JP2003118241A - Multicolor reversible heat sensitive recording medium - Google Patents
Multicolor reversible heat sensitive recording mediumInfo
- Publication number
- JP2003118241A JP2003118241A JP2001316278A JP2001316278A JP2003118241A JP 2003118241 A JP2003118241 A JP 2003118241A JP 2001316278 A JP2001316278 A JP 2001316278A JP 2001316278 A JP2001316278 A JP 2001316278A JP 2003118241 A JP2003118241 A JP 2003118241A
- Authority
- JP
- Japan
- Prior art keywords
- color
- recording
- multicolor
- recording medium
- reversible
- 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
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は書き換え可能な感熱
記録媒体とその使用方法に属するものである。特に、２
色以上の発色やフルカラーの可能な多色可逆感熱記録媒
体とその使用方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rewritable thermal recording medium and a method of using the same. Especially 2
The present invention relates to a multicolor reversible thermosensitive recording medium capable of coloring in more than three colors and full color and a method of using the same.
【０００２】[0002]
【従来の技術】近年、画像の記録消去が可能な可逆感熱
記録媒体が注目されている。その代表的なものが、通常
無色ないし淡色のロイコ染料と加熱により該ロイコ染料
を発色させ、これを再加熱して消色させる可逆顕色剤か
らなる可逆感熱記録媒体である。このような記録材料と
して特開平６−２１０９５４号公報、特開平６−１７１
２２５号公報、特開平７−６８９３３号公報、特開平７
−６８９３４号公報等に、良好なコントラストで画像の
記録・消去が可能で、日常生活の環境下で経時的に安定
な画像を保持することが可能な可逆顕色剤が報告され、
現在実用化されている。2. Description of the Related Art In recent years, reversible thermosensitive recording media capable of recording and erasing images have been attracting attention. A typical example thereof is a reversible thermosensitive recording medium comprising a colorless or light-colored leuco dye and a reversible color developer that develops a color of the leuco dye by heating and then reheats it to decolorize it. As such recording materials, JP-A-6-210954 and JP-A-6-171 are available.
225, JP-A-7-68933, JP-A-7
JP-A-68934 discloses a reversible color developer capable of recording / erasing an image with good contrast and capable of holding a stable image over time in an environment of daily life.
It is currently in practical use.
【０００３】この種の記録媒体は、記録には通常サーマ
ルヘッドが用いられるが、その場合、加熱による画像の
記録と消去を繰り返すと、表面が加熱されながらこすら
れるため、記録層表面に傷が発生し、ひどくなると均一
な画像が記録できないという不都合が見られていた。こ
れに対し、特開平６−３４４６７３号公報、特開平８−
１５６４１０号公報では、そうした可逆性記録材料の表
面に保護層を設け、サーマルヘッドを用いた際の記録層
表面の傷を低減させることが提案されている。In this type of recording medium, a thermal head is usually used for recording. In this case, when recording and erasing of an image by heating are repeated, the surface is rubbed while being heated, so that the surface of the recording layer is scratched. When it occurs and becomes aggravated, there is a problem that a uniform image cannot be recorded. On the other hand, JP-A-6-344673 and JP-A-8-
Japanese Patent No. 156410 proposes that a protective layer is provided on the surface of such a reversible recording material to reduce scratches on the surface of the recording layer when a thermal head is used.
【０００４】一方、レーザー等の光を使用し、非接触で
記録する方法が報告されている。特開平５−８５３７号
公報では可逆感熱媒体にヒートモード光記録層を設ける
ことで、光照射により記録・消去する方法が報告されて
いる。また、特開２０００−１５９３１号公報では可逆
感熱記録層を光熱変換層でサンドイッチする方法などが
報告されている。On the other hand, there has been reported a non-contact recording method using light from a laser or the like. Japanese Patent Application Laid-Open No. 5-8537 reports a method of recording / erasing by light irradiation by providing a heat mode optical recording layer on a reversible thermosensitive medium. Further, Japanese Patent Laid-Open No. 2000-15931 reports a method of sandwiching a reversible thermosensitive recording layer with a photothermal conversion layer.
【０００５】この種の記録媒体は単色でカード等の用途
において実用化されているが、特に表示媒体として使う
場合、多色やフルカラー表示への期待が大きいものがあ
る。公開特許公報によれば、この種の記録媒体を使い２
色以上の発色と消去を行う方法が提案されている。This type of recording medium is monochromatic and has been put to practical use in applications such as cards. However, when used as a display medium, there are some that have great expectations for multicolor or full color display. According to the published patent publication, this type of recording medium is used.
A method of coloring and erasing more than a color has been proposed.
【０００６】特開平６−７９９７０号公報において、発
色色調及び消色開始温度の異なる複数種の可逆感熱記録
組成物を積層したりするなどして多色を表現する方法が
提案されている。また、特開平６−３０５２４７号公報
では、発色色調が異なりかつ発色体を得るのに必要な発
色状態維持最小冷却温度の異なる２種類の可逆感熱記録
組成物を、分離・独立して存在させ、２色の記録と消去
を行う方法が提案されている。これらの方法では、媒体
の製造面や装置の開発面で難しいところがあると考えら
れる。[0006] Japanese Patent Laid-Open No. 6-79970 proposes a method of expressing multiple colors by laminating a plurality of types of reversible thermosensitive recording compositions having different color tones and decoloring start temperatures. Further, in JP-A-6-305247, two types of reversible thermosensitive recording compositions having different color tones and different color-maintaining minimum cooling temperatures required for obtaining a color-developing substance are present separately and independently. A method of recording and erasing two colors has been proposed. It is considered that these methods are difficult in terms of manufacturing the medium and developing the device.
【０００７】特開平７−１７１３２号公報では支持体上
に異なる色調の可逆感熱記録層をエリアを決めて形成
し、多色を表現する方法が提案されている。この方法で
は表現が制限される。Japanese Unexamined Patent Publication (Kokai) No. 7-17132 proposes a method of expressing multiple colors by forming areas of reversible thermosensitive recording layers of different color tones on a support. This method has limited expression.
