JP2003237232A - Reversible heat-sensitive recording medium and heat- sensitive recording device mounted with the same - Google Patents
Reversible heat-sensitive recording medium and heat- sensitive recording device mounted with the sameInfo
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- JP2003237232A JP2003237232A JP2002037385A JP2002037385A JP2003237232A JP 2003237232 A JP2003237232 A JP 2003237232A JP 2002037385 A JP2002037385 A JP 2002037385A JP 2002037385 A JP2002037385 A JP 2002037385A JP 2003237232 A JP2003237232 A JP 2003237232A
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- Japan
- Prior art keywords
- recording medium
- reversible thermosensitive
- color
- state
- sensitive recording
- Prior art date
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- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子供与性呈色性
化合物と電子受容性化合物との間の発色反応を利用した
可逆性感熱発色組成物を用い、熱エネルギーを制御する
ことにより発色画像の形成と消去が可能な可逆性感熱記
録媒体、および該可逆性感熱記録媒体を搭載した感熱記
録装置に関する。TECHNICAL FIELD The present invention relates to a reversible thermosensitive color-forming composition utilizing a color-forming reaction between an electron-donating color-forming compound and an electron-accepting compound and controlling a thermal energy to form a color image. The present invention relates to a reversible thermosensitive recording medium capable of forming and erasing, and a thermosensitive recording device equipped with the reversible thermosensitive recording medium.
【０００２】[0002]
【従来の技術】従来、電子供与性呈色性化合物（以下、
発色剤またはロイコ染料ともいう）と電子受容性化合物
（以下、顕色剤ともいう）との間の発色反応を利用した
感熱記録媒体は広く知られており、ファクシミリ、ワー
ドプロセッサー、科学計測機などのプリンターに使用さ
れている。しかし、これらの実用化されている従来の記
録媒体はいずれも不可逆的な発色であり、一度記録した
画像を消去して繰り返して使用することはできない。一
方、特許公報によれば発色と消色を可逆的に行うことが
できる記録媒体も提案されており、たとえば、顕色剤と
して没食子酸とフロログルシノールを組合せを用いる特
開昭６０−１９３６９１号公報、顕色剤にフェノールフ
タレインやチモールフタレインなどの化合物を用いる特
開昭６１−２３７６８４号公報、発色剤と顕色剤とカル
ボン酸エステルの均質相溶体を記録層に含有する特開昭
６２−１３８５５６号、特開昭６２−１３８５６８号お
よび特開昭６２−１４０８８１号公報、顕色剤にアスコ
ルビン酸誘導体を用いた特開昭６３−１７３６８４号公
報、顕色剤にビス（ヒドロキシフェニル）酢酸または没
食子酸と高級脂肪族アミンとの塩を用いる特開平２−１
８８２９３号公報および特開平２−１８８２９４号公報
などが開示されている。2. Description of the Related Art Conventionally, electron-donating color-forming compounds (hereinafter referred to as
Thermosensitive recording media that utilize the color-forming reaction between a color former or leuco dye) and an electron-accepting compound (hereinafter also referred to as a developer) are widely known, and can be used in facsimiles, word processors, scientific measuring instruments, etc. Used in printers. However, all of these conventional recording media that have been put to practical use have irreversible color development, and it is not possible to erase an image once recorded and repeatedly use it. On the other hand, according to the patent publication, a recording medium capable of reversibly developing and erasing color is also proposed. For example, JP-A-60-193691 uses a combination of gallic acid and phloroglucinol as a developer. JP-A-61-237684, which uses a compound such as phenolphthalein or thymolphthalein as a color developer, and JP-A-61-237684, which contains a homogenous solution of a color developer, a color developer, and a carboxylic acid ester in a recording layer. 62-138556, JP-A-62-138568 and JP-A-62-140881, JP-A-63-173684 using an ascorbic acid derivative as a developer, and bis (hydroxyphenyl) as a developer. Use of a salt of acetic acid or gallic acid and a higher aliphatic amine
Japanese Patent Laid-Open No. 88293 and Japanese Patent Laid-Open No. 2-188294 are disclosed.
