a cyanine infrared absorbing dye (manufactured by HW SANDS, SDA5688, absorption wavelength peak 861 nm in the recording layer). A cyanine-based infrared absorbing dye (manufactured by HW SANDS, SDA7775, absorption wavelength peak in recording layer: 933 nm) was used.
Other conditions were the same as in Example 1, and a reversible multicolor recording medium as a sample was produced.
〔光学特性の評価方法〕
上述したようにして作製した実施例１〜８、及び比較例１〜４の可逆性多色記録媒体について、それぞれ光学特性の評価を行った。
先ず、可逆性多色記録媒体全体の地肌の反射濃度（Ｏ．Ｄ．）を、マクベス濃度計によって測定した。
次に、可逆性多色記録媒体を構成する各記録層１１〜１３に対し、記録用レーザー光の当該波長における各記録層単独での吸光度を測定し、また分光光度計で吸収曲線を測定した。その結果、記録層１１〜１３の、記録用レーザー光の当該波長における各記録層単独の吸光度は、１．０であった。
なお、吸収曲線は、一つの記録層のみを吸光度測定用透明ＰＥＴフィルム上に形成し、これを用いて評価した。
[Evaluation method of optical characteristics]
The optical characteristics of the reversible multicolor recording media of Examples 1 to 8 and Comparative Examples 1 to 4 produced as described above were evaluated.
First, the background reflection density (OD) of the entire reversible multicolor recording medium was measured with a Macbeth densitometer.
Next, for each recording layer 11 to 13 constituting the reversible multicolor recording medium, the absorbance of each recording layer alone at the wavelength of the recording laser beam was measured, and the absorption curve was measured with a spectrophotometer. . As a result, the absorbance of each recording layer in the recording layers 11 to 13 at the wavelength of the recording laser beam was 1.0.
The absorption curve was evaluated using only one recording layer formed on a transparent PET film for measuring absorbance.
〔レーザー記録評価〕
次に、上述したようにして作製した実施例１〜８、及び比較例１〜４の可逆性多色記録媒体について、以下の条件で半導体レーザーの照射を行い、記録線幅、及びベタ画像記録の反射濃度を測定した。
発振中心波長が、８００ｎｍ、８６０ｎｍ、９４０ｎｍの半導体レーザー光を、それぞれ、スポット形状３０μｍ×２００μｍ、出力４００ｍＷの条件下で照射しながら走査させた。
走査条件は、スポット形状２００μｍの軸の方向に、速度５．４ｍ／ｓ、走査間隔１５μｍとし、記録されたベタ画像のＣＭＹ(シアン、マゼンダ、イエロー)それぞれの反射濃度の変化をマクベス濃度計により評価した。
次に、１２０℃のホットスタンプを１秒押し当て画像を消去した。
上述したような記録と消去の作業を１００回繰り返し、１００回目の記録を行ったときのベタ画像と、１００回目に消去を行ったときのＣＭＹ(シアン、マゼンダ、イエロー)それぞれの反射濃度の変化をマクベス濃度計により評価した。
[Laser recording evaluation]
Next, the reversible multicolor recording media of Examples 1 to 8 and Comparative Examples 1 to 4 manufactured as described above were irradiated with a semiconductor laser under the following conditions, and the recording line width and solid image recording were performed. The reflection density of was measured.
Scanning was performed while irradiating semiconductor laser beams having oscillation center wavelengths of 800 nm, 860 nm, and 940 nm under the conditions of a spot shape of 30 μm × 200 μm and an output of 400 mW, respectively.
The scanning conditions were a spot shape of 200 μm in the direction of the axis, a speed of 5.4 m / s, a scanning interval of 15 μm, and the change in reflection density of each recorded solid image of CMY (cyan, magenta, yellow) was measured with a Macbeth densitometer. evaluated.
Next, a 120 ° C. hot stamp was pressed for 1 second to erase the image.