【０００８】特開２０００−２５３３８号公報では、発
色が異なる可逆感熱組成物を印刷などにより、規則的に
配列させ、その上に近赤外吸収層を設け、レーザー光に
より各色を発色させ、多色を表現する方法が提案されて
いる。この場合、どの色相も同じレーザーで発色するの
で、媒体の画素の配置に狂いがあってはならず、狙った
色の画素にレーザーを正確に照射する必要があり、記録
装置が非常に大がかりになると思われる。In Japanese Patent Laid-Open No. 2000-25338, reversible thermosensitive compositions having different colors are regularly arranged by printing or the like, a near infrared absorption layer is provided thereon, and each color is colored by laser light. Methods of expressing colors have been proposed. In this case, all hues are colored by the same laser, so there should be no misalignment of the pixels on the medium, and it is necessary to precisely irradiate the laser on the pixels of the target color, which makes the recording device very large. I think it will be.
【０００９】また、特開２００１−１６４５号公報で
は、支持体上にある発色色相の可逆感熱記録層とその上
にその記録層を発色させるレーザー光の吸収層の組合せ
で、断熱層を介し、発色色相とそれに対応するレーザー
吸収層の組合せで３種組み合わせて形成した記録媒体を
作り、それぞれの吸収波長に相当するレーザー光を照射
し、カラー画像を作る方法が提案されている。この方法
では下の発色層になるほど、レーザー光は多くの層を通
過する必要があり、それらの層にレーザー光が吸収され
効率が悪くなる。また、既に発色した層がレーザーを吸
収する事で、目的の発色層の発色を妨害したり、既に発
色した目的外の色相を薄くするという欠点が考えられ
る。Further, in Japanese Patent Laid-Open No. 2001-1645, a combination of a reversible thermosensitive recording layer of a coloring hue on a support and a laser light absorbing layer for coloring the recording layer on the support is provided via a heat insulating layer, A method has been proposed in which a recording medium formed by combining three types of colored hues and a corresponding laser absorption layer is formed, and a laser beam corresponding to each absorption wavelength is irradiated to form a color image. In this method, the lower the color forming layer, the more the laser light needs to pass through many layers, and the laser light is absorbed by those layers, resulting in poor efficiency. In addition, it is considered that the already-developed layer absorbs the laser, thereby disturbing the coloring of the intended coloring layer or reducing the already-developed unintended hue.
【００１０】[0010]
【発明が解決しようとする課題】本発明は、通常無色な
いし淡色のロイコ染料と加熱により該ロイコ染料を発色
させ、これを再加熱して消色させる可逆顕色剤からなる
可逆感熱記録材料を用い、鮮明な２色以上の発色やフル
カラーの発色と消去が可能な媒体を提供することをその
課題とする。DISCLOSURE OF THE INVENTION The present invention provides a reversible thermosensitive recording material comprising a colorless or light-colored leuco dye and a reversible developer which develops the color of the leuco dye by heating and reheats it to decolorize it. It is an object of the present invention to provide a medium which can be used for clear and two-color or full-color coloring and erasing.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく、鋭意研究を進めた結果、上述の特開２０
０１−１６４５号公報を改良することで本発明を完成す
るに至った。すなわち、本発明によれば、ロイコ染料
（Ｒｎ）と可逆顕色剤と該ロイコ染料に対応する光熱変
換材料（Ｔｎ）からなる光発色記録体（Ｍｎ）を、Ｍ１
（Ｒ１，Ｔ１）,Ｍ２（Ｒ２，Ｔ２），・・・，Ｍｎ
（Ｒｎ，Ｔｎ）の組合せで２以上有し、該２以上の光発
色記録体、すなわちＭ１，Ｍ２，・・・，Ｍｎ（ｎ≧
２）を１ユニットとし、このユニットが支持体上に均一
に配置されたことを特徴とする多色可逆記録媒体が提供
される。Means for Solving the Problems The inventors of the present invention have conducted earnest research to solve the above problems, and as a result, the above-mentioned Japanese Unexamined Patent Application Publication No.
The present invention has been completed by improving JP-A No. 01-1645. That is, according to the present invention, a photochromic recording material (Mn) comprising a leuco dye (Rn), a reversible color developer, and a photothermal conversion material (Tn) corresponding to the leuco dye is used as M1.
(R1, T1), M2 (R2, T2), ..., Mn
The combination of (Rn, Tn) has two or more, and the two or more photocolor recording materials, that is, M1, M2, ..., Mn (n ≧
There is provided a multicolor reversible recording medium characterized in that 2) is set as one unit and this unit is uniformly arranged on a support.
【００１２】また、本発明によれば、ロイコ染料（Ｒ
ｎ）と可逆顕色剤と該ロイコ染料に対応する光熱変換材
料（Ｔｎ）からなる光発色記録体（Ｍｎ）を、Ｍ１（Ｒ
１，Ｔ１）,Ｍ２（Ｒ２，Ｔ２），・・・，Ｍｎ（Ｒ
ｎ，Ｔｎ）の組合せで２以上有し、該２以上の光発色記
録体、すなわちＭ１，Ｍ２，・・・，Ｍｎ（ｎ≧２）を
１ユニットとし、該ユニットが均一に配置された多色可
逆記録層を支持体上に複数有し、その複数層に存在する
光発色記録体の種類がすべて異なることを特徴とする多
色可逆記録媒体が提供される。According to the present invention, the leuco dye (R
n), a reversible developer and a photothermal conversion material (Tn) corresponding to the leuco dye, a photochromic recording material (Mn) is added to M1 (R
1, T1), M2 (R2, T2), ..., Mn (R
n, Tn) in two or more, and the two or more photochromic recording materials, that is, M1, M2, ..., Mn (n ≧ 2) are regarded as one unit, and the units are uniformly arranged. There is provided a multicolor reversible recording medium having a plurality of color reversible recording layers on a support and different types of photochromic recording bodies existing in the plurality of layers.
【００１３】また、本発明によれば、上記の光発色記録
体が印刷により支持体上に配置されたことを特徴とする
多色可逆記録媒体が提供される。Further, according to the present invention, there is provided a multicolor reversible recording medium characterized in that the above photochromic recording medium is arranged on a support by printing.
【００１４】また、本発明によれば、上記の多色可逆記
録媒体が有する光発色記録体を、それぞれの光発色記録
体に含まれる光熱変換材料の光熱変換に有効な波長の光
を順次照射し、発色させ、多色画像を形成させる方法が
提供される。Further, according to the present invention, the photochromic recording bodies of the multicolor reversible recording medium are sequentially irradiated with light having a wavelength effective for photothermal conversion of the photothermal conversion materials contained in the respective photochromic recording bodies. A method of forming a multicolor image by forming a multicolor image is provided.