【０００３】さらに本発明者らは、先に特開平５−１２
４３６０号公報において顕色剤として長鎖脂肪族炭化水
素基をもつ有機リン酸化合物、脂肪族カルボン酸化合物
またはフェノール化合物を用い、これと発色剤であるロ
イコ染料と組み合わせることによって、発色と消色を加
熱冷却条件により容易に行わせることができ、しかもそ
の発色状態と消色状態を常温において安定に保持させる
ことが可能であり、しかも発色と消色を繰り返すことが
可能な可逆性感熱発色組成物およびこれを記録層に用い
た可逆性感熱記録媒体を提案した。またその後、長鎖脂
肪族炭化水素基をもつフェノール化合物について特定の
構造の使用が提案されている（特開平６−２１０９５
４）。Furthermore, the present inventors have previously disclosed in Japanese Patent Laid-Open No. 5-12
No. 4360, an organic phosphoric acid compound, an aliphatic carboxylic acid compound or a phenol compound having a long-chain aliphatic hydrocarbon group is used as a color developing agent, and by combining this with a leuco dye which is a color developing agent, color development and decolorization. Can be easily carried out under heating and cooling conditions, and its colored and decolored states can be stably maintained at room temperature, and a reversible thermosensitive coloring composition capable of repeating coloring and decoloring And a reversible thermosensitive recording medium using the same as a recording layer. Also, since then, it has been proposed to use a specific structure for a phenol compound having a long-chain aliphatic hydrocarbon group (JP-A-6-21095).
4).
【０００４】[0004]
【発明が解決しようとする課題】前記材料を用いて作製
された可逆性感熱記録媒体はサーマルヘッドによる発色
や、ホットスタンプなどによる消去ができ、繰り返して
の発色／消色が可能なものである。しかし、近年、記録
媒体の書き換え時間の短縮が求められており、これらの
可逆性感熱記録媒体ではそれら低温域での高速消去に対
応できない。本発明の課題は、低温域での高速消去生と
発色画像の安定性に優れる可逆性感熱記録媒体を提供す
ることである。The reversible thermosensitive recording medium produced by using the above material is capable of color development by a thermal head, erasing by hot stamping, etc., and repeated color development / erasing. . However, in recent years, there has been a demand for shortening the rewriting time of recording media, and these reversible thermosensitive recording media cannot support high-speed erasing in the low temperature region. An object of the present invention is to provide a reversible thermosensitive recording medium which is excellent in high-speed erasure in a low temperature range and stability of a color image.
【０００５】[0005]
【課題を解決するための手段】本発明者らは可逆性感熱
記録媒体の消色温度および高速消去性に関して種々の検
討を行ったところ、発色消色制御剤として結合基Ｙおよ
び末端に２つの長鎖アルキル基を有する構造の化合物を
用いることにより、記録媒体の低温域での高速消去性が
向上することがわかった。特に、発色消色制御剤として
長鎖アルキル基を両末端にそれぞれ２つずつ有する構造
の化合物として、下記式（１）の化合物が前記課題の解
決のために有効なことを見出した。The inventors of the present invention have made various studies on the decoloring temperature and high-speed erasability of a reversible thermosensitive recording medium. It was found that the use of a compound having a structure having a long-chain alkyl group improves the high-speed erasability of the recording medium at low temperature. In particular, it has been found that the compound of the following formula (1) is effective for solving the above-mentioned problems as a compound having a structure having two long-chain alkyl groups at each end as a color-decoloration controlling agent.
【０００６】[0006]
【化２】
（Ｒ１は置換基を有してもよい炭素数１〜２２の２価の
炭化水素基、Ｒ２，Ｒ３は炭素数８以上のアルキル基を
それぞれ表す。ｎは７以上の整数、Ｘはヘテロ原子を含
む３価の結合基を、Ｙはヘテロ原子を含む２価の結合基
をそれぞれ示す）[Chemical 2] (R 1 represents a divalent hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, R 2 and R 3 each represent an alkyl group having 8 or more carbon atoms, n is an integer of 7 or more, X Represents a trivalent linking group containing a hetero atom, and Y represents a divalent linking group containing a hetero atom.)
【０００７】前記式（１）の化合物が前記解決しようと
する課題の解決に有効である詳細な理由は定かではない
が、発色状態を形成するロイコ染料および顕色剤と本発
明の下記式（１）で示される発色消色制御剤からなる凝
集構造中において、これらの発色消色制御剤は末端に２
つの長鎖アルキル基を有するためアルキル鎖の凝集力が
非常に高く、消去装置で加熱された際に安定な状態であ
る消色状態になりやすく、また会合基Ｙの会合性により
発色状態も安定するため高い発色画像安定性を有すると
考えられる。さらに、溶融状態からの急冷条件では発色
状態を取るが徐冷条件あるいは溶融温度以下の熱が加え
られると顕色剤の長鎖アルキル基との相互作用により容
易に消色状態になると考えられる。Although the detailed reason why the compound of the formula (1) is effective in solving the problem to be solved is not clear, the leuco dye and the developer which form a color-developed state and the following formula (1) of the present invention ( In the aggregation structure composed of the color-decoloring control agent represented by 1), these color-decoloring control agents have 2 terminals at the end.