The above-described recording and erasing operations are repeated 100 times, and the reflection density changes of the solid image when the 100th recording is performed and the CMY (cyan, magenta, yellow) when the erasing is performed for the 100th time. Was evaluated with a Macbeth densitometer.
〔評価結果〕
実施例１〜８、及び比較例１〜４の光学特性の評価の結果と、レーザー記録評価の結果を下記表１に示した。
〔Evaluation results〕
The results of evaluation of optical characteristics of Examples 1 to 8 and Comparative Examples 1 to 4 and the results of laser recording evaluation are shown in Table 1 below.
表１から明らかなように、実施例１〜８においては、発振中心波長８００ｎｍ、８６０ｎｍ、９４０ｎｍの各レーザー光を用いて記録を行ったとき、良好なイエロー、マゼンタ、シアンの発色が得られ、色かぶりも生じなかった。
また、複数のレーザー光を同時に照射すると、それに対応する中間色が得られることが確かめられた。
また、レーザー光の出力を変化させることにより、発色の色調を変化させることができた。
また、レーザーで記録を行った後、１２０℃のホットスタンプを１秒間接触させることにより、すべての画像を消去することができた。また、レーザー光を照射すると、さらに繰り返して記録を行うことができた。
As is apparent from Table 1, in Examples 1 to 8, when recording was performed using each laser beam having an oscillation center wavelength of 800 nm, 860 nm, and 940 nm, good yellow, magenta, and cyan colors were obtained. There was no color cast.
In addition, it was confirmed that when a plurality of laser beams were irradiated simultaneously, a corresponding intermediate color was obtained.
In addition, the color tone of color development could be changed by changing the output of the laser beam.
Further, after recording with a laser, all images could be erased by bringing a hot stamp at 120 ° C. into contact for 1 second. Further, when the laser beam was irradiated, the recording could be further repeated.
さらに実施例１〜８においては、１００回記録と消去とを繰り返した後においても、良好なイエロー、マゼンタ、シアンの発色が維持されており、色かぶりも生じないことが確かめられた。
また、１２０℃のホットスタンプを１秒間接触させた場合の、記録消去後の反射濃度が低く、すなわち消え残りが非常に小さく、優れた消去特性が維持され、多数回使用後においてもほぼすべての画像を消去することができることが確かめられた。
Further, in Examples 1 to 8, it was confirmed that good yellow, magenta, and cyan color development were maintained even after 100 times of recording and erasing were repeated, and no color fogging occurred.
In addition, when a 120 ° C. hot stamp is contacted for 1 second, the reflection density after recording and erasing is low, that is, the unerased residue is very small, and excellent erasing characteristics are maintained. It was confirmed that the image can be erased.
比較例１、及び比較例２においては、表１に示した結果から明らかなように、発振中心波長が８００ｎｍ、８６０ｎｍ、９４０ｎｍの各レーザー光を用いて記録を行ったとき、良好なイエロー、マゼンタ、シアンの発色が得られ、色かぶりも生じなかった。また複数のレーザー光を同時に照射すると、それに対応する中間色が得られた。
しかし、１００回記録及び消去を繰り返した後は、イエロー、マゼンタ、シアンの発色が劣化した。
また、１２０℃のホットスタンプを１秒間接触させて消去を行った後には、消え残りがあり、すべての画像を消去することができなかった。これは、比較例１においては、呈色性化合物（ロイコ染料）及び顕・減色剤を樹脂ポリマーに含有させず、光−熱変換組成物内に添加・混合させたため、光−熱変換材料あるいはロイコ染料、顕・減色剤が劣化したためである。また比較例２においては、イソシアネート化合物を使用しなかったため、混合プロセスにおいて発色組成物と光−熱変換組成物が相溶してしまい、その結果、光−熱変換材料あるいはロイコ染料、顕・減色剤が劣化したためである。
In Comparative Example 1 and Comparative Example 2, as is apparent from the results shown in Table 1, when recording was performed using laser beams with oscillation center wavelengths of 800 nm, 860 nm, and 940 nm, good yellow and magenta Cyan color was obtained, and no color cast occurred. Moreover, when a plurality of laser beams were irradiated at the same time, a corresponding intermediate color was obtained.