【００１５】また、本発明によれば、上記の方法におい
て、多色光発色可逆記録層の最下層から順次上層に向け
て発色させ、多色画像を形成させることを特徴とする方
法。According to the present invention, in the above method, a multicolor image is formed by sequentially developing color from the lowermost layer to the upper layer of the multicolor light reversible recording layer.
【００１６】[0016]
【発明の実施の形態】本発明の多色可逆記録媒体におけ
る各光発色記録体は、ロイコ染料と可逆顕色剤からなる
感熱発色体と、この感熱発色体を発色させるための吸収
波長を持つ光熱変換材料からなる。光熱変換材料は感熱
発色体を有効に発色させるため、感熱発色体内部や周辺
に存在させる。光熱変換剤を周辺に存在させる方法の例
として、球状をした光発色記録体の周りに光熱変換材料
含んだ皮膜が包んでいる状態のものや、光発色記録体が
層状に存在し、感熱発色体の層の前後に光熱変換剤の層
が存在する等の状態のものが考えられる。BEST MODE FOR CARRYING OUT THE INVENTION Each photochromic recording material in the multicolor reversible recording medium of the present invention has a thermosensitive colorant composed of a leuco dye and a reversible color developer, and an absorption wavelength for coloring the thermosensitive colorant. It consists of a photothermal conversion material. The photothermal conversion material is present inside or around the heat-sensitive color developing body in order to effectively develop the color of the heat-sensitive color developing body. As an example of the method of allowing the photothermal conversion agent to be present in the periphery, there is a state in which a film containing a photothermal conversion material is wrapped around a spherical photochromic recording material, or the photochromic recording material is present in a layered form, and a thermosensitive coloring A state in which a layer of the photothermal conversion agent exists before and after the body layer is considered.
【００１７】本発明の光発色記録体に含まれるロイコ染
料と光熱変換材料は１：１で対応する。すなわち、ある
光発色記録体のロイコ染料は特定の光熱変換材料と存在
し、その光熱変換材料の光熱変換に有効な波長の光を照
射することで、対応するロイコ染料が発色する。本発明
に使用されるロイコ染料は発色色相の異なるものが使用
され、光熱変換材料も光熱変換に有効な波長が異なるも
のが使用される。その結果、特定の波長の光の照射で特
定の色相が発色することになる。The leuco dye contained in the photochromic recording material of the present invention corresponds to the photothermal conversion material in a ratio of 1: 1. That is, the leuco dye of a certain photochromic recording material exists with a specific photothermal conversion material, and the corresponding leuco dye develops color when irradiated with light having a wavelength effective for photothermal conversion of the photothermal conversion material. The leuco dyes used in the present invention have different coloring hues, and the photothermal conversion materials having different effective wavelengths for photothermal conversion are also used. As a result, a specific hue is developed by irradiation with light having a specific wavelength.
【００１８】本発明の多色可逆記録媒体において、ロイ
コ染料が異なる２種以上の光発色記録体を多色記録層上
に形成させるが、各光発色可逆記録体が１個づつ集まっ
たものを１ユニットとし、このユニットを平面的に均一
に配置させる。In the multicolor reversible recording medium of the present invention, two or more photochromic recording materials having different leuco dyes are formed on the multicolor recording layer. Each photochromic reversible recording material is collected one by one. One unit is used, and the units are uniformly arranged in a plane.
【００１９】本発明では上記のユニットを印刷方式を利
用することにより容易に均一に配置できることを見いだ
した。すなわち、印刷機を使い、各色相のインキを印刷
する要領で、各光発色可逆記録体を印刷し、各光発色可
逆記録体のドットがユニットを形成するよう、またその
ユニットが均一に配置するように行う。印刷機は特に限
定するものではないが、グラビア印刷機、オフセット印
刷機、スクリーン印刷機などが考えられ、凸版、平版、
凹版、孔版などの方式のすべての印刷機の使用が考えら
れる。さらに、インクジェットによる方法も考えられ
る。In the present invention, it has been found that the above units can be easily and uniformly arranged by using a printing method. That is, by using a printing machine, each photochromic reversible recording medium is printed in the same manner as printing ink of each hue, and the dots of each photochromic reversible recording medium form units, and the units are evenly arranged. To do so. The printing machine is not particularly limited, but a gravure printing machine, an offset printing machine, a screen printing machine, and the like are conceivable.
It is conceivable to use all printing presses such as intaglio and stencil. Furthermore, an inkjet method is also conceivable.
【００２０】本発明の多色可逆記録媒体の製造におい
て、多色記録層の上に、この層を保護するため中間層や
保護層が設けるのが好ましい。これら中間層や保護層は
全面に設けるのが好ましいが、部分的に光発色記録体の
部分だけ設ける方法も考えられる。多色可逆記録媒体が
多色記録層を複数層有する場合、光発色記録体の記録用
の熱で別の上下の多色記録層に存在する光発色記録体に
影響しない様、その層間を断熱する必要がある。断熱の
方法として、塗工層を入れたり、フィルムの層を入れた
りすることが考えられる。In the production of the multicolor reversible recording medium of the present invention, it is preferable to provide an intermediate layer or a protective layer on the multicolor recording layer in order to protect this layer. It is preferable to provide these intermediate layer and protective layer on the entire surface, but it is also possible to partially provide only the photochromic recording material. When the multicolor reversible recording medium has a plurality of multicolor recording layers, heat between the layers is insulated so that the recording heat of the photocolor recording medium does not affect the photocolor recording bodies in the upper and lower multicolor recording layers. There is a need to. As a method of heat insulation, it is possible to add a coating layer or a film layer.
【００２１】また、この複合層を発色させる場合、レー
ザーなど特定の波長を持つ光が適している。照射するレ
ーザーの波長は発色させようとする複合層に存在する光
熱変換材料の光吸収が大きいものを選択する。また、そ
のレーザーで他の光熱変換材料が吸収して目的以外の色
相が発色したり、発色したものが消色しないよう、レー
ザーの波長及び光熱変換材料を選択する必要がある。Further, when the color of the composite layer is developed, light having a specific wavelength such as a laser is suitable. The wavelength of the laser to be irradiated is selected so that the photothermal conversion material existing in the composite layer to be colored is large in light absorption. Further, it is necessary to select the wavelength of the laser and the photothermal conversion material so that the laser absorbs the other photothermal conversion material to develop a hue other than the intended color and does not erase the developed color.