Since it has two long-chain alkyl groups, the cohesive force of the alkyl chains is very high, and when it is heated by an erasing device, it tends to be in a stable decolored state, and the associative property of the associative group Y also stabilizes the colored state. Therefore, it is considered to have high color image stability. Further, it is considered that a coloring state is obtained under the rapid cooling condition from the molten state, but when the cooling is performed under the slow cooling condition or the melting temperature or less, the decolored state is easily obtained by the interaction with the long-chain alkyl group of the developer.
【０００８】すなわち、本発明においては、支持体上に
電子供与性呈色性化合物と電子受容性化合物を用い、加
熱温度及び／又は加熱後の冷却速度の違いにより相対的
に発色した状態を形成しうる可逆性感熱組成物を含有す
る可逆性感熱記録層を有する可逆性感熱記録媒体におい
て、該可逆性感熱記録層中に発色消色制御剤として前記
式（１）の化合物を用いることを特徴とする可逆性感熱
記録媒体が提供される。That is, in the present invention, an electron-donating color-forming compound and an electron-accepting compound are used on a support to form a relatively colored state due to the difference in heating temperature and / or cooling rate after heating. In a reversible thermosensitive recording medium having a reversible thermosensitive recording layer containing a reversible thermosensitive composition, a compound of the above formula (1) is used as a coloring and decoloring control agent in the reversible thermosensitive recording layer. A reversible thermosensitive recording medium is provided.
【０００９】以下に本発明で用いる発色消色制御剤を説
明する。前式（１）中のＲ１は炭素数１〜２２の２価の
炭化水素基を表し前記炭化水素基は置換基を有していて
もよいが、好ましくは炭素数１〜１８の２価の炭化水素
基が用いられる。Ｒ２，Ｒ３はそれぞれ独立に炭素数８
以上の飽和あるいは不飽和のアルキル基を表わし、該ア
ルキル基は分岐していてもよく置換基を含んでいてもよ
い、またエーテル結合、エステル結合、チオエーテル結
合を含んでいてもよいが、好ましくは炭素数１２から２
２の直鎖状のアルキル基が用いられる。末端の長鎖アル
キル基はその凝集力により消去性の向上に寄与するが、
ある程度の長さを持たないとその効果が不十分であり、
また、長すぎると画像の安定性が低下するので、前記の
ように炭素数１２から２２の直鎖状のアルキル基が好ま
しい。また、Ｒ２とＲ３はその炭素数が等しいことが好
ましい。The color-decoloring control agent used in the present invention will be described below. R 1 in the above formula (1) represents a divalent hydrocarbon group having 1 to 22 carbon atoms, and the hydrocarbon group may have a substituent, but preferably has 1 to 18 carbon atoms. Hydrocarbon groups are used. R 2 and R 3 each independently have 8 carbon atoms
The above saturated or unsaturated alkyl group is represented, and the alkyl group may be branched or may contain a substituent, and may contain an ether bond, an ester bond or a thioether bond, but is preferably 12 to 2 carbon atoms
Two linear alkyl groups are used. The long-chain alkyl group at the terminal contributes to the improvement of erasability due to its cohesive force,
The effect is insufficient if it does not have a certain length,
Further, if the length is too long, the stability of the image is deteriorated. Therefore, as described above, a linear alkyl group having 12 to 22 carbon atoms is preferable. Further, it is preferable that R 2 and R 3 have the same carbon number.
【００１０】下記化３にＲ１の好ましい構造の例を挙げ
るが，特に化３に示すものに限られるものではない。化
３の構造式中、ｎ，ｎ’’，ｎ’’’は０以上の整数を
表す。Examples of preferable structures of R 1 are shown in the following chemical formula 3, but not limited to those shown in the chemical formula 3. In the structural formula of Chemical formula 3, n, n ″, and n ′ ″ represent an integer of 0 or more.
【化３】 [Chemical 3]
【００１１】また、下記化４にＲ２，Ｒ３の好ましい構
造の例を挙げるが，特に化４に示すものに限られるもの
ではない。化４の構造式中、ｎ，ｎ’，ｎ’’は０以上
の整数を表すが、それぞれの構造において総炭素数は８
以上とする。Further, the following chemical formula 4 gives examples of preferable structures of R 2 and R 3 , but the structure is not limited to the chemical formula 4. In the structural formula of Chemical formula 4, n, n ′, and n ″ represent integers of 0 or more, but the total number of carbon atoms in each structure is 8
That is all.
【化４】 [Chemical 4]
【００１２】また、式（１）中のＸはヘテロ原子を含む
３価の結合基であるが、下記化５の基が消色能の点で好
ましい。X in the formula (1) is a trivalent linking group containing a hetero atom, and the group represented by the following chemical formula 5 is preferable from the viewpoint of decoloring ability.
【化５】 [Chemical 5]
【００１３】前記化５に示される結合基Ｘの中でも、下
記化６および７で示される基が特に好ましい。Of the linking groups X shown in Chemical formula 5, the groups shown in Chemical formulas 6 and 7 below are particularly preferable.