However, after 100 times of recording and erasing, yellow, magenta and cyan coloration deteriorated.
Further, after erasing by contacting a 120 ° C. hot stamp for 1 second, there was an unerased residue, and all images could not be erased. This is because, in Comparative Example 1, the color developing compound (leuco dye) and the developer / color-reducing agent were not contained in the resin polymer, but were added and mixed in the light-heat conversion composition. This is because the leuco dye and the developer / color reducing agent deteriorated. In Comparative Example 2, since the isocyanate compound was not used, the coloring composition and the light-heat conversion composition were compatible with each other in the mixing process. As a result, the light-heat conversion material or leuco dye, visible / subtractive color reduction was obtained. This is because the agent has deteriorated.
また、比較例３においては、記録層の膜厚に対し、発色組成物の平均粒径が大きすぎ、光−熱変換効率が悪化し、良好な反射濃度は得られなかった。 Further, in Comparative Example 3, the average particle size of the color forming composition was too large for the film thickness of the recording layer, the light-heat conversion efficiency was deteriorated, and a good reflection density was not obtained.
また、比較例４においては、所定の吸収ピーク波長の光−熱変換材料が存在する記録層１１〜１３を、実施例１と積層順が逆であるものとしたため、最上層では良好な反射濃度が得られたものの、それより下層では反射濃度が低下し、記録特性が劣化した。
これは、光−熱変換材料は、吸収ピークより長波長側の吸収帯が非常に狭く、逆に低波長側が広いため、記録層の最上層に、最も吸収波長の長い光−熱変換材料を含有させると、それより下層の記録層に書き込みを行う際、上層にてレーザー光が吸収され、下層へのレーザー光の到達量が低減してしまうためである。
In Comparative Example 4, since the recording layers 11 to 13 in which the light-to-heat conversion material having a predetermined absorption peak wavelength is present have the reverse stacking order from Example 1, the uppermost layer has a good reflection density. However, in the lower layers, the reflection density decreased and the recording characteristics deteriorated.
This is because the light-to-heat conversion material has a very narrow absorption band on the longer wavelength side than the absorption peak, and conversely, the lower wavelength side is wide, so the light-to-heat conversion material with the longest absorption wavelength is formed on the top layer of the recording layer. When it is contained, when writing is performed on the lower recording layer, the laser light is absorbed by the upper layer, and the amount of laser light reaching the lower layer is reduced.
１……支持基板、１０……可逆性多色記録媒体、１１……第１の記録層、１２……第２の記録層、１３……第３の記録層、１４，１５……断熱層、１６……保護層、２１……発色組成物、２２……光−熱変換組成物
DESCRIPTION OF SYMBOLS 1 ... Support substrate, 10 ... Reversible multicolor recording medium, 11 ... 1st recording layer, 12 ... 2nd recording layer, 13 ... 3rd recording layer, 14, 15 ... Heat insulation layer , 16 ... protective layer, 21 ... coloring composition, 22 ... light-heat conversion composition
Claims (3)
前記記録層には、少なくとも、電子供与性を有する呈色性化合物と、電子受容性を有する顕・減色剤とが、樹脂中に含有されてなる粒子径が３μｍ以下の微粒子状の発色組成物と、
少なくとも、それぞれ異なる波長域の赤外線を吸収する光−熱変換材料を含有する光−熱変換組成物とが、分離・独立した状態で混合されてなり、
前記複数の記録層に含有されている光−熱変換組成物それぞれの吸収波長（λmaxn）が、λmax1＞λmax2＞・・・＞λmaxnの関係にあって、前記光−熱変換組成物が、それぞれ異なる波長域の赤外線を吸収し、発熱することにより、前記呈色性化合物と前記顕・減色剤との間の可逆的反応を起こさせるようになされており、
前記発色組成物を構成する樹脂が、その周囲に存する記録層中の樹脂と相溶せず、前記発色組成物が、前記記録層中において分離・独立した状態で存在する可逆性多色記録媒体。 A plurality of recording layers that reversibly develop different color tones in the surface direction of the support substrate become a first recording layer, a second recording layer,..., An nth recording layer from the support substrate side. So as to be separated and laminated,