【００２２】さらに、本発明での多色記録層を複数有す
る多色可逆記録媒体を発色させる方法として、既に発色
した層が次に発射されたレーザー光を吸収し、目的の色
相の発色を妨害することを避けるため、最下層の多色記
録層から順次、上層に向かって発色させる。Further, as a method of developing a color of a multicolor reversible recording medium having a plurality of multicolor recording layers according to the present invention, a layer which has already developed a color absorbs laser light emitted next and interferes with the development of a desired hue. In order to avoid this, color is sequentially developed from the lowermost multicolor recording layer toward the upper layer.
【００２３】次に、本発明の構成物の詳細について説明
する。本発明で用いられるロイコ染料としては、一般的
に感圧記録紙や感熱記録紙などに用いられるものに代表
されるが、特に限定されず、トリアリール系メタン化合
物、キサンテン化合物、ジフェニルメタン系化合物、チ
アジン系化合物、スピロ系化合物などが考えられる。ま
た、これらの化合物を混合して使用することも考えられ
る。Next, details of the components of the present invention will be described. The leuco dye used in the present invention is typically represented by those used for pressure-sensitive recording paper and heat-sensitive recording paper, but is not particularly limited, and triaryl methane compounds, xanthene compounds, diphenylmethane compounds, Thiazine compounds and spiro compounds are considered. It is also conceivable to use a mixture of these compounds.
【００２４】本発明で用いられる可逆顕色剤としては、
例えば、特開平６−２１０９５４号公報で提案されてい
るフェノール化合物、特開平１１−５８９６３号公報で
提案された化合物などが考えられるが、加熱によりロイ
コ染料に可逆的な色調変化を生じせしめる化合物であれ
ば特に限定されない。The reversible color developer used in the present invention includes
For example, a phenol compound proposed in JP-A-6-210954, a compound proposed in JP-A-11-58963, and the like are conceivable, but a compound that causes a reversible color change in a leuco dye by heating. There is no particular limitation as long as it exists.
【００２５】本発明に用いられる光熱変換材料光熱変換
材料として、特に限定されるものではないが、以下のも
のが上げられる。例えば白金、金、銀、銅、チタン、シ
リコン、クロム、ニッケル、ゲルマニウム、アルミニウ
ムなどの金属または半金族があり、これらを蒸着膜など
の薄膜を形成して光熱変換する。また、色素系の光熱変
換材料としてはアゾ系色素、シアニン系色素、ナフトキ
ノン系色素、アントラキノン系色素、スクアリリウム系
色素、フタロシアニン系色素、ナフトキノン系色素、ポ
リフィリン系色素、インジゴ系色素、ジチオール金属錯
体色素、アズレニウム系色素、キノンイミド系色素、キ
ノンジイミン系色素などがある。さらに、有機顔料など
も光熱変換材料として使うことも可能である。３色以上
や以上の中で特に好ましいものは、可視領域での吸収が
少なく、吸収波長がある領域で明確な吸収を示し、それ
以外の領域では光を吸収しない特性のものである。しか
し、目的によっては、可視領域で吸収があるものや、あ
る程度幅が広い波長領域を持ったものも使用は可能であ
る。Light-to-heat conversion material used in the present invention The light-to-heat conversion material is not particularly limited, but the following can be mentioned. For example, there are metals such as platinum, gold, silver, copper, titanium, silicon, chromium, nickel, germanium, and aluminum, or semi-metals, which are subjected to photothermal conversion by forming a thin film such as a vapor deposition film. Further, as the dye-based photothermal conversion material, azo dye, cyanine dye, naphthoquinone dye, anthraquinone dye, squarylium dye, phthalocyanine dye, naphthoquinone dye, porphyrin dye, indigo dye, dithiol metal complex dye , Azurenium dyes, quinone imide dyes, quinone diimine dyes, and the like. Furthermore, organic pigments and the like can also be used as the photothermal conversion material. Particularly preferred among the three colors or more are those having a property of low absorption in the visible region, showing clear absorption in a region having an absorption wavelength, and not absorbing light in other regions. However, depending on the purpose, it is possible to use one that has absorption in the visible region and one that has a wavelength region that is somewhat wide.
【００２６】本記録媒体に非接触の記録手段として、特
に限定するものではないが、各種の半導体レーザー、炭
酸ガスレーザー、ＹＡＧレーザーやキセノンランプなど
が考えられる。また、記録したものを消去する方法は、
特に限定するものではないが、発色の時に使ったものと
同じレーザー光で消去する方法や熱ロールを通したり、
熱スタンプや熱風などで媒体全体を温める方法などが考
えられる。The non-contact recording means for the recording medium is not particularly limited, but various semiconductor lasers, carbon dioxide gas lasers, YAG lasers, xenon lamps, etc. can be considered. Also, the method to erase the recorded one is
Although it is not particularly limited, it is possible to erase with the same laser light as that used for coloring, pass through a heat roll,
A method of heating the entire medium with a hot stamp or hot air can be considered.
【００２７】[0027]
【実施例】以下に前記発明をより詳細に説明するが、本
発明はこの実施例で限定されるものではない。なお、以
下に示す部はいずれも重量基準である。EXAMPLES The present invention will be described in more detail below, but the present invention is not limited to these examples. All parts shown below are based on weight.
【００２８】（Ａ）黒発色用インクの作成、ロイコ染料
として３−ジ−ｎ−ブチルアミノ−６−メチル−７−ア
ニリノフルオランを２０部、可逆顕色剤としてＮ−［３
−（ｐ−ヒドロキシフェニル）プロピオノ］−Ｎ′−ｎ
−オクタデカノヒドラジドを１００部、光熱変換材料と
してフタロシアニン（商品名、ＳＩＲ−１３２、最大吸
収波長域１０５０ｎｍ近辺、山本化成製）３０部、バイ
ンダー樹脂として塩化ビニル酢酸ビニル共重合樹脂（商
品名、ＶＡＧＨ、ユニオンカーバイト社製）５０部、溶
媒としてトルエン６００部を加え、ボールミルで２４時
間粉砕し、黒発色の光発色記録体用インクを作成した。(A) Preparation of black coloring ink, 20 parts of 3-di-n-butylamino-6-methyl-7-anilinofluorane as leuco dye, N- [3 as reversible developer
-(P-Hydroxyphenyl) propiono] -N'-n
100 parts of octadecanohydrazide, 30 parts of phthalocyanine (trade name, SIR-132, maximum absorption wavelength range near 1050 nm, manufactured by Yamamoto Kasei) as a photothermal conversion material, vinyl chloride vinyl acetate copolymer resin (trade name, 50 parts of VAGH, manufactured by Union Carbide Co., Ltd.) and 600 parts of toluene as a solvent were added, and the mixture was pulverized with a ball mill for 24 hours to prepare an ink for photochromic recording material of black color.