【化６】 [Chemical 6]
【化７】 [Chemical 7]
【００１４】式（１）中のＹはヘテロ原子を含む２価の
結合基であるが、結合基Ｙとしては、下記化８で表され
る基を含んだものが、ＮＨＣＯ基の会合性による発色画
像安定性に優れているので好ましい。Y in the formula (1) is a divalent linking group containing a hetero atom. As the linking group Y, a group containing a group represented by the following chemical formula 8 is used because of the association property of the NHCO group. It is preferable because the stability of the color image is excellent.
【化８】 [Chemical 8]
【００１５】本発明で用いられる発色消色制御剤に好ま
しく用いられる結合基Ｘの具体的な例としては下記化９
の基が挙げられる。Specific examples of the linking group X which is preferably used in the color-decoloration controlling agent used in the present invention are shown below.
Groups.
【００１６】[0016]
【化９】 [Chemical 9]
【００１７】以下に本発明で用いられる発色消色制御剤
の具体例を下記化１０に挙げる。しかしながら、本発明
で用いることができる発色消色制御剤は下記化１０のも
のに限られるわけではない。Specific examples of the color development / decoloration control agent used in the present invention are shown below in Chemical Formula 10. However, the color-decoloring control agent that can be used in the present invention is not limited to the following chemical formula 10.
【００１８】[0018]
【化１０】 [Chemical 10]
【００１９】本発明において用いられるロイコ染料とし
ては、この種の可逆性感熱記録媒体に用いられる化合物
を１種または２種以上用いることができ、たとえば、フ
タリド化合物、アザフタリド化合物、フルオラン化合物
など公知の染料前駆体である。また、記録層中に用いら
れるは顕色剤としては、代表例として、たとえば特開平
５−１２４３６０号公報、特開平６−２１０９５４号公
報、特開平１０−９５１７５号公報などに記載の記録層
である。ここで用いる顕色剤は、分子内にロイコ染料を
発色させる顕色能をもつ構造、たとえばフェノール性水
酸基、カルボン酸基、リン酸基などと、分子間の凝集力
を制御する構造、たとえば長鎖炭化水素基が連結した構
造を一つ以上もつ化合物である。連結部分にはヘテロ原
子を含む２価以上の連結基を介していても良く、また長
鎖炭化水素基中にも同様の連結基および／または芳香族
基が含まれていても良い。このような可逆性顕色剤の具
体例はたとえば特開平９−２９０５６３号公報、特開平
１１−１８８９６９号公報に記載に示されている。As the leuco dye used in the present invention, one or more compounds used in this type of reversible thermosensitive recording medium can be used. For example, phthalide compounds, azaphthalide compounds, fluoran compounds, etc. It is a dye precursor. Further, as the color developer used in the recording layer, a recording layer described in, for example, JP-A-5-124360, JP-A-6-210954, and JP-A-10-95175 is a typical example. is there. The color developer used here has a structure capable of developing a leuco dye in the molecule, such as a phenolic hydroxyl group, a carboxylic acid group or a phosphoric acid group, and a structure for controlling the cohesive force between molecules, such as a long chain. It is a compound having one or more structures in which chain hydrocarbon groups are linked. The linking part may be via a divalent or higher valent linking group containing a hetero atom, and the long-chain hydrocarbon group may also contain the same linking group and / or aromatic group. Specific examples of such a reversible developer are described in, for example, JP-A 9-290563 and JP-A 11-188969.
【００２０】これらのロイコ染料および顕色剤を用いた
可逆性記録層は図１に示すプロセスで発色・消色する。
初期の消色状態（Ａ）を加熱すると温度Ｔ１以上でロイ
コ染料と顕色剤が溶融混合して発色し（Ｂ）、この状態
を急冷すると発色状態が固定される。発色状態（Ｃ）を
加熱すると、発色温度より低い温度Ｔ２で消色し、冷却
すれば初期と同様の消色状態となる。このように記録層
は加熱温度および加熱後の冷却速度の制御によって記録
消去ができる。この記録層による印字は、コントラスト
が高く優れた画像品質が得られる。また、保存安定性や
印字消去の繰り返し耐久性にも優れ、本発明の文書用書
き替え型記録媒体としてとくに適している。この記録層
を用いた可逆性記録媒体の印字は通常の感熱記録と同様
にサーマルヘッドで行うことができ、消去は温度制御さ
れたヒートローラ、セラミックヒータ等の発熱体および
サーマルヘッドなどによってできるため、小型で簡易な
書き替え記録装置で使用できる。The reversible recording layer using these leuco dye and developer develops and decolors by the process shown in FIG.
