JP2004042635A - Reversible multicolor thermal recording medium and reversible multicolor thermally color developable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reversible multicolor thermal recording medium, utilizing a reaction of a color former with a developer, that can easily realize color development and erasure simply by heating, can stably maintain the color developed state and the erased state at room temperature, and has a color erasure temperature which is below the color development temperature. <P>SOLUTION: In this reversible multicolor thermal recording medium, a plurality of different reversible thermally color developable compositions different from each other in color tone and color erasure-starting temperature each are present in a separate and independent form on a support, and the compositions are contained in respective independent microcapsules. <P>COPYRIGHT: (C)2004,JPO

Description

【００１６】
表１及び図２は、代表的顕色剤である各種鎖長のホスホン酸と、２−（ｏ−クロルアニリノ）−６−ジブチルアミノフルオランから得られる可逆的熱発色性組成物について、その発色・消色開始温度とホスホン酸のアルキル鎖長との関係を示すものである。図２の曲線に付記したＰ１４〜Ｐ２０の数字はそれぞれのアルキル鎖長を示す。
図２は発色体の温度を上げていったとき、その発色体を通過する光量の変化を測定した結果を示すもので、初期の光量を１．０としている。従って、カーブの立ち上がるところが消色開始温度であり、カーブが降下して初期と同じになるところが発色開始温度である。図２から、アルキル鎖が長くなるほど消色開始温度が高温側へシフトし、かつ発色開始温度も高温側へシフトすることが明確に観察される。
【００１７】
本発明で用いる可逆的熱発色性組成物は、基本的にアルキル鎖構造を持つ前記顕色剤と発色剤とを組合せた組成物であり、個々の顕色剤に対して好ましい発色剤が存在する。該可逆的熱発色性組成物を構成する顕色剤と発色剤の組合せは、両者を溶融温度以上に加熱して得られる発色状態の組成物を、溶融温度より低い温度へ加熱したときに起きる消色のし易さ、すなわち消色性と、発色状態の色調等の特性により適当に選択される。このうち消色性については、その組合せによって得られる発色状態組成物の示差熱分析（ＤＴＡ）、又は示差走査熱量分析（ＤＳＣ）における昇温過程に現れる発熱ピークの有無で判断できる。この発熱ピークは組成物を特徴づける消色現象と対応するものであり、消色性の良好な組合せを選択する基準となる。なお、組成物中には第３物質が存在しても講わず、例えば高分子化合物が存在してもその可逆的な消発色挙動を保つことができる。
【００１８】
次に、本発明による多色画像形成機構について詳細に説明するが、本発明の可逆的多色感熱記録媒体では、積層された複数の記録層又は複数種のマイクロカプセルが、それぞれ異なった色調及び消色開始温度を持つことを特徴にしている。前記のように、本発明では複数の記録層又はマイクロカプセルの全てを発色させた後に、その一部の記録層又はマイクロカプセルを消色することで、任意の混合色及び単一色より成る画像を得ることができる。これが可能となったのは、本発明に使用される可逆的熱発色性組成物が発色温度より低温側にその消色開始温度を持つことと、該組成物の発色開始温度と消色開始温度のコントロールが材料―――特に顕色剤―――の選択で可能になったためであり、本発明の可逆的多色感熱記録媒体は、従来技術の類推からは考えられない画期的な可逆的多色感熱記録媒体である。
【００１９】
本発明の可逆的多色感熱記録媒体は、発色色調及び消色開始温度が異なる複数種の組成物を用意し、これら組成物を各独立して含有する複数の記録層を積層して作成することができる他、それら組成物を各独立して含有するマイクロカプセルを複数種作製し、これらのマイクロカプセル混合物を一つの記録層に含有させることによっても作製することもできる。また、本発明の記録媒体は、不可逆的熱発色性組成物（消色温度が発色温度よりも高いか、或いは消色温度を持たず消色困難な熱発色性組成物を言う）を含有していても良い。更に、本発明の可逆的多色感熱記録媒体は、前記した記録層相互が加熱時に溶融・混合するのを防止するため、各記録層間に樹脂中間層を設置しても良い。
【００２０】
次に、本発明による多色画像形成機構を図３を参照して説明する。
図３は本発明の複数の記録層を有する可逆的多色感熱記録媒体の基本的構成図を示す。図３は支持体Ｓの上に発色色調及び消色開始温度の異なった可逆的感熱記録層Ａ，Ｂ，Ｃが積層されたものであり、Ｍは樹脂中間層を示し、Ｐは保護層を示している。
図３の各可逆的感熱記録層Ａ，Ｂ，Ｃについて、その発色開始温度と消色開始温度の関係を図４（ａ）、（ｂ）、（ｃ）に示す。図４において、横軸は温度、縦軸は発色濃度を示す。図中、実線のカーブは消色状態から温度を上げていったときの濃度変化を示しており、例えば記録層Ａでは濃度が温度ＴＡ_１で立ち上り、この温度以上で発色状態になる。このＴＡ_１を記録層Ａの発色開始温度とする。同様に記録層Ｂ，Ｃの発色開始温度はＴＢ_１，ＴＣ_１である。また、図中鎖線のカーブは発色状態の記録層温度を室温から上げていったときの濃度変化を示しており、例えば記録層Ａでは濃度がＴＡ_２で急に低下し消色する。このＴＡ_２を記録層Ａの消色開始温度とする。記録層Ｂ，Ｃについても同様にＴＢ_２，ＴＣ_２が消色開始温度である。
記録層Ａ，Ｂ，Ｃの発色開始温度と消色開始温度はそれぞれ異なっており、発色開始温度と消色開始温度の間の矢印で示した領域、すなわち消色温度領域は各記録層の間でずれている。
【００２１】
次に、図４に示す発色開始温度と消色開始温度を持つ３層の可逆的感熱記録層からなる記録媒体を例に、その記録方法を説明する。図４（ａ）、（ｂ）、（ｃ）から、各層の消色開始温度はＡが最も低温側、Ｃが最も高温側にあり、Ｂがこれらの中間にあることが分る。今、この記録媒体を記録層Ｃの発色開始温度ＴＣ_１より高い温度Ｔ_１に一時的に加熱し冷却すると、記録層Ｃだけでなく記録層Ａ，Ｂも発色するため、記録媒体の色は、Ａ，Ｂ，Ｃの３層の混合色になる。
次に、この混合色（Ａ，Ｂ，Ｃ）に発色した記録媒体を、記録層Ｂの消色温度領域にある温度Ｔ_３（ＴＡ_１＜Ｔ_３＜ＴＣ_２）に一時的に加熱し冷却すると、温度Ｔ_３で記録層Ｂは消色するが、Ｔ_３は記録層Ａの発色開始温度ＴＡ_１以上で記録層Ｃの消色開始温度ＴＣ_２以下にあるから記録層Ａ及びＣは消色しない。それゆえ、混合色（Ａ，Ｂ，Ｃ）の記録媒体を温度Ｔ_３に一時的に加熱すると混合色（Ａ，Ｃ）が得られる。
【００２２】
混合色（Ａ，Ｃ）に発色した記録媒体を、記録層Ａの消色温度領域にある温度Ｔ_４（ＴＡ_２＜Ｔ_４＜ＴＢ_２）に一時的に加熱し冷却すると記録層Ａのみが消色し、記録層Ｃは発色のままであるから記録媒体の色は記録層Ｃのみの色になる。同様にして、記録層の全部が消色状態にある記録媒体を記録層Ｂの発色開始温度以上で記録層Ｃの消色温度領域にある温度Ｔ_２に加熱すれば混合色（Ａ，Ｂ）が得られ、この発色状態にある記録媒体をＴ_４に一時的に加熱すれば記録層Ｂの発色した色が得られる。また、Ｔ_１に一時的に加熱して得た混合色（Ａ，Ｂ，Ｃ）の記録媒体を温度Ｔ_４に加熱すれば、記録層Ａのみが消色して混合色（Ｂ，Ｃ）が得られる。更に、記録層の全部が消色状態にある記録媒体を温度Ｔ_３に一時的に加熱すれば、記録層Ａのみが発色した色が得られる。