【００２９】（Ｂ）赤発色用インクの作成、ロイコ染料
として３−ジエチルアミノ−６−メチル−７−クロロフ
ルオランを２０部、可逆顕色剤としてＮ−［３−（ｐ−
ヒドロキシフェニル）プロピオノ］−Ｎ′−ｎ−オクタ
デカノヒドラジドを１００部、光熱変換材料としてフタ
ロシアニン（商品名、ＭＩＲ−３６９、最大吸収波長域
８３０ｎｍ近辺、山本化成製）３０部、バインダー樹脂
として塩化ビニル酢酸ビニル共重合樹脂（商品名、ＶＡ
ＧＨ、ユニオンカーバイト社製）５０部、溶媒としてト
ルエン６００部を加え、ボールミルで２４時間粉砕し、
赤発色の光発色記録体用インクを作成した。(B) Preparation of red coloring ink, 20 parts of 3-diethylamino-6-methyl-7-chlorofluorane as leuco dye, and N- [3- (p-
100 parts of hydroxyphenyl) propiono] -N'-n-octadecanohydrazide, 30 parts of phthalocyanine (trade name, MIR-369, maximum absorption wavelength range near 830 nm, manufactured by Yamamoto Kasei) as a photothermal conversion material, chloride as a binder resin Vinyl vinyl acetate copolymer resin (trade name, VA
GH, manufactured by Union Carbide Co., Ltd.), and 600 parts of toluene as a solvent are added, and the mixture is crushed by a ball mill for 24 hours,
An ink for a red color photochromic recording material was prepared.
【００３０】（Ｃ）青発色用インクの作成、ロイコ染料
として３、３−ビス（４−ジメチルアミノフェニル）−
６−ジメチルアミノフタリドを２０部、可逆顕色剤とし
てＮ−［３−（ｐ−ヒドロキシフェニル）プロピオノ］
−Ｎ′−ｎ−オクタデカノヒドラジドを１００部、光熱
変換材料としてフタロシアニン（商品名、ＹＫＲ−４０
１０、最大吸収波長域７８０ｎｍ近辺、山本化成製）３
０部、バインダー樹脂として塩化ビニル酢酸ビニル共重
合樹脂（商品名、ＶＡＧＨ、ユニオンカーバイト社製）
５０部、溶媒としてトルエン６００部を加え、ボールミ
ルで２４時間粉砕し、青発色の光発色記録体用インクを
作成した。
（Ｄ）緑発色用インクの作成、ロイコ染料として２−ア
ニリノ−６−（Ｎ−エチル−Ｎ−ｎ−ヘキシルアミノ）
フルオランを２０部、可逆顕色剤としてＮ−［３−（ｐ
−ヒドロキシフェニル）プロピオノ］−Ｎ′−ｎ−オク
タデカノヒドラジドを１００部、光熱変換材料としてフ
タロシアニン（商品名、ＭＩＲ−３７０、最大吸収波長
域９１０ｎｍ近辺、山本化成製）３０部、バインダー樹
脂として塩化ビニル酢酸ビニル共重合樹脂（商品名、Ｖ
ＡＧＨ、ユニオンカーバイト社製）５０部、溶媒として
トルエン６００部を加え、ボールミルで２４時間粉砕
し、緑発色の光発色記録体用インクを作成した。(C) Preparation of blue coloring ink, 3,3-bis (4-dimethylaminophenyl)-as leuco dye
20 parts of 6-dimethylaminophthalide, N- [3- (p-hydroxyphenyl) propiono] as a reversible developer
100 parts of -N'-n-octadecanohydrazide, phthalocyanine as a photothermal conversion material (trade name, YKR-40
10, near the maximum absorption wavelength range of 780 nm, manufactured by Yamamoto Kasei) 3
0 parts, vinyl chloride vinyl acetate copolymer resin as a binder resin (trade name, VAGH, manufactured by Union Carbide)
50 parts and 600 parts of toluene as a solvent were added, and the mixture was crushed by a ball mill for 24 hours to prepare an ink for blue color photochromic recording material. (D) Preparation of green coloring ink, 2-anilino-6- (N-ethyl-Nn-hexylamino) as leuco dye
20 parts of fluoran, N- [3- (p
-Hydroxyphenyl) propiono] -N'-n-octadecanohydrazide 100 parts, as a photothermal conversion material phthalocyanine (trade name, MIR-370, maximum absorption wavelength range near 910 nm, manufactured by Yamamoto Kasei) 30 parts, as a binder resin Vinyl chloride vinyl acetate copolymer resin (trade name, V
AGH, manufactured by Union Carbide Co., Ltd.) (50 parts) and toluene (600 parts) as a solvent were added, and the mixture was crushed for 24 hours with a ball mill to prepare an ink for photo-coloring recording material of green color.
【００３１】（Ｅ）保護層インクの作成、アロニックス
Ｍ８０３０（東亞合成化学工業製）９０部にＮ−ビニル
−２−ピロリドン５部、イルガキュア５００（日本チバ
ガイギー社製）５部、ミズカシルＰ−５２７（水澤化学
製）１０部を加え、十分に攪拌し、紫外線硬化性の保護
層塗布液を作成した。(E) Preparation of ink for protective layer, 90 parts of Aronix M8030 (manufactured by Toagosei Chemical Industry Co., Ltd.), 5 parts of N-vinyl-2-pyrrolidone, 5 parts of Irgacure 500 (manufactured by Japan Ciba-Geigy), Mizukasil P-527 ( 10 parts (manufactured by Mizusawa Chemical Co., Ltd.) was added and sufficiently stirred to prepare an ultraviolet curable protective layer coating liquid.