When the initial decolored state (A) is heated, the leuco dye and the color developer are melt-mixed at the temperature T1 or higher to develop a color (B), and when this state is rapidly cooled, the colored state is fixed. When the color-developed state (C) is heated, the color is erased at a temperature T2 lower than the color-developing temperature. In this way, the recording layer can be erased by controlling the heating temperature and the cooling rate after heating. Printing with this recording layer provides high contrast and excellent image quality. Further, it is excellent in storage stability and durability against repeated printing and erasing, and is particularly suitable as the rewritable recording medium for documents of the present invention. Printing on a reversible recording medium using this recording layer can be performed by a thermal head as in normal thermal recording, and erasing can be performed by a temperature-controlled heat roller, a heating element such as a ceramic heater, or a thermal head. Can be used with a small and simple rewrite device.
【００２１】本発明の可逆性感熱記録媒体はロイコ染
料、顕色剤および発色消色制御剤は樹脂とともに記録層
を形成する。このとき用いられる樹脂は支持体上にこれ
らの材料を結着できれば良く、従来公知の樹脂が広く用
いられる。なかでも、繰り返し時の耐久性を向上させる
ため、熱や紫外線、電子線などによって硬化可能な樹脂
が好ましく用いられ、とくにイソシアネート化合物など
を架橋剤として用いた熱硬化型の樹脂がとくに好ましく
用いられる。The reversible thermosensitive recording medium of the present invention forms a recording layer together with a leuco dye, a color developer and a color-decoloration controlling agent together with a resin. The resin used at this time may be any resin as long as it can bind these materials to the support, and conventionally known resins are widely used. Among them, a resin curable by heat, ultraviolet rays, electron rays or the like is preferably used in order to improve durability during repetition, and a thermosetting resin using an isocyanate compound or the like as a crosslinking agent is particularly preferably used. .
【００２２】本発明の可逆性感熱記録媒体においては、
発色感度の向上、耐久性の向上、耐光性の向上等のため
にアンダー層や保護層、バック層などを設けても良く、
これらの層中には樹脂とともに、有機／無機フィラー、
紫外線吸収剤、滑材、着色顔料などを用いることができ
る。本発明の可逆性感熱記録媒体の支持体としては、記
録層を保持できればよく、好ましくは、紙、合成紙、Ｐ
ＥＴフィルム等が用いられる。また、これらの支持体を
介して他のものに貼付けて用いても良い。In the reversible thermosensitive recording medium of the present invention,
An under layer, a protective layer, a back layer, or the like may be provided to improve color development sensitivity, durability, light resistance, and the like.
In these layers, together with the resin, organic / inorganic filler,
An ultraviolet absorber, a lubricant, a coloring pigment, etc. can be used. The support for the reversible thermosensitive recording medium of the present invention is only required to be able to retain the recording layer, and is preferably paper, synthetic paper or P
ET film or the like is used. Further, it may be used by being attached to other things via these supports.
【００２３】前記式（１）の発色消色制御剤を用いた本
発明の可逆性感熱記録媒体を有する熱可逆性記録部と情
報記録部の両方を設けることにより、情報記憶部に記憶
された情報を熱可逆性記録部に表示することで、特別な
装置がなくても情報を確認することができ、利便性が向
上する。その際に用いられる記憶部は磁気記録層やＩＣ
記録部などが好ましく用いられる。By storing both the thermoreversible recording section and the information recording section having the reversible thermosensitive recording medium of the present invention using the coloring / discoloring control agent of the formula (1), the information is stored in the information storage section. By displaying the information on the thermoreversible recording unit, the information can be confirmed without a special device, and the convenience is improved. The storage unit used at that time is a magnetic recording layer or an IC.
A recording section or the like is preferably used.
【００２４】本発明の可逆性感熱記録媒体は、その用途
に応じた形に容易に加工することができ、例えばカード
状、シート状、ロール状などに加工される。カード状に
加工されたものについてはプリペイドカードやポイント
カードさらにはクレジットカードなどへの応用が挙げら
れ、また、シート状に加工されたものは、Ａ４サイズな
ど一般文書サイズに加工された場合、印字／消去装置を
用いることにより、試し印字はもちろんのこと、回覧文
書や会議資料など一時出力用途などに広く用いることが
できる。さらに、ロール状に加工されたものは、印字／
消去部を有した装置に組み込まれるなどして、表示板・
掲示板または電子黒板に用いることができる。このよう
な表示装置は塵、ゴミなどの発生がないため、クリーン
ルームなどに好ましく用いることができる。The reversible thermosensitive recording medium of the present invention can be easily processed into a shape suitable for the intended use, for example, a card shape, a sheet shape, a roll shape or the like. For cards processed, it can be applied to prepaid cards, point cards, credit cards, etc. In addition, sheets processed can be printed when processed to general document size such as A4 size. By using the erasing device, it can be widely used not only for trial printing but also for temporary output such as circulation documents and conference materials. In addition, if it is processed into a roll,
As it is installed in a device that has an erasing unit,
It can be used for bulletin boards or electronic blackboards. Since such a display device does not generate dust or dirt, it can be preferably used in a clean room or the like.