【００２３】
図４に示した３種の記録層Ａ，Ｂ，Ｃを有する記録媒体において、その加熱温度と得られる色の関係を表２にまとめる。
【表２】

【００２４】
ここで、加熱温度とはその温度に一時的に加熱することを意味しており、例えばＴ_１→Ｔ_３ということは、一時的にＴ_１に加熱・冷却後、再びＴ_３に一時的に加熱・冷却することを意味する。
ここでは可逆的感熱記録層が３層の場合について説明したが、２層の場合、或いは４層以上の場合も同様に多色の記録を行うことができる。２層の場合は混合色と単一色を合せて３色の画像が可能であり、３層では７色、４層では１５色の画像が得られる。以上の説明から分るように、発色している各記録層を、消色開始温度が高温側にある記録層から順次消色していくことで全記録層を消色すれば、初期状態にすることができる。また、この操作によって記録媒体は多色画像の形成を繰り返し行うことが可能になる。
【００２５】
次に、図５（ａ）（ｂ）（ｃ）に示す消色開始温度、発色開始温度をもつ３層より成る記録媒体の多色記録について説明する。
この３層は発色開始温度がほぼ等しく、消色開始温度のみが異なる。始めに３層すべてを発色させる温度Ｔ_１に一時的に加熱し、混合色（Ａ，Ｂ，Ｃ）を得る。この状態の記録媒体をＴ_４に一時的に加熱するとＡ層のみが消色して混合色（Ｂ，Ｃ）となる。また、混合色（Ａ，Ｂ，Ｃ）或いは混合色（Ｂ，Ｃ）を一時的にＴ_３に加熱すると、Ａ，Ｂ層又はＢ層が消色してＣ層のみの発色となる。従って、この場合には３色の記録が可能である。
以上の説明からも分かるように、発色開始温度が同一であっても消色開始温度に差があれば多色画像を形成することができる。
【００２６】
本発明の可逆的感熱記録媒体において、発色剤と組合せて用いられる顕色剤は、基本的に分子内に発色剤を発色させることができる顕色能を示す構造と、分子間の凝集力をコントロールするアルキル鎖構造部分を併せ持つ化合物であり、炭素数１２以上の脂肪族基を持つ有機リン酸化合物や脂肪族カルボン酸化合物やフェノール化合物、又は炭素数１０〜１８の脂肪族基を持つメルカプト酢酸の金属塩、或いは炭素数５〜８のアルキル基を持つカフェー酸のアルキルエステル等である。脂肪族基には、直鎖状又は分枝状のアルキル基、アルケニル基が包含され、ハロゲン、アルコキシ基、エステル基等の置換基を持っていてもよい。以下に、その顕色剤について具体的に例示する。
【００２７】
（ａ）有機リン酸化合物
下記一般式（１）で表されるものが好ましく用いられる。
【化１】
Ｒ_１−ＰＯ（ＯＨ）_２　　　　　　　　　　　　　　　　　（１）
（ただし、Ｒ_１は炭素数１２以上の脂肪族基を表す）
一般式（１）で表される有機リン酸化合物の具体例としては、例えば以下のものが挙げられる。
ドデシルホスホン酸、テトラデシルホスホン酸、ヘキサデシルホスホン酸、オクタデシルホスホン酸、エイコシルホスホン酸、ドコシルホスホン酸、テトラコシルホスホン酸、ヘキサコシルホスホン酸、オクタコシルホスホン酸等。
【００２８】
有機リン酸化合物としては、下記一般式（２）で表されるα−ヒドロキシアルキルホスホン酸も好ましく使用される。
【化２】

（ただし、Ｒ_２は炭素数１１〜２９の脂肪族基である）
一般式（２）で表されるα−ヒドロキシアルキルホスホン酸を具体的に示すと、α−ヒドロキシドデシルホスホン酸、α−ヒドロキシテトラデシルホスホン酸、α−ヒドロキシヘキサデシルホスホン酸、α−ヒドロキシオクタデシルホスホン酸、α−ヒドロキシエイコシルホスホン酸、α−ヒドロキシドコシルホスホン酸、α−ヒドロキシテトラコシルホスホン酸等があげられる。
【００２９】
（ｂ）脂肪族カルボン酸化合物
下記一般式（３）で表されるα−ヒドロキシ脂肪酸が好ましく用いられる。
【化３】
Ｒ_３−ＣＨ（ＯＨ）−ＣＯＯＨ　　　　　　　　　　　　　（３）
（ただし、Ｒ_３は炭素数１２以上の脂肪族基を表す）
一般式（３）で表されるα−ヒドロキシ脂肪族カルボン酸化合物としては、例えば以下のものが挙げられる。
α−ヒドロキシドデカン酸、α−ヒドロキシテトラデカン酸、α−ヒドロキシヘキサデカン酸、α−ヒドロキシオクタデカン酸、α−ヒドロキシペンタデカン酸、α−ヒドロキシエイコサン酸、α−ヒドロキシドコサン酸、α−ヒドロキシテトラコサン酸、α−ヒドロキシヘキサコサン酸、α−ヒドロキシオクタコサン酸等。
【００３０】
脂肪族カルボン酸化合物としては、ハロゲン元素で置換された炭素数１２以上の脂肪族基を持つ脂肪族カルボン酸化合物で、その少なくともα位又はβ位の炭素にハロゲン元素を持つものも好ましく用いられる。このような化合物の具体例としては、例えば以下のものを挙げることができる。
２−ブロモヘキサデカン酸、２−ブロモヘプタデカン酸、２−ブロモオクタデカン酸、２−ブロモエイコサン酸、２−ブロモドコサン酸、２−ブロモテトラコサン酸、３−ブロモオクタデカン酸、３−ブロモエイコサン酸、２，３−ジブロモオクタデカン酸、２−フロルドデカン酸、２−フロルテトラデカン酸、２−フロルヘキサデカン酸、２−フロルオクタデカン酸、２−フロルエイコサン酸、２−フロルドコサン酸、２−ヨードヘキサデカン酸、２−ヨードオクタデカン酸、３−ヨードヘキサデカン酸、３−ヨードオクタデカン酸、パーフロルオクタデカン酸等。
【００３１】
脂肪族カルボン酸化合物としては、炭素鎖中にオキソ基を持つ炭素数１２以上の脂肪族基がある脂肪族カルボン酸化合物で、その少なくともα位、β位又はγ位の炭素がオキソ基となっているものも好ましく用いられる。このような化合物の具体例としては、例えば以下のものを挙げることができる。
２−オキソドデカン酸、２−オキソテトラデカン酸、２−オキソヘキサデカン酸、２−オキソオクタデカン酸、２−オキソエイコサン酸、２−オキソテトラコサン酸、３−オキソドデカン酸、３−オキソテトラデカン酸、３−オキソヘキサデカン酸、３−オキソオクタデカン酸、３−オキソエイコサン酸、３−オキソテトラコサン酸、４−オキソヘキサデカン酸、４−オキソオクタデカン酸、４−オキソドコサン酸等。
【００３２】
脂肪族カルボン酸化合物としては、下記一般式（４）で表される二塩基酸も好ましく用いられる。
【化４】

（ただし、Ｒ_４は炭素数１２以上の脂肪族基を表し、Ｘは酸素原子又はイオウ原子を表し、ｎは１又は２を表すが、Ｘｎが−ＳＯ_２−基であっても良い）
一般式（４）で表される二塩基酸の具体例としては、例えば以下のものが挙げられる。
ドデシルリンゴ酸、テトラデシルリンゴ酸、ヘキサデシルリンゴ酸、オクタデシルリンゴ酸、エイコシルリンゴ酸、ドコシルリンゴ酸、デトラコシルリンゴ酸、ドデシルチオリンゴ酸、テトラデシルチオリンゴ酸、ヘキサデシルチオリンゴ酸、オクタデシルチオリンゴ酸、エイコシルチオリンゴ酸、ドコシルチオリンゴ酸、テトラコシルチオリンゴ酸、ドデシルジチオリンゴ酸、テトラデシルジチオリンゴ酸、ヘキサデシルジチオリンゴ酸、オクタデシルジチオリンゴ酸、エイコシルジチオリンゴ酸、ドコシルジチオリンゴ酸、テトラコシルジチオリンゴ酸、ドデシルスルホンブタン二酸、テトラデシルスルホンブタン二酸、ヘキサデシルスルホンブタン二酸、オクタデシルスルホンブタン二酸、エイコシルスルホンブタン二酸、ドコシルスルホンブタン二酸等。
【００３３】
脂肪族カルボン酸化合物としては、下記一般式（６）で表される二塩基酸も好ましく用いられる。
【化５】

（ただし、Ｒ_５，Ｒ_６，Ｒ_７は水素又は脂肪族基を表し、このうち少なくとも一つは炭素数１２以上の脂肪族基である）
一般式（５）で表される二塩基酸の具体例としては、例えば以下のものが挙げられる。