【００３２】実施例１
支持体として厚さ１００μｍ白色ポリエステルフィルム
上に、印刷機を用いて、（Ｃ）で作成した青発色用イン
キを使用し、乾燥後５μｍの厚さになるよう、８０μｍ
角の正方形を前後、左右１６０μｍの間隔を開け、等間
隔に配列し、黒発色の光発色記録体を形成した。次に、
（Ｄ）で作成した緑発色用インクを、同じく乾燥後５μ
ｍの厚さになるよう、８０μｍ角の正方形を前後、左右
１６０μｍの間隔を開けかつ青発色の光発色記録体から
４０μｍの間隔を開け、青発色インキを乗せていないエ
リアに配列した。（図１参照）さらに、それらの印刷の
上に、同じく印刷機により、（Ｅ）で作成した保護層イ
ンクを使用し乾燥後２μｍの厚さになるよう保護層を全
面に形成し、多色可逆記録媒体を作成した。Example 1 As a support, a blue-coloring ink prepared in (C) was used on a white polyester film having a thickness of 100 μm by using a printing machine to give a thickness of 5 μm and a thickness of 80 μm.
Square corners were arranged at equal intervals in the front and back and left and right 160 μm to form a black color photochromic recording material. next,
After the green coloring ink created in (D) was dried,
The squares of 80 μm square were arranged in the front and rear, the space of 160 μm on the left and right, and the space of 40 μm from the photo-coloring recording material of blue color so as to have a thickness of m, and were arranged in an area not coated with the blue color ink. (Refer to FIG. 1) Furthermore, a protective layer was formed on the entire surface by a printing machine using the protective layer ink prepared in (E) to a thickness of 2 μm after drying. A reversible recording medium was created.
【００３３】この媒体を円筒に巻き付け、レーザー照射
装置（波長、７８０ｎｍ、出力４５０ｍＷ）にて、円筒
の回転速度を変えることで走査速度を５０〜６００ｍｍ
／秒まで変化させ照射し描線した。５０〜３００ｍｍ／
秒で青の発色を目視で確認した。この時、緑の発色は認
められなかった。次に発色させる緑との混色を作るた
め、１００ｍｍ／秒で描線し青の発色部分を作った。This medium is wound around a cylinder, and the laser irradiation device (wavelength, 780 nm, output 450 mW) is used to change the rotation speed of the cylinder, thereby making the scanning speed 50 to 600 mm.
/ Second was changed and irradiation was performed to draw a line. 50-300 mm /
The blue color was visually confirmed in seconds. At this time, no green color was observed. Next, in order to create a color mixture with green to be colored, a blue colored portion was created by drawing at 100 mm / sec.
【００３４】次に、青で描線したものを９０°角度を変
え、再度同じ円筒に巻き付け、レーザー照射装置（波
長、９１０ｎｍ、出力４５０ｍＷ）にて、未発色部で走
査速度を５０〜６００ｍｍ／秒と変化させ照射し描線し
た。５０〜２５０ｍｍ／秒で緑の発色が確認された。こ
の時青の発色は認められなかった。また、青の発色部を
１００ｍｍ／秒で描線したところ、緑と青の混色が目視
で確認された。さらに、これら発色したものを１２０℃
の乾燥器に１０分入れ、青、緑の色相とも消去すること
が確認された。Next, the line drawn in blue was changed by 90 ° and wound again on the same cylinder, and a laser irradiation device (wavelength, 910 nm, output 450 mW) was used to scan the uncolored portion at a scanning speed of 50 to 600 mm / sec. It was changed and irradiated and the line was drawn. Green coloration was confirmed at 50 to 250 mm / sec. At this time, no blue color was observed. Further, when the blue colored portion was drawn at 100 mm / sec, a mixed color of green and blue was visually confirmed. Furthermore, these colored ones are heated at 120 ° C.
It was confirmed that both the hues of blue and green were erased by putting them in the drying machine for 10 minutes.
【００３５】実施例２
支持体として厚さ１００μｍ透明ポリエステルフィルム
のおもて面に、印刷機を用いて、（Ａ）で作成した黒発
色用インキと（Ｂ）で作成した赤発色用インクを使用
し、実施例１で行った全く同じパターンで、それぞれ乾
燥後５μｍの厚さになるよう印刷した。さらに、それら
の印刷の上に、同じく印刷機により、（Ｅ）で作成した
保護層インクを使用し乾燥後２μｍの厚さになるよう保
護層を全面に形成し、透明な多色可逆媒体を作った。こ
の媒体を記録面を上にし、実施例１にて作成した青と緑
の多色可逆記録媒体の記録面に重ね、４色の多色可逆記
録媒体を作った。Example 2 Using a printing machine, the black coloring ink prepared in (A) and the red coloring ink prepared in (B) were applied to the front surface of a 100 μm thick transparent polyester film as a support. The same pattern as that used in Example 1 was used and printed so as to have a thickness of 5 μm after drying. Furthermore, a protective multi-layered reversible medium is formed on the entire surface of the printed matter by forming a protective layer on the entire surface with a printing machine using the protective layer ink prepared in (E) to a thickness of 2 μm after drying. Had made. This medium was overlaid on the recording surface of the blue and green multicolor reversible recording medium prepared in Example 1 with the recording surface facing upward to prepare a multicolor reversible recording medium of four colors.
【００３６】この４色の媒体を円筒に巻き付け、円筒に
巻き付け、レーザー照射装置（波長、７８０ｎｍ、出力
４５０ｍＷ）にて、円筒の回転速度を変えることで走査
速度を５０〜６００ｍｍ／秒まで変化させ照射し描線し
た。５０〜３００ｍｍ／秒で青の発色が目視で確認され
た。この時、目的以外の緑、黒、赤の発色は認められな
かった。次に１００ｍｍ／秒で青を発色させ、他の色の
発色確認用に作った。The medium of four colors was wound around a cylinder, and wound around the cylinder, and the laser irradiation device (wavelength, 780 nm, output 450 mW) was used to change the scanning speed of the cylinder to change the scanning speed from 50 to 600 mm / sec. Irradiated and drawn. Blue coloring was visually confirmed at 50 to 300 mm / sec. At this time, no green, black, or red color other than the intended color was observed. Next, blue was developed at 100 mm / sec, and it was made to confirm the development of other colors.