【００２５】[0025]
【実施例】以下に実施例によって本発明をさらに詳しく
説明する。なお、実施例中の「部」および「％」はいず
れも重量を基準とするものである。The present invention will be described in more detail with reference to the following examples. In the examples, "parts" and "%" are based on weight.
【００２６】 実施例１ 記録層の作成 １）２−アニリノ−３−メチル−６ジブチルアミノフルオラン ２．５部 ２）下記化１１の構造式の顕色剤 １０部[0026] Example 1 Create recording layer 1) 2-anilino-3-methyl-6 dibutylaminofluorane 2.5 parts 2) 10 parts of the color developer of the structural formula shown below.
【化１１】 ３）下記化１２の構造式の発色消色制御剤 ３．５部[Chemical 11] 3) 3.5 parts of coloring and decoloring control agent having the structural formula shown below.
【化１２】
４）アクリルポリオール樹脂の１５％テトラヒドロフラン（ＴＨＦ）溶液
１６０部
上記組成物をボールミルを用いて平均粒径約１μｍまで
粉砕分散した。得られた分散液に日本ポリウレタン社製
コロネートＨＬ（アダクト型ヘキサメチレンジイソシア
ネート ７５％酢酸エチル溶液）２０部を加え、良く攪
拌し記録層塗布液を調製した。上記組成の記録層塗布液
を、厚さ１２５μｍの白色ポリエステルフィルム上にワ
イヤーバーを用い塗布し、１００℃２分で乾燥した後、
６０℃２４時間加熱して、膜厚約９．０μｍの記録層を
設けた。
［保護層の作成］
１）ウレタンアクリレート系紫外線硬化性樹脂
（大日本インキ社製Ｃ７−１５７） １５部
２）酢酸エチル ８５部
上記組成物を、よく溶解攪拌し保護層塗布液を調製し
た。上記組成の保護層塗布液を、上記記録層上にワイヤ
ーバーを用いて塗工し９０℃１分で乾燥した後、照射エ
ネルギー８０Ｗ／ｃｍの紫外線ランプ下を９ｍ／分の搬
送速度で通して硬化して膜厚３μｍの保護層を設け、本
発明の可逆性感熱記録媒体を作製した。[Chemical 12] 4) 15% tetrahydrofuran (THF) solution of acrylic polyol resin 160 parts The above composition was pulverized and dispersed by a ball mill to an average particle size of about 1 μm. 20 parts of Coronate HL (75% ethyl acetate solution of adduct-type hexamethylene diisocyanate) manufactured by Nippon Polyurethane Industry Co., Ltd. was added to the obtained dispersion liquid and well stirred to prepare a recording layer coating liquid. The coating solution for recording layer having the above composition was coated on a white polyester film having a thickness of 125 μm using a wire bar and dried at 100 ° C. for 2 minutes.
It was heated at 60 ° C. for 24 hours to form a recording layer having a film thickness of about 9.0 μm. [Preparation of protective layer] 1) Urethane acrylate UV curable resin (C7-157 manufactured by Dainippon Ink and Chemicals, Inc.) 15 parts 2) Ethyl acetate 85 parts The above composition was well dissolved and stirred to prepare a protective layer coating solution. The coating solution for the protective layer having the above composition was applied onto the recording layer using a wire bar and dried at 90 ° C. for 1 minute, and then passed under an ultraviolet lamp with irradiation energy of 80 W / cm at a conveying speed of 9 m / min. A reversible thermosensitive recording medium of the present invention was prepared by curing and providing a protective layer having a film thickness of 3 μm.
【００２７】実施例２
実施例１の発色消色制御剤を下記化１３の構造式の化合
物に代えた以外は実施例１と同様にして可逆性感熱記録
媒体を作成した。Example 2 A reversible thermosensitive recording medium was prepared in the same manner as in Example 1 except that the color-decoloration controlling agent of Example 1 was replaced with the compound having the structural formula of the following chemical formula 13.
【化１３】 [Chemical 13]
【００２８】実施例３
実施例１の顕色剤と発色消色制御剤を下記化１４および
１５の構造式の化合物に代えた以外は実施例１と同様に
して可逆性感熱記録媒体を作成した。顕色剤Example 3 A reversible thermosensitive recording medium was prepared in the same manner as in Example 1 except that the color developer and the color-decoloration controlling agent of Example 1 were replaced with the compounds of the structural formulas 14 and 15 below. . Developer
【００２９】[0029]
【化１４】 発色消色制御剤[Chemical 14] Color development / decoloration control agent
【化１５】 [Chemical 15]
【００３０】比較例１
実施例１中の発色消色制御剤を除いた以外は実施例１と
同様にして可逆性感熱記録媒体を作製した。Comparative Example 1 A reversible thermosensitive recording medium was prepared in the same manner as in Example 1 except that the coloring / decoloring control agent in Example 1 was omitted.