ドデシルブタン二酸、トリデシルブタン二酸、テトラデシルブタン二酸、ペンタデシルブタン二酸、オクタデシルブタン二酸、エイコシルブタン二酸、ドコシルブタン二酸、２，３−ジヘキサデシルブタン二酸、２，３−ジオクタデシルブタン二酸、２−メチル−３−ドデシルブタン二酸、２−メチル−３−テトラデシルブタン二酸、２−メチル−３−ヘキサデシルブタン二酸、２−エチル−３−ドデシルブタン二酸、２−プロピル−３−ドデシルブタン二酸、２−オクチル−３−ヘキサデシルブタン二酸、２−テトラデシル−３−オクタデシルブタン二酸等。
【００３４】
脂肪族カルボン酸化合物としては、下記一般式（６）で表される二塩基酸も好ましく用いられる。
【化６】

（ただし、Ｒ_８，Ｒ_９は水素又は脂肪族基を表し、このうち少なくとも一つは炭素数１２以上の脂肪族基である）
一般式（６）で表される二塩基酸の具体例としては、例えば以下のものが挙げられる。
ドデシルマロン酸、テトラデシルマロン酸、ヘキサデシルマロン酸、オクタデシルマロン酸、エイコシルマロン酸、ドコシルマロン酸、テトラコシルマロン酸、ジドデシルマロン酸、ジテトラデシルマロン酸、ジヘキサデシルマロン酸、ジオクタデシルマロン酸、ジエイコシルマロン酸、ジドコシルマロン酸、メチルオクタデシルマロン酸、メチルエイコシルマロン酸、メチルドコシルマロン酸、メチルテトラコシルマロン酸、エチルオクタデシルマロン酸、エチルエイコシルマロン酸、エチルドコシルマロン酸、エチルテトラコシルマロン酸等。
【００３５】
脂肪族カルボン酸化合物としては、下記一般式（７）で表される二塩基酸も好ましく用いられる。
【化７】

（ただし、Ｒ_１０は炭素数１２以上の脂肪族基を表し、ｎは０又は１を表し、ｍは１，２又は３を表し、ｎが０の場合、ｍは２又は３であり、ｎが１の場合はｍは１又は２を表す）
一般式（７）で表される二塩基酸の具体例としては、例えば以下のものが挙げられる。
２−ドデシル−ペンタン二酸、２−ヘキサデシル−ペンタン二酸、２−オクタデシル−ペンタン二酸、２−エイコシル−ペンタン二酸、２−ドコシル−ペンタン二酸、２−ドデシル−ヘキサン二酸、２−ペンタデシル−ヘキサン二酸、２−オクタデシル−ヘキサン二酸、２−エイコシル−ヘキサン二酸、２−ドコシル−ヘキサン二酸等。
【００３６】
脂肪族カルボン酸化合物としては、長鎖脂肪酸によりアシル化されたクエン酸等の三塩基酸も好ましく用いられる。その具体例としては、例えば以下のものが挙げられる。
【化８】

【００３７】
（ｃ）フェノール化合物
下記一般式（８）で表される化合物が好ましく用いられる。
【化９】

（ただし、Ｙは−Ｓ−，−Ｏ−，−ＣＯＮＨ−又は−ＣＯＯ−を表し、Ｒ_１１は炭素数１２以上の脂肪族基を表し、ｎは１，２又は３の整数である）
一般式（８）で表されるフェノール化合物の具体例としては、例えば以下のものが挙げられる。
ｐ−（ドデシルチオ）フェノール、ｐ−（テトラデシルチオ）フェノール、ｐ−（ヘキサデシルチオ）フェノール、ｐ−（オクタデシルチオ）フェノール、ｐ−（エイコシルチオ）フェノール、ｐ−（ドコシルチオ）フェノール、ｐ−（テトラコシルチオ）フェノール、ｐ−（ドデシルオキシ）フェノール、ｐ−（テトラデシルオキシ）フェノール、ｐ−（ヘキサデシルオキシ）フェノール、ｐ−（オクタデシルオキシ）フェノール、ｐ−（エイコシルオキシ）フェノール、ｐ−（ドコシルオキシ）フェノール、ｐ−（テトラコシルオキシ）フェノール、ｐ−ドデシルカルバモイルフェノール、ｐ−テトラデシルカルバモイルフェノール、ｐ−ヘキサデシルカルバモイルフェノール、ｐ−オクタデシルカルバモイルフェノール、ｐ−エイコシルカルバモイルフェノール、ｐ−ドコシルカルバモイルフェノール、ｐ−テトラコシルカルバモイルフェノール、没食子酸ヘキサデシルエステル、没食子酸オクタデシルエステル、没食子酸エイコシルエステル、没食子酸ドコシルエステル、没食子酸テトラコシルエステル等。
【００３８】
フェノール化合物としては、下記一般式（９）で表されるカフェー酸アルキルエステルを使用することもできる。
【化１０】

（但し、Ｒ_１２は炭素数５〜８のアルキル基である）
一般式（９）で表されるカフェー酸アルキルエステルを具体的に示すと、カフェー酸−Ｎ−ペンチル、カフェー酸−ｎ−ヘキシル、カフェー酸−ｎ−ヘプチル、カフェー酸−ｎ−オクチル等が挙げられる。
【００３９】
（ｄ）メルカプト酢酸の金属塩
一般式（１０）で表されるアルキル又はアルケニルメルカプト酢酸の金属塩も好ましく使用される。
【化１１】
（Ｒ_１３−Ｓ−ＣＨ_２−ＣＯＯ）_２　Ｍ　　　　　　　　　（１０）
（ただし、Ｒ_１３は炭素数１０〜１８の脂肪族基を表し、Ｍはスズ、マグネシウム、亜鉛又は銅を表す）
一般式（１０）で表されるメルカプト酢酸金属塩の具体例としては、例えば以下のものが挙げられる。
デシルメルカプト酢酸スズ塩、ドデシルメルカプト酢酸スズ塩、テトラデシルメルカプト酢酸スズ塩、ヘキサデシルメルカプト酢酸スズ塩、オクタデシルメルカプト酢酸スズ塩、デシルメルカプト酢酸マグネシウム塩、ドデシルメルカプト酢酸マグネシウム塩、テトラデシルメルカプト酢酸マグネシウム塩、ヘキサデシルメルカプト酢酸マグネシウム塩、オクタデシルメルカプト酢酸マグネシウム塩、デシルメルカプト酢酸亜鉛塩、ドデシルメルカプト酢酸亜鉛塩、テトラデシルメルカプト酢酸亜鉛塩、ヘキサデシルメルカプト酢酸亜鉛塩、オクタデシルメルカプト酢酸亜鉛塩、デシルメルカプト酢酸銅塩、ドデシルメルカプト酢酸銅塩、テトラデシルメルカプト酢酸銅塩、ヘキサデシルメルカプト酢酸銅塩、オクタデシルメルカプト酢酸銅塩等。
【００４０】
本発明で用いる発色性組成物は、基本的には前記顕色剤と発色剤を組合せて形成されるものである。本発明で用いる発色剤は電子供与性を示すものであり、それ自体無色或いは淡色の染料前駆体であり、特に限定されず、従来公知のもの、例えばトリフェニルメタンフタリド系化合物、フルオラン系化合物、フェノチアジン系化合物、ロイコオーラミン系化合物、インドリノフタリド系化合物等が用いられる。その発色剤の具体例を以下に示す。
本発明に用いる好ましい発色剤として下記一般式（１１）のフルオラン化合物がある。
【化１２】

（式中、Ｒ_１４は水素原子、アルキル基、アリル基、環状アルキル基又はアルコキシアルキル基を、Ｒ_１５はアルキル基、環状アルキル基、アリル基、アルコキシアルキル基又は置換されていても良いフェニル基を表す。Ｘは水素原子、低級アルキル基、低級アルコキシ基、アルコキシアルキル基又はハロゲン原子を、Ｙは低級アルキル基、アミノ基、置換アミノ基、シアノ基又はハロゲン原子を表す。）
【００４１】
一般式（１１）の化合物を具体的に示すと、以下の化合物が例示される。
２−アニリノ−３−メチル−６−（Ｎ−ｎ−ヘキシル−Ｎ−ｉｓｏ−アミルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（ジ−ｎ−オクチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−イソプロピル−Ｎ−メチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−オクチル−Ｎ−エチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−オクチル−Ｎ−ｉｓｏ−プロピルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−アミル−Ｎ−ｎ−プロピルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−アミル−Ｎ−ｎ−ブチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−アミル−Ｎ−エチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−アミル−Ｎ−メチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｉｓｏ−アミル−Ｎ−エチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−プロピル−Ｎ−イソプロピルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−ブチル−Ｎ−ｎ−プロピルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エチル−Ｎ−ｓｅｃ−ブチルアミノ