【００３７】次に、再度同じ円筒に巻き付け、レーザー
照射装置（波長、９１０ｎｍ、出力４５０ｍＷ）にて、
走査速度を５０〜６００ｍｍ／秒と変化させ照射し描線
した。未発色部にて５０〜２５０ｍｍ／秒で緑の発色を
確認した。この時、目的以外の色相の発色は認められな
かった。また、次に青の発色部を１００ｍｍ／秒で描線
したところ、緑と青の混色が目視で確認された。さら
に、１００ｍｍ／秒で描線し、緑単色と、緑と青の混色
部分を作り、次の発色確認用とした。Next, the same cylinder was wound again and the laser irradiation device (wavelength, 910 nm, output 450 mW) was used.
The scanning speed was changed from 50 to 600 mm / sec and irradiation was performed to draw a line. In the uncolored portion, green coloring was confirmed at 50 to 250 mm / sec. At this time, no coloring other than the intended hue was observed. Further, when the blue colored portion was drawn at 100 mm / sec, a mixed color of green and blue was visually confirmed. Further, a line was drawn at 100 mm / sec to form a monochromatic green color and a mixed color portion of green and blue, which was used for the next color confirmation.
【００３８】次に、再度同じ円筒に巻き付け、レーザー
照射装置（波長、１０５０ｎｍ、出力６００ｍＷ）に
て、走査速度を５０〜６００ｍｍ／秒と変化させ照射し
描線した。未発色部にて５０〜３００ｍｍ／秒で黒の発
色を確認した。この時、目的以外の色相の発色は認めら
れなかった。また、次に緑単色部を１００ｍｍ／秒で描
線したところ、黒と緑の重色が確認された。また、次に
緑と青の混色部を１００ｍｍ／秒で描線したところ、こ
の混色と黒の重色が確認された。さらに、１００ｍｍ／
秒で描線し、黒の単色、黒と緑の重色、緑と青の混色と
黒の重色部分をそれぞれ作り、次の発色確認用とした。Next, the sample was wound again on the same cylinder, irradiated with a laser irradiation device (wavelength: 1050 nm, output 600 mW) while changing the scanning speed from 50 to 600 mm / sec, and drawn. In the uncolored portion, black coloring was confirmed at 50 to 300 mm / sec. At this time, no coloring other than the intended hue was observed. Further, when the green monochromatic portion was drawn at 100 mm / sec, a black and green overlapping color was confirmed. Further, when the mixed color portion of green and blue was drawn at 100 mm / sec, the mixed color and the black superposed color were confirmed. Furthermore, 100 mm /
The lines were drawn in seconds, and black single color, black and green multiple colors, green and blue mixed colors and black multiple colors were created, respectively, for the next color confirmation.
【００３９】次に、再度同じ円筒に巻き付け、レーザー
照射装置（波長、８３０ｎｍ、出力６００ｍＷ）にて、
走査速度を５０〜６００ｍｍ／秒と変化させ照射し描線
した。未発色部にて５０〜３００ｍｍ／秒で赤の発色を
確認した。この時、目的以外の色相の発色は認められな
かった。また、次に１００ｍｍ／秒で、黒の単色部、黒
と緑の重色部、緑と青の混色と黒の重色部を描線したと
ころ、それぞれ、黒と赤の混色、黒と赤の混色と緑の重
色、緑と青の混色と黒と赤の混色との重色が確認され
た。これらの発色したものを１２０℃の乾燥器に１０分
入れ、すべての発色が消去することを確認した。Then, the same cylinder was wound again, and a laser irradiation device (wavelength, 830 nm, output 600 mW) was used.
The scanning speed was changed from 50 to 600 mm / sec and irradiation was performed to draw a line. In the uncolored part, red coloration was confirmed at 50 to 300 mm / sec. At this time, no coloring other than the intended hue was observed. Next, at 100 mm / sec, the black single color part, the black and green multicolored part, the green and blue mixed color and the black multicolored part were drawn, and the black and red mixed color and the black and red respectively were drawn. A mixed color of green and green, a mixed color of green and blue, and a mixed color of black and red were confirmed. It was confirmed that all of the developed colors were erased by putting the developed products in a dryer at 120 ° C. for 10 minutes.
【００４０】比較例２
実施例２において作成した４色の多色可逆記録媒体を円
筒に巻き付け、レーザー照射装置（波長、８３０ｎｍ、
出力４５０ｍＷ）にて、円筒の回転速度を変えることで
走査速度を５０〜６００ｍｍ／秒まで変化させ照射し描
線した。５０〜３００ｍｍ／秒で赤の発色が目視で確認
された。この時、目的以外の緑、黒、赤の発色は認めら
れなかった。次に１００ｍｍ／秒で描線し、赤を発色さ
せ、他の色の発色確認用に作った。Comparative Example 2 The four-color multicolor reversible recording medium prepared in Example 2 was wound around a cylinder, and a laser irradiation device (wavelength, 830 nm,
At an output of 450 mW), the scanning speed was changed to 50 to 600 mm / sec by changing the rotation speed of the cylinder, and irradiation was performed to draw a line. A red color was visually confirmed at 50 to 300 mm / sec. At this time, no green, black, or red color other than the intended color was observed. Next, a line was drawn at 100 mm / sec to develop red color, and it was made to confirm the color development of other colors.
【００４１】次に、再度同じ円筒に巻き付け、レーザー
照射装置（波長、１０５０ｎｍ、出力６００ｍＷ）に
て、走査速度を５０〜６００ｍｍ／秒と変化させ照射し
描線した。未発色部で５０〜３００ｍｍ／秒で黒の発色
を確認した。この時、目的以外の色相の発色は認められ
なかった。また、次に赤の発色部を１００ｍｍ／秒で描
線したところ、黒と赤の混色が確認された。さらに、１
００ｍｍ／秒で描線し、黒の単色部と黒と赤の混色部を
作り、次の発色確認用とした。Next, the sample was again wound on the same cylinder, irradiated with a laser irradiation device (wavelength: 1050 nm, output 600 mW) while changing the scanning speed from 50 to 600 mm / sec, and drawn. Black coloring was confirmed at 50 to 300 mm / sec in the uncolored portion. At this time, no coloring other than the intended hue was observed. Further, when the red colored part was drawn at 100 mm / sec, a mixed color of black and red was confirmed. Furthermore, 1
A line was drawn at 00 mm / sec to form a black single color portion and a black and red mixed color portion, which was used for the next color confirmation.