【００３１】比較例２
実施例１中の記発色消色制御剤を下記化１６の化合物に
変えた以外は実施例１と同様にして可逆性感熱記録媒体
を作製した。Comparative Example 2 A reversible thermosensitive recording medium was prepared in the same manner as in Example 1 except that the recording / decoloring / decoloring controlling agent in Example 1 was changed to the compound represented by the following chemical formula 16.
【化１６】 [Chemical 16]
【００３２】比較例３
実施例１中の記発色消色制御剤を下記化１７の化合物に
変えた以外は実施例１と同様にして可逆性感熱記録媒体
を作製した。Comparative Example 3 A reversible thermosensitive recording medium was prepared in the same manner as in Example 1 except that the recording / decoloring / decoloring controlling agent in Example 1 was changed to the compound represented by the following chemical formula 17.
【化１７】 [Chemical 17]
【００３３】試験１ 発色濃度
作製した記録媒体を大倉電機社製感熱印字装置にて、電
圧１３．３Ｖ、パルス幅１．２ｍｓｅｃで印字し、得ら
れた発色画像をマクベス濃度計ＲＤ−９１４で測定し
た。
試験２ 消去特性
試験１で得られた発色画像を、東洋精機社製熱傾斜試験
機で１２０℃ １秒の条件で消色して消色後の画像部の
濃度と地肌濃度を試験１と同様に測定した。以上の結果
を表１に示した。Test 1 Color density The recording medium prepared was printed with a thermal printing device manufactured by Okura Electric Co., Ltd. at a voltage of 13.3 V and a pulse width of 1.2 msec, and the obtained color image was measured with a Macbeth densitometer RD-914. did. Test 2 Erasure characteristics The color-developed image obtained in Test 1 is erased with a thermal gradient tester manufactured by Toyo Seiki Co., Ltd. under the condition of 120 ° C. for 1 second, and the density of the image portion and the background density after erasing are the same as in Test 1. Measured. The above results are shown in Table 1.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【発明の効果】本発明は低温域での高速消去生と発色画
像の安定性に優れる可逆性感熱記録媒体、および該記録
媒体を搭載した感熱記録装置を提供することができた。INDUSTRIAL APPLICABILITY The present invention can provide a reversible thermosensitive recording medium which is excellent in high-speed erasure in a low temperature range and stability of a color image, and a thermosensitive recording device equipped with the recording medium.
【図１】本発明の可逆性感熱記録媒体の発色・消色特性
を示す図である。FIG. 1 is a diagram showing color developing / decoloring characteristics of a reversible thermosensitive recording medium of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｇ０６Ｋ 19/07 Ｇ０６Ｋ 19/00 Ｊ Ｂ (72)発明者 古屋 浩美 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 (72)発明者 筒井 恭治 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 Ｆターム(参考） 2C005 HA06 HA22 HB04 HB14 HB20 JA01 JA26 JB32 JC02 KA15 KA27 KA29 LA18 LB08 LB26 LB28 LB34 MA12 MA28 MB02 MB10 QB03 2H026 AA07 AA09 AA21 BB01 DD03 DD43 DD45 DD53 FF24 FF25 5B035 BA03 BB02 BB09 BB11 CA01 CA06 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 Identification code FI theme code (reference) G06K 19/07 G06K 19/00 JB (72) Inventor Hiromi Furuya 1-3-3 Nakamagome, Ota-ku, Tokyo No. 6 in Ricoh Co., Ltd. (72) Inventor Kyoji Tsutsui 1-3-6 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Co., Ltd. (reference) 2C005 HA06 HA22 HB04 HB14 HB20 JA01 JA26 JB32 JC02 KA15 KA27 KA29 LA18 LB08 LB26 LB28 LB34 MA12 MA28 MB02 MB10 QB03 2H026 AA07 AA09 AA21 BB01 DD03 DD43 DD45 DD53 FF24 FF25 5B035 BA03 BB02 BB09 BB11 CA01 CA06
Claims (6)
子受容性化合物を用い、発色と消色を加熱冷却条件の変
更により行わせることができる可逆性感熱組成物を含有
する可逆性感熱記録層を設けた可逆性感熱記録媒体にお
いて、該可逆性感熱記録層中に発色消色制御剤として下
記式（１）の化合物を用いることを特徴とする可逆性感
熱記録媒体。 【化１】 （Ｒ１は置換基を有してもよい炭素数１〜２２の２価の
炭化水素基、Ｒ２，Ｒ３は炭素数８以上のアルキル基を
それぞれ表す。ｎは７以上の整数、Ｘはヘテロ原子を含
む３価の結合基を、Ｙはヘテロ原子を含む２価の結合基
をそれぞれ示す）1. A reversible thermosensitive composition containing a reversible thermosensitive composition, which comprises an electron-donating color-forming compound and an electron-accepting compound on a support, and can develop and decolor by changing heating and cooling conditions. A reversible thermosensitive recording medium provided with a thermal recording layer, characterized in that a compound represented by the following formula (1) is used as a color-decoloration controlling agent in the reversible thermosensitive recording layer. [Chemical 1] (R 1 represents a divalent hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, R 2 and R 3 each represent an alkyl group having 8 or more carbon atoms, n is an integer of 7 or more, X Represents a trivalent linking group containing a hetero atom, and Y represents a divalent linking group containing a hetero atom.)