）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−ブチル−Ｎ−ｉｓｏ−プロピルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−ブチル−Ｎ−エチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−イソブチル−Ｎ−メチルアミノ）フルオラン。
【００４２】
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−テトラデシルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ドデシルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−デシルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−オクチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−ｉｓｏ−アミルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ブチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−プロピルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−エチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（ジシクロヘキシルエチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシルエチル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシルエチル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（ジシクロヘキシルメチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシルメチル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシルメチル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシルメチル−Ｎ−ｎ−ブチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシルメチル−Ｎ−シクロヘキシルアミノ）フルオラン。
【００４３】
２−アニリノ−３−メチル−６−（ジアリルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−オクチル−Ｎ−アリルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−ヘキシル−Ｎ−アリルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−アミル−Ｎ−アリルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エチル−Ｎ−アリルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−２−エトキシプロピル−Ｎ−エチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（ジエトキシエチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エトキシエチル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エトキシエチル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エトキシエチル−Ｎ−ｉｓｏ−アミルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エトキシエチル−Ｎ−ｎ−ブチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エトキシエチル−Ｎ−エチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エトキシメチル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エトキシメチル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エトキシメチル−Ｎ−ｉｓｏ−アミルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−ヘキサデシルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−オクチルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−アニリノ−３−メチル−６−（Ｎ−メチル−ｐ−トルイジノ）フルオラン、
【００４４】
２−アニリノ−３−メトキシ−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−３−メトキシ−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−３−メトキシ−６−（Ｎ−ｎ−ヘキシル−Ｎ−ｉｓｏ−アミルアミノ）フルオラン、
２−アニリノ−３−メトキシ−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−３−エトキシ−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−３−エトキシ−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−アニリノ−３−エトキシ−６−ジエチルアミノフルオラン、
２−アニリノ−３−エトキシ−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−３−エトキシ−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−３−エトキシエチル−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−３−エトキシエチル−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−アニリノ−３−エトキシエチル−６−ジエチルアミノフルオラン、
２−アニリノ−３−エトキシメチル−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−アニリノ−３−エトキシメチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−３−エトキシメチル−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−３−メトキシメチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−ベンジルアミノ−３−メチル−６−（ジ−ｎ−ブチルアミノ）フルオラン、　２−ベンジルアミノ−３−メチル−６−（ジ−ｎ−アミルアミノ）フルオラン
、
２−ベンジルアミノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−（ｍ−トリクロルメチルアニリノ）−３−メチル−６−ジエチルアミノフルオラン、
２−（ｍ−トリフロルメチルアニリノ）−３−メチル−６−ジエチルアミノフルオラン、