【００４２】次に、レーザー照射装置（波長、９１０ｎ
ｍ、出力４５０ｍＷ）にて、走査速度を５０〜６００ｍ
ｍ／秒と変化させ照射し描線した。未発色部にて５０〜
２５０ｍｍ／秒で緑の発色を確認した。この時、目的以
外の色相の発色は認められなかった。次に黒の単色部と
黒と赤の混色部を１００ｍｍ／秒で描線したところ、黒
の単色部では緑の発色は認められたが、黒と赤の混色部
では緑の発色は認められなかった。Next, a laser irradiation device (wavelength: 910n)
m, output 450 mW), scanning speed 50-600 m
It was changed to m / sec and irradiated to draw a line. 50 ~ in the uncolored part
A green color was confirmed at 250 mm / sec. At this time, no coloring other than the intended hue was observed. Next, when the black single color part and the mixed color part of black and red were drawn at 100 mm / sec, green coloration was observed in the black single color part, but green coloration was not observed in the black and red mixed color part. It was
【００４３】[0043]
【発明の効果】本発明は前記の通り、レーザー光の波長
を選定し目的の色を発色させるので、鮮明な高画質の発
色を得ることが可能である。レーザー光とその波長を有
効に吸収する光熱変換材料を組み合わせることで、４色
で表現するフルカラーも可能である。As described above, according to the present invention, since the wavelength of the laser beam is selected and a desired color is developed, it is possible to obtain a clear and high quality color development. By combining laser light and a photothermal conversion material that effectively absorbs its wavelength, full-color expression with four colors is also possible.
【００４４】多色可逆感熱層を複数層有する多色可逆感
熱記録媒体を発色させる場合、最下層から発色させるこ
とで、発色部がレーザー光を吸収し、目的の色の発色を
妨害するのを防止できる。When a multicolor reversible thermosensitive recording medium having a plurality of multicolor reversible thermosensitive layers is used for color development, the color development part absorbs laser light and interferes with the development of a desired color by developing the color from the lowermost layer. It can be prevented.
【図１】本発明実施例１でいう多色記録をしめすもので
ある。FIG. 1 illustrates multicolor recording as described in Example 1 of the present invention.
Claims (5)
イコ染料に対応する光熱変換材料（Ｔｎ）からなる光発
色記録体（Ｍｎ）を、Ｍ１（Ｒ１，Ｔ１）,Ｍ２（Ｒ
２，Ｔ２），・・・，Ｍｎ（Ｒｎ，Ｔｎ）の組合せで２
以上有し、該２以上の光発色記録体、すなわちＭ１，Ｍ
２，・・・，Ｍｎ（ｎ≧２）を１ユニットとし、該ユニ
ットが支持体上に均一に配置されていることを特徴とす
る多色可逆記録媒体1. A photochromic recording material (Mn) comprising a leuco dye (Rn), a reversible color developer, and a photothermal conversion material (Tn) corresponding to the leuco dye is used as M1 (R1, T1), M2 (R).
2, T2), ..., 2 in combination of Mn (Rn, Tn)
The above-mentioned two or more photo-coloring recording materials, that is, M1 and M
2, ..., Mn (n ≧ 2) as one unit, and the unit is uniformly arranged on a support, and a multicolor reversible recording medium is provided.
イコ染料に対応する光熱変換材料（Ｔｎ）からなる光発
色記録体（Ｍｎ）を、Ｍ１（Ｒ１，Ｔ１）,Ｍ２（Ｒ
２，Ｔ２），・・・，Ｍｎ（Ｒｎ，Ｔｎ）の組合せで２
以上有し、該２以上の光発色記録体、すなわちＭ１，Ｍ
２，・・・，Ｍｎ（ｎ≧２）を１ユニットとし、該ユニ
ットが均一に配置された多色記録層を支持体上に複数有
し、該複数層に存在する該光発色記録体の種類がすべて
異なることを特徴とする多色可逆記録媒体2. A photochromic recording material (Mn) comprising a leuco dye (Rn), a reversible color developer, and a photothermal conversion material (Tn) corresponding to the leuco dye is used as M1 (R1, T1), M2 (R).
2, T2), ..., 2 in combination of Mn (Rn, Tn)
The above-mentioned two or more photo-coloring recording materials, that is, M1 and M
2, ..., Mn (n ≧ 2) is set as one unit, and a plurality of multicolor recording layers in which the units are uniformly arranged are provided on the support, and Multicolor reversible recording medium characterized by different types
置されていることを特徴とする請求項１及び請求項２の
多色可逆記録媒体3. The multicolor reversible recording medium according to claim 1, wherein the photochromic recording medium is arranged on the support by printing.
載の多色可逆記録媒体が有する光発色記録体を、それぞ
れの該光発色記録体に含まれる光熱変換材料の光熱変換
に有効な波長の光を順次照射し、発色させ、多色画像を
形成させる方法4. The photochromic recording medium of the multicolor reversible recording medium according to claim 1, 2 or 3 is effective for photothermal conversion of the photothermal conversion material contained in each photochromic recording medium. Method of forming multicolor image by sequentially irradiating light with different wavelengths to develop color
最下層から順次上層に向けて発色させ、多色画像を形成
させることを特徴とする方法5. The method according to claim 4, wherein a color is developed from the lowermost layer of the multicolor recording layer to the upper layer sequentially to form a multicolor image.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001316278A JP3784295B2 (en) | 2001-10-15 | 2001-10-15 | Multicolor reversible thermosensitive recording medium |
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|---|---|
| JP2003118241A true JP2003118241A (en) | 2003-04-23 |
| JP2003118241A5 JP2003118241A5 (en) | 2005-04-07 |
| JP3784295B2 JP3784295B2 (en) | 2006-06-07 |
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ID=19134314
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210016588A1 (en) * | 2017-12-08 | 2021-01-21 | Agfa Nv | Near infrared (nir) laser processing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000025338A (en) * | 1998-07-08 | 2000-01-25 | Gunze Ltd | Thermal reversible multi-color recording medium |
| JP2001001645A (en) * | 1999-06-24 | 2001-01-09 | Gunze Ltd | Thermally reversible multiple color recording medium |
-
2001
- 2001-10-15 JP JP2001316278A patent/JP3784295B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000025338A (en) * | 1998-07-08 | 2000-01-25 | Gunze Ltd | Thermal reversible multi-color recording medium |
| JP2001001645A (en) * | 1999-06-24 | 2001-01-09 | Gunze Ltd | Thermally reversible multiple color recording medium |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210016588A1 (en) * | 2017-12-08 | 2021-01-21 | Agfa Nv | Near infrared (nir) laser processing |
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|---|---|
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