色が、初期の消色状態（Ａ）を加熱させると発色状態
（Ｂ）を形成、該発色状態（Ｂ）の急冷却によって前記
発色状態（Ｂ）を固定した発色状態（Ｃ）を形成、該発
色状態（Ｃ）を加熱し前記発色温度より低い温度で消色
状態（Ｄ）を形成、および前記発色状態（Ｃ）を冷却す
ると初期の消色状態（Ａ）を形成の各プロセスで発色お
よび消色を可逆的に行うことができるものであることを
特徴とする請求項１記載の可逆性感熱記録媒体。2. The coloring and decoloring performed by changing the heating and cooling conditions form a coloring state (B) when the initial decoloring state (A) is heated, and the coloring is caused by rapid cooling of the coloring state (B). When a colored state (C) in which the state (B) is fixed is formed, the colored state (C) is heated to form a decolored state (D) at a temperature lower than the coloring temperature, and the colored state (C) is cooled. The reversible thermosensitive recording medium according to claim 1, wherein color development and color erasing can be performed reversibly in each process of forming the initial color erasing state (A).
と情報記憶部とを有することを特徴とする請求項１また
は２に記載の可逆性感熱記録媒体。3. The reversible thermosensitive recording medium according to claim 1 or 2, wherein the reversible thermosensitive recording medium has a thermoreversible recording unit and an information storage unit.
あることを特徴とする請求項１〜３のいずれかに記載の
可逆性感熱記録媒体。4. The reversible thermosensitive recording medium according to claim 1, wherein the information storage unit is a magnetic recording layer or an IC.
逆性感熱記録媒体を搭載した感熱記録装置。5. A thermal recording apparatus equipped with the reversible thermal recording medium according to claim 1.
セラミックヒーター、面状ローラー、およびヒートロー
ラーからなる群から選ばれたヒーターであることを特徴
とする請求項５記載の感熱記録装置。6. The heating portion of the erasing device is a thermal head,
The heat-sensitive recording apparatus according to claim 5, which is a heater selected from the group consisting of a ceramic heater, a sheet roller, and a heat roller.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002037385A JP2003237232A (en) | 2002-02-14 | 2002-02-14 | Reversible heat-sensitive recording medium and heat- sensitive recording device mounted with the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002037385A JP2003237232A (en) | 2002-02-14 | 2002-02-14 | Reversible heat-sensitive recording medium and heat- sensitive recording device mounted with the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003237232A true JP2003237232A (en) | 2003-08-27 |
| JP2003237232A5 JP2003237232A5 (en) | 2005-08-25 |
Family
ID=27779002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002037385A Pending JP2003237232A (en) | 2002-02-14 | 2002-02-14 | Reversible heat-sensitive recording medium and heat- sensitive recording device mounted with the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003237232A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2390723A1 (en) * | 2010-05-25 | 2011-11-30 | Toshiba TEC Kabushiki Kaisha | Method for erasing image |
-
2002
- 2002-02-14 JP JP2002037385A patent/JP2003237232A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2390723A1 (en) * | 2010-05-25 | 2011-11-30 | Toshiba TEC Kabushiki Kaisha | Method for erasing image |
| CN102262386A (en) * | 2010-05-25 | 2011-11-30 | 东芝泰格有限公司 | Method for erasing image |
| US8541156B2 (en) | 2010-05-25 | 2013-09-24 | Toshiba Tec Kabushiki Kaisha | Method for erasing image |
| US9298143B2 (en) | 2010-05-25 | 2016-03-29 | Toshiba Tec Kabushiki Kaisha | Method for erasing image |
| US9671727B2 (en) | 2010-05-25 | 2017-06-06 | Toshiba Tec Kabushiki Kaisha | Method for erasing image |
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