２−（ｍ−トリフロルメチルアニリノ）−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）フルオラン、
２−（２，４−ジメチルアニリノ）−３−メチル−６−（Ｎ−ｎ−ヘキシル−Ｎ−ｉｓｏ−アミルアミノ）フルオラン、
２−（２，４−ジメチルアニリノ）−３−メチル−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
２−（２，４−ジメチルアニリノ）−３−メチル−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−（２，４−ジメチルアニリノ）−３−メチル−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−（２，４−ジメチルアニリノ）−３−メチル−６−ジエチルアミノフルオラン、
２−（Ｎ−エチル−ｐ−トルイジノ）−３−メチル−６−（Ｎ−エチルアニリノ）フルオラン、
２−（Ｎ−メチル−ｐ−トルイジノ）−３−メチル−６−（Ｎ−プロピル−ｐ−トルイジノ）フルオラン、
【００４５】
２−アニリノ−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−６−（Ｎ−ｎ−ヘキシル−Ｎ−ｉｓｏ−アミルアミノ）フルオラン、
２−アニリノ−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−６−ジエチルアミノフルオラン、
２−アニリノ−６−（Ｎ−ｎ−ヘキシル−Ｎ−エチルアミノ）フルオラン、
２−アニリノ−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−６−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）フルオラン、
２−アニリノ−６−（ジエトキシエチルアミノ）フルオラン、
２−アニリノ−６−（Ｎ−エトキシエチル−Ｎ−ｉｓｏ−アミルアミノ）フルオラン、
２−アニリノ−６−（Ｎ−エトキシエチル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−アニリノ−６−（Ｎ−エトキシエチル−Ｎ−ｎ−ブチルアミノ）フルオラン、
２−アニリノ−６−（Ｎ−ｎ−オクチルアミノ）フルオラン、
２−アニリノ−６−（Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−アニリノ−６−（Ｎ−ｎ−アミルアミノ）フルオラン、
２−（Ｎ−メチルアニリノ）−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−（ｏ−クロルアニリノ）−６−ジエチルアミノフルオラン、
２−（ｏ−ブロモアニリノ）−６−ジエチルアミノフルオラン、
２−（ｏ−クロルアニリノ）−６−ジブチルアミノフルオラン、
２−（ｏ−フロルアニリノ）−６−ジブチルアミノフルオラン、
２−（ｐ−クロルアニリノ）−６−（Ｎ−ｎ−オクチルアミノ）フルオラン、
２−（ｐ−クロルアニリノ）−６−（Ｎ−ｎ−パルミチルアミノ）フルオラン、
２−（ｐ−クロルアニリノ）−６−（ジ−ｎ−オクチルアミノ）フルオラン、
２−（ｍ−トリフロルメチルアニリノ）−６−ジエチルアミノフルオラン、
２−（ｐ−アセチルアニリノ）−６−ジエチルアミノフルオラン、
２−（ｐ−アセチルアニリノ）−６−（Ｎ−ｎ−ヘキシル−Ｎ−ｉｓｏ−ヘキシルアミノ）フルオラン、
２−（ｐ−アセチルアニリノ）−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
２−（ｐ−アセチルアニリノ）−６−（Ｎ−ｎ−ヘキシル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−（ｐ−アセチルアニリノ）−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−（ｐ−アセチルアニリノ）−６−（Ｎ−ｎ−アミル−Ｎ−ｎ−ブチルアミノ）フルオラン、
２−（ｐ−アセチルアニリノ）−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−（ｐ−アセチルアニリノ）−６−（Ｎ−エトキシエチル−Ｎ−ｉｓｏ−アミルアミノ）フルオラン、
２−（ｐ−アセチルアニリノ）−６−（Ｎ−エトキシエチル−Ｎ−ｎ−アミルアミノ）フルオラン、
【００４６】
２−ベンジルアミノ−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−ベンジルアミノ−６−（Ｎ−メチル−２，４−ジメチルアニリノ）フルオラン、
２−ベンジルアミノ−６−（Ｎ−エチル−２，４−ジメチルアニリノ）フルオラン、
２−ベンゾイルアミノ−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−（ｏ−メトキシベンゾイルアミノ）−６−（Ｎ−メチル−ｐ−トルイジノ）フルオラン、
２−ジベンジルアミノ−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−ジベンジルアミノ−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−ジベンジルアミノ−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
２−ジベンジルアミノ−６−（Ｎ−ｎ−ヘキシル−Ｎ−ｉｓｏ−アミルアミノ）フルオラン、
２−ジベンジルアミノ−６−（ジ−ｎ−プロピルアミノ）フルオラン、
２−ジベンジルアミノ−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−ジベンジルアミノ−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−ジベンジルアミノ−６−（Ｎ−メチル−ｐ−トルイジノ）フルオラン、
２−ジベンジルアミノ−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−（ジ−ｐ−メチルベンジルアミノ）−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−ジベンジルアミノ−４−メチル−６−ジエチルアミノフルオラン、
２−ジベンジルアミノ−４−メチル−６−（ジ−ｎ−プロピルアミノ）フルオラン、
２−ジベンジルアミノ−４−メチル−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−ジベンジルアミノ−４−メチル−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−ジベンジルアミノ−４−メトキシ−６−（Ｎ−メチル−Ｐ−トルイジノ）フルオラン、
２−ベンジルアミノ−４−メチル−６−（Ｎ−エチル−Ｐ−トルイジノ）フルオラン、
２−（α−フェニルエチルアミノ）−４−メチル−６−ジエチルアミノフルオラン、
２−（ｐ−トルイジノ）−３−（ｔ−ブチル）−６−（Ｎ−メチル−ｐ−トルイジノ）フルオラン、
２−（α−フェニルエチルアミノ）−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−（ｏ−メトキシカルボニルアニリノ）−６−ジエチルアミノフルオラン、
【００４７】
２−メチルアミノ−６−（Ｎ−メチルアニリノ）フルオラン、
２−メチルアミノ−６−（Ｎ−エチルアニリノ）フルオラン、
２−メチルアミノ−６−（Ｎ−プロピルアニリノ）フルオラン、
２−エチルアミノ−６−（Ｎ−メチル−ｐ−トルイジノ）フルオラン、
２−エチルアミノ−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−メチルアミノ−６−（Ｎ−メチル−２，４，−ジメチルアニリノ）フルオラン、
２−エチルアミノ−６−（Ｎ−エチル−２，４，−ジメチルアニリノ）フルオラン、
２−ジメチルアミノ−６−（Ｎ−メチルアニリノ）フルオラン、
２−ジメチルアミノ−６−（Ｎ−エチルアニリノ）フルオラン、