In the recording layer, at least a color developing compound having an electron donating property and a developer / color reducing agent having an electron accepting property are contained in a resin. When,
At least, a light-heat conversion composition containing a light-heat conversion material that absorbs infrared rays of different wavelength ranges is mixed in a separated and independent state,
The absorption wavelengths (λmaxn) of the light-to-heat conversion compositions contained in the plurality of recording layers are in a relationship of λmax1>λmax2>...> Λmaxn, and the light-to-heat conversion compositions are respectively By absorbing infrared rays in different wavelength ranges and generating heat, a reversible reaction between the color former and the developer / color-reducing agent is caused,
The reversible multicolor recording medium in which the resin constituting the coloring composition is incompatible with the resin in the recording layer existing around the resin and the coloring composition is present in a separated and independent state in the recording layer .
前記記録層には、少なくとも、電子供与性を有する呈色性化合物と、電子受容性を有する顕・減色剤とが、樹脂中に含有されてなる粒子径が３μｍ以下の微粒子状の発色組成物と、
少なくとも、それぞれ異なる波長域の赤外線を吸収する光−熱変換材料を含有する光−熱変換組成物とが、分離・独立した状態で混合されてなり、
前記複数の記録層に含有されている光−熱変換組成物それぞれの吸収波長（λmaxn）が、λmax1＞λmax2＞・・・＞λmaxnの関係にあって、前記光−熱変換組成物が、それぞれ異なる波長域の赤外線を吸収し、発熱することにより、前記呈色性化合物と前記顕・減色剤との間の可逆的反応を起こさせるようになされている可逆性多色記録媒体の製造工程として、
前記電子供与性を有する呈色性化合物と、電子受容性を有する顕・減色剤とを、樹脂中に含有させて発色組成物を作製する工程と、
前記発色組成物と、前記光−熱変換組成物とを混合し、前記記録層を成膜する工程とを有し、
前記発色組成物を構成する樹脂として、前記発色組成物が、前記記録層中において分離・独立した状態で存在するように当該発色組成物の周囲に存する記録層中の成分と相溶しないものを選定する可逆性多色記録媒体の製造方法。 A plurality of recording layers that reversibly develop different color tones in the surface direction of the support substrate become a first recording layer, a second recording layer,..., An nth recording layer from the support substrate side. So as to be separated and laminated,
In the recording layer, at least a color developing compound having an electron donating property and a developer / color reducing agent having an electron accepting property are contained in a resin. When,
At least, a light-heat conversion composition containing a light-heat conversion material that absorbs infrared rays of different wavelength ranges is mixed in a separated and independent state,
The absorption wavelengths (λmaxn) of the light-to-heat conversion compositions contained in the plurality of recording layers are in a relationship of λmax1>λmax2>...> Λmaxn, and the light-to-heat conversion compositions are respectively As a process for producing a reversible multicolor recording medium adapted to cause a reversible reaction between the color former and the developer / color reducing agent by absorbing infrared rays in different wavelength ranges and generating heat. ,
A step of preparing a coloring composition by containing the color-providing compound having electron donating property and a developer / color-reducing agent having electron acceptability in a resin;
Mixing the coloring composition and the light-heat conversion composition, and forming the recording layer,
As the resin constituting the coloring composition, a resin that is incompatible with the components in the recording layer around the coloring composition so that the coloring composition exists in a separated and independent state in the recording layer. A method for producing a reversible multicolor recording medium to be selected.
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