２−ジエチルアミノ−６−（Ｎ−メチル−ｐ−トルイジノ）フルオラン、
２−ジエチルアミノ−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−ジプロピルアミノ−６−（Ｎ−メチルアニリノ）フルオラン、
２−ジプロピルアミノ−６−（Ｎ−エチルアニリノ）フルオラン、
２−アセチルアミノ−３−メチル−６−ジエチルアミノフルオラン、
２−アセチルアミノ−３−メチル−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−アセチルアミノ−３−メチル−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−アセチルアミノ−３−メチル−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
２−アセチルアミノ−６−（Ｎ−メチル−ｐ−トルイジノ）フルオラン、
【００４８】
２−アミノ−６−ジエチルアミノフルオラン、
２−アミノ−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−アミノ−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−アミノ−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
２−アミノ−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−アミノ−６−（Ｎ−メチルアニリノ）フルオラン、
２−アミノ−６−（Ｎ−エチルアニリノ）フルオラン、
２−アミノ−６−（Ｎ−プロピルアニリノ）フルオラン、
２−アミノ−６−（Ｎ−メチル−ｐ−トルイジノ）フルオラン、
２−アミノ−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−アミノ−６−（Ｎ−プロピル−ｐ−トルイジノ）フルオラン、
２−アミノ−６−（Ｎ−メチル−ｐ−エチルアニリノ）フルオラン、
２−アミノ−６−（Ｎ−エチル−ｐ−エチルアニリノ）フルオラン、
２−アミノ−６−（Ｎ−プロピル−ｐ−エチルアニリノ）フルオラン、
２−アミノ−６−（Ｎ−メチル−２，４−ジメチルアニリノ）フルオラン、
２−アミノ−６−（Ｎ−エチル−２，４−ジメチルアニリノ）フルオラン、
２−アミノ−６−（Ｎ−プロピル−２，４−ジメチルアニリノ）フルオラン、
２−アミノ−６−（Ｎ−メチル−ｐ−クロルアニリノ）フルオラン、
２−アミノ−６−（Ｎ−エチル−ｐ−クロルアニリノ）フルオラン、
２−アミノ−６−（Ｎ−プロピルル−ｐ−クロルアニリノ）フルオラン、
２−アミノ−３−メチル−６−ジエチルアミノフルオラン、
２−アミノ−３−メチル−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−アミノ−３−メチル−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−アミノ−３−メチル−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
２−アミノ−３−メトキシ−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−アミノ−３−メトキシ−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−アミノ−３−メトキシ−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
【００４９】
１，３−ジメチル−６−ジエチルアミノフルオラン、
１，３−ジメチル−６−（ジ−ｎ−ブチルアミノ）フルオラン、
１，３−ジメチル−６−（ジ−ｎ−アミルアミノ）フルオラン、
１，３−ジメチル−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
１，３−ジメチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ブチルアミノ）フルオラン、
２，３−ジメチル−６−ジメチルアミノフルオラン、
２−メチル−６−ジメチルアミノフルオラン、
２−メチル−６−ジエチルアミノフルオラン、
２−メチル−６−（ジ−ｎ−プロピルアミノ）フルオラン、
２−メチル−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−メチル−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−メチル−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
２−メチル−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−アミルアミノ）フルオラン、
２−メチル−６−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）フルオラン、
３−ジエチルアミノ−６−（ｍ−トリフロルメチルアニリノ）フルオラン、
３−メチル−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−メチル−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
４−メトキシ−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−シアノ−６−ジエチルアミノフルオラン、
２−シアノ−６−（ジ−ｎ−ブチルアミノ）フルオラン、
２−シアノ−６−（ジ−ｎ−アミルアミノ）フルオラン、
２−シアノ−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
２−シアノ−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−ヘキシルアミノ）フルオラン、
２−シアノ−６−（Ｎ−シクロヘキシル−Ｎ−ｎ−デシルアミノ）フルオラン。
【００５０】
２−クロル−６−ジエチルアミノフルオラン、
２−ブロモ−６−ジエチルアミノフルオラン、
２−クロル−６−ジプロピルアミノフルオラン、
２−クロル−６−ジブチルアミノフルオラン、
３−クロル−６−シクロヘキシルアミノフルオラン、
３−ブロモ−６−シクロヘキシルアミノフルオラン、
２−クロル−６−（Ｎ−エチル−Ｎ−イソアミルアミノ）フルオラン、
２−クロル−３−メチル−６−ジエチルアミノフルオラン、
２−アニリノ−３−クロル−６−ジエチルアミノフルオラン、
２−（ｏ−クロルアニリノ）−３−クロル−６−シクロヘキシルアミノフルオラン、
２−（ｍ−トリフロルメチルアニリノ）−３−クロル−６−ジエチルアミノフルオラン、
２−（２，３−ジクロルアニリノ）−３−クロル−６−ジエチルアミノフルオラン、
２−エトキシエチルアミノ−３−クロル−６−ジブチルアミノフルオラン、
２−ベンジルアミノ−４−クロル−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−ジベンジルアミノ−４−クロル−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
２−（α−フェニルエチルアミノ）−４−クロル−６−ジエチルアミノフルオラン、
２−（Ｎ−ベンジル−ｐ−トリフロルメチルアニリノ）−４−クロル−６−ジエチルアミノフルオラン等。
【００５１】
一般式（１０）以外にも本発明に用いる発色剤として好ましいフルオラン化合物は多数あり、具体的には以下の化合物が例示される。
２−アニリノ−３−メチル−６−ピロリジノフルオラン、
２−アニリノ−３−クロル−６−ピロリジノフルオラン、
２−アニリノ−３−メチル−６−（Ｎ−エチル−Ｎ−テトラヒドロフルフリルアミノ）フルオラン、
２−メシジノ−３−メチル−４′，５′−ベンゾ−６−ジエチルアミノフルオラン、
２−（ｍ−トリフロルメチルアニリノ）−３−メチル−６−ピロリジノフルオラン、
２−（α−ナフチルアミノ）−３，４−ベンゾ−４′−ブロモ−６−（Ｎ−ベンジル−Ｎ−シクロヘキシルアミノ）フルオラン、
２−ピペリジノ−６−ジエチルアミノフルオラン、
２−（Ｎ−ｎ−プロピル−ｐ−トリフロルメチルアニリノ）−６−モルフォリノフルオラン、
２−（ジ−Ｎ−ｐ−クロルフェニル−メチルアミノ）−６−ピロリジノフルオラン、
２−（Ｎ−ｎ−プロピル−ｍ−トリフロルメチルアニリノ）−６−モルフォリノフルオラン、
１，２−ベンゾ−６−ジエチルアミノフルオラン、
１，２−ベンゾ−６−（Ｎ−エチル−Ｎ−イソアミルアミノ）フルオラン、
１，２−ベンゾ−６−ジブチルアミノフルオラン、
１，２−ベンゾ−６−（ジ−ｎ−アミルアミノ）フルオラン、
１，２−ベンゾ−６−（ジ−ｎ−ヘキシルアミノ）フルオラン、
１，２−ベンゾ−６−（Ｎ−メチル−Ｎ−シクロヘキシルアミノ）フルオラン、
１，２−ベンゾ−６−（Ｎ−エチル−Ｎ−ｎ−オクチルアミノ）フルオラン、
１，２−ベンゾ−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン、
１，２−ベンゾ−６−ジアリルアミノフルオラン、
１，２−ベンゾ−６−（Ｎ−エトキシエチル−Ｎ−エチルアミノ）フルオラン等。
【００５２】
フルオラン化合物以外でも本発明に用いる発色剤として好ましい化合物は多数あり、具体的には以下の化合物が挙げられる。
ベンゾロイコメチレンブルー、
２−〔３，６−ビス（ジエチルアミノ）〕−６−（０−クロルアニリノ）キサンチル安息香酸ラクタム、
２−〔３，６−ビス（ジエチルアミノ）〕−９−（０−クロルアニリノ）キサンチル安息香酸ラクタム、
３，３−ビス（ｐ−ジメチルアミノフェニル）−フタリド、
３，３−ビス（ｐ−ジメチルアミノフェニル）−６−ジメチルアミノフタリド（別名クリスタルバイオレットラクトン）、
３，３−ビス（ｐ−ジメチルアミノフェニル）−６−ジエチルアミノフタリド、
３，３−ビス（ｐ−ジメチルアミノフェニル）−６−クロルフタリド、
３，３−ビス（ｐ−ジブチルアミノフェニル）フタリド、
３−（２−メトキシ−４−ジメチルアミノフェニル）−３−（２−ヒドロキシ−４，５−ジクロルフェニル）フタリド、
３−（２−ヒドロキシ−４−ジメチルアミノフェニル）−３−（２−メトキシ−５−クロルフェニル）フタリド、
３−（２−ヒドロキシ−４−ジメトキシアミノフェニル）−３−（２−メトキシ−５−クロルフェニル）フタリド、
３−（２−ヒドロキシ−４−ジメチルアミノフェニル）−３−（２−メトキシ−５−ニトロフェニル）フタリド、
３−（２−ヒドロキシ−４−ジエチルアミノフェニル）−３−（２−メトキシ−５−メチルフェニル）フタリド、
３−（２−メトキシ−４−ジメチルアミノフェニル）−３−（２−ヒドロキシ−４−クロル−５−メトキシフェニル）フタリド、
３，６−ビス（ジメチルアミノ）フルオレンスピロ（９，３′）−６′−ジメチルアミノフタリド、
６′−クロル−８′−メトキシ−ベンゾインドリノ−スピロピラン、
６′−ブロモ−２′−メトキシ−ベンゾインドリノ−スピロピラン等。
【００５３】
本発明で用いる組成物に含まれる発色剤と顕色剤の割合は、使用する化合物の物性によって適切な比率を選択する必要があるが、その範囲はモル比で発色剤１に対し顕色剤が１から２０の範囲、好ましくは２から１０の範囲である。顕色剤及び発色剤は単独でも２種以上混合して使用しても良いが、発色剤と顕色剤の割合によって消色特性が変化し、比較的顕色剤が多い場合は消色開始温度が低くなり、比較的少ない場合は消色が温度に対してシャープになる。従って、この割合は用途や目的に応じて適当に選択すればよい。
本発明で用いる熱発色性組成物は、基本的に前記の顕色剤と発色剤によって成り立つものであるが、種々の特性、例えば消色性や保存性等の改善を目的に、顕色剤の結晶化をコントロールする効果のある添加剤等を含有させることができる。
【００５４】
本発明において、可逆的感熱記録層を複数層設けることによって該記録媒体を多色化させる場合は、支持体上に熱発色性組成物を１種類だけ含有する可逆的感熱記録層を複数層積層させるだけでも良いが、積層させる記録層の間に樹脂中間層を設けるのがより望ましい。ここで用いられる樹脂中間層は、加熱時に記録層相互が混ざらないようにするためのものであり、耐熱性樹脂で形成するのが好ましい。また、支持体は紙、合成紙、プラスチックフィルム或いはこれらの複合体、ガラス板等であり、記録層を保持できるものであればよい。
可逆的感熱記録層は、前記の熱発色性組成物が存在すればどのような態様のものでも良く、例えば顕色剤と発色剤を混合・溶融して膜とし、これを冷却して可逆的感熱記録層としても良い。しかし、通常はバインダー樹脂内に顕色剤及び発色剤を充分良く分散して可逆的感熱記録層とするのが良く、この方法で長寿命の可逆的多色感熱記録媒体が得られる。
【００５５】
バインダー樹脂としては、例えばヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メトキシセルロース、カルボキシメチルセルロース、メチルセルロース、酢酸セルロース、ゼラチン、カゼイン、澱粉、ポリアクリル酸ソーダ、ポリビニルピロリドン、ポリアクリルアミド、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、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類、ポリメタクリル酸エステル類、アクリル酸共重合体、マレイン酸共重合体、ポリビニルアルコール、塩素化塩化ビニル樹脂、これらの樹脂の混合物等が用いられる。
【００５６】
顕色剤及び発色剤は、そのまま或いはマイクロカプセル中に内包して用いることができる。顕色剤、発色剤のマイクロカプセル化は、コアセルベーション法、界面重合法、インサイチュ重合法など公知の方法によって行えばよい。
可逆的感熱記録層の形成は、従来公知の方法に従い、発色剤及び顕色剤をバインダー樹脂と共に水又は有機溶剤により均一に分散もしくは溶解して、これを支持体上又は中間層の上に塗布・乾燥することによって行うことができる。
可逆的感熱記録層のバインダー樹脂の役割は、発色・消色の繰り返しによって熱発色性組成物が凝集するのを防止し、熱発色性組成物が均一に分散した状態を保持することにある。特に、発色時の熱の印加で熱発色性組成物が凝集して不均一化することが多いため、バインダー樹脂は耐熱性の高いものが好ましい。
本発明の可逆的多色感熱記録媒体においては、必要に応じて塗布特性或いは記録特性の向上を目的に、通常の感熱記録紙に用いられている種々の添加剤、例えば分散剤、界面活性剤、高分子カチオン系導電剤、填料、発色画像安定剤、酸化防止剤、光安定化剤、滑剤等を記録層に加えることも出来る。
【００５７】
樹脂中間層は、前記のように隣接する可逆的感熱記録層が消発色時の加熱・加圧で混合するのを防止することが目的の分離層である。
本発明の可逆的多色感熱記録媒体は、多色のため複数の可逆的感熱記録層を持つが、記録層を構成する各層のバインダー樹脂として同一樹脂を用いた場合、熱印加時の加圧・加熱によって隣接記録層が部分的に混合する傾向を持つことが認められる。樹脂中間層はこのような問題を解決する。
樹脂中間層は、隣接する記録層のバインダー樹脂と相溶しにくい樹脂又は相溶しない樹脂や、記録温度では溶融しない樹脂を記録層上に塗工することにより形成することができる。記録層が有機溶媒を含む塗工液で形成される場合には、水性溶媒を含む水溶性樹脂塗工液を用いて中間層を形成するのがよい。また、樹脂中間層は、耐熱性樹脂フィルムを記録層の上に貼り合わせることにより形成させることも可能であり、記録媒体の発色性や画像保存性等の点から、樹脂フィルムをドライラミネート法で接着させて形成させるのが特に好ましい。
【００５８】
中間層形成用の樹脂フィルムとしては、ポリエチレンテレフタレート等のポリエステルフィルムが好ましく使用される。また、ポリアミド、ポリイミド、ポリアミドイミド、ポリパラバン酸等のフィルムも好ましく用いられる。樹脂フィルムの接着に使用する接着剤は、ドライラミネート法で使用される接着剤がいずれも使用可能であり、熱可塑性樹脂ではアイオノマー樹脂、アクリル樹脂（水系エマルジョンを含む）、変性エチレン−酢酸ビニル共重合体、ポリブタジエン、フェノキシ樹脂、ポリビニルエーテル、ポリビニルホルマール、酢酸ビニル樹脂、ポリエステル等が使用される。熱硬化性樹脂ではウレタン樹脂、エポキシ樹脂、キシレン樹脂、フェノール樹脂、尿素樹脂等が使用される。
樹脂中間層の厚さは、記録・消去の繰り返しによる熱及び圧力の印加で破損を生じない程度の厚さであればよい。しかし、樹脂中間層が厚すぎると伝熱性が悪くなるから出来るだけ薄いものが良く、通常は１０μｍ以下が好ましい。
【００５９】
本発明の記録媒体は、発色色調及び消色開始温度の異なる組成物のそれぞれをマイクロカプセル化し、これを混合したものを支持体上に塗工することによって作製することができる。
すなわち、常法によって、発色色調及び消色温度の異なる組成物をそれぞれ独立して含有する複数種のマイクロカプセル混合物を作製し、これを常法に従って支持体上に塗工すれば良い。マイクロカプセル壁形成用樹脂としては、従来公知の熱可塑性樹脂や熱硬化性樹脂が用いられる。
マイクロカプセルを支持体上に塗工するのに使用するバインダー樹脂としては、通常の記録層形成用耐熱性樹脂を使用すれば良く、前記の各種バインダー樹脂が用いられる。また、マイクロカプセルを含有する記録層の熱的及び機械的強度を向上させるために、該層のバインダー樹脂に硬化性樹脂を使用し、設層後に硬化させる方法は該層の設層方法として推奨される。
【００６０】
本発明の可逆的多色感熱記録媒体は、その表面に保護層を形成させることができる。保護層は、熱印加時の熱と圧力で表面が変形したり変色したりすることを防止する役割のほか、耐薬品性、耐水性、耐摩擦性、ヘッドマッチング性等を向上させる役割も行うものである。保護層を形成する材料は、耐熱性で且つ強度の大きい樹脂フィルムを使用するのが望ましく、ポリアミドフィルム、ポリイミドフィルム、芳香族ポリエステルフィルム、ポリパラバン酸フィルム等が使用される。このような保護層の形成で、前記のように耐熱性が向上すると共に、有機溶剤、可塑剤、油、汗、水等の接触に対する抵抗力も増加し、悪い環境でも画像の形成及び消去を問題なく繰り返すことのできる記録媒体を得ることができる。また、保護層中に光安定化剤を含有させることで画像及び地肌の耐光性が著しく改良された記録媒体が得られ、高分子カチオン系導電剤の添加で帯電防止を可能とし、さらに保護層に有機又は無機フィラー及び滑剤を含有させることにより、サーマルヘッド等との接触で生じるスティッキング等の問題もなく、信頼性及びヘッドマッチング性にすぐれた感熱記録媒体を得ることができる。
【００６１】
本発明の可逆的多色感熱記録媒体では、必要に応じて支持体と記録層の間にアンダーコート層を設置しても良い。
アンダーコート層は、断熱性向上、支持体と記録層間の接着性向上、記録層作成時の溶剤に対する支持体の耐性向上、熱印加時の支持体による熱溶融性インクの吸収防止等の目的で設置するものであり、支持体の種類を勘案して設置の有無を定めれば良い。アンダーコート層の重要な役割の一つは断熱性向上であるが、これは印加熱エネルギーを無駄なく熱記録形成や熱消去に役立たせるためのものであり、断熱層の設置で発色及び消色をシャープに行うことができる。断熱を目的とするアンダーコート層の形成は、支持体上に有機又は無機材質より成る微小中空体粒子を塗工すれば良く、具体的にはガラス又はセラミックス、或いはプラスチック等で形成された粒径１０〜５０μｍ程度の微小中空体を、バインダー樹脂と共に溶剤に良く分散させて支持体上に均一に塗布・乾燥させれば良い。
【００６２】
本発明の可逆的多色感熱記録媒体は種々の手順で製造可能であり、例えば支持体上に記録層Ａを塗布し、その上に接着剤を塗布した樹脂フィルムをラミネートし、次に記録層Ｂを塗布してから樹脂フィルムをラミネートするようにして製造することができる。なお、ラミネート法では貼り合せた後にヒートローラー等で加圧・加熱して強固に接着させるが、この加圧・加熱は保護層を含めた全層を貼り合せてから行っても良いし、一つの中間層を形成する度に行っても良い。
また、前記のように発色色調及び消色開始温度の異なる各種のマイクロカプセル化組成物を支持体上に塗工して記録層を形成させることもできる。更に、複数層の記録層を積層させたうちの少なくとも一層をマイクロカプセル含有層とし、その他の層は通常の熱発色性組成物含有層とすることも可能である。
本発明では、支持体に透明フィルムを使用することで透明記録媒体を得ることができ、これは表示媒体に好ましく使用される。この場合は、中間層及び保護層に使用するフィルムも透明度の高い方が好ましいことは言うまでもない。
【００６３】
本発明の可逆的多色感熱記録媒体を初期状態にするためには、該記録媒体の記録層に含まれている可逆的熱発色性組成物の全部が発色する温度に一時的に加熱して、可逆的熱発色性組成物の全部を発色状態にしてから、発色した該組成物のうち消色開始温度が高温側にある組成物から低温側にある組成物の順に、消色温度領域に加熱して記録層に存在する可逆的熱発色性組成物の全部を消色状態にすれば良い。
記録画像の形成は、使用目的によって熱ペン、サーマルヘッド、レーザー加熱等特に限定されない。同様に、記録画像の消去も加熱ローラー、面状発熱体、恒温槽、温風、サーマルヘッド等消去の温度条件が与えられるものであれば特に限定されない。
【００６４】
本発明で多色画像を得るためには前記の可逆的多色感熱記録媒体を使用し、２種以上の組成物を加熱・発色させた後、所定の色の組成物をその消色温度に加熱・消去されば良い。ところで、表２に記載したように３層構成の多色記録層で多色画像を得るためには、複数の熱印加が必要である。そこで、熱印加可能な発熱体が一個の記録装置では画像形成に長時間を要するから、複数個の発熱体を備えた装置を用いることが好ましい。
本発明の多色画像形成用記録装置は、複数種の組成物のうちの任意の組成物をその発色温度以上になるように画像状に熱印加できる発熱体と、任意の組成物をその消色温度になるように画像状に熱印加できる発熱体と、各組成物をその消色温度に全体に熱印加できる発熱体を備えたものである。この場合、各発熱体は複数の発熱体からなる発熱体群であることができる。
【００６５】
図６は、３層の可逆的記録層を持つ記録媒体のための記録装置の基本的構成を示しており、Ｌ_１、Ｌ_２、Ｌ_３は３つの各層を全面的にその消色温度に加熱する消色用発熱体、Ｈ_１、Ｈ_２、Ｈ_３は各層を画像状に加熱するための発熱体である。記録媒体の各記録層の消色温度領域が図４と同じである場合、全体消色用の発熱体Ｌ_１、Ｌ_２、Ｌ_３は、それぞれ記録層を温度Ｔ_２、Ｔ_３、Ｔ_４に順次加熱できるように設定されており、記録媒体が既に多色画像を形成していても、この部分を通過させれば全部の記録層が消色される。その後、記録媒体は画像状に熱印加できる発熱体Ｈ_１、Ｈ_２、Ｈ_３からなる画像形成部を通過する。このうちＨ_１の発熱体は発色用であり、必要に応じて画像状に温度Ｔ_１、Ｔ_２又はＴ_３に加熱できるように発熱する。続くＨ_２、Ｈ_３はそれぞれ温度Ｔ_３及びＴ_４に記録層を加熱できるように必要に応じ画像状に発熱し、Ｈ_１で発色した記録層のうちの所要の色を消色する。具体的には、例えば図４のＣ層の色のみ必要な画像部分であれば、Ｈ_１はＴ_１に加熱できるように、Ｈ_２及びＨ_３はそれぞれＴ_３、Ｔ_４に加熱できるように設定しておく。Ｈ_１通過でＡ、Ｂ、Ｃの全層が発色するが、Ｈ_２を通過するとＢ層が消色しＨ_３を通過すればＡ層が消色するので、その画像部分はＣ層のみの色となる。また、記録媒体が複数種のマイクロカプセルで構成されている場合は、上記の各記録層を各マイクロカプセルと同一に考えれば良く、図６の装置で多色画像を効率良く形成させることができる。
【００６６】
発熱体としては、画像状に熱を加える記録部分は一般的な熱記録用サーマルヘッドを、全体消色部分の発熱体はヒートローラー又はサーマルヘッドを用いることができる。なお、可逆的記録層又はマイクロカプセルの全消色を記録部分の発熱体で行うこともでき、この場合は全体消色部分の発熱体を省略できる。
本発明の可逆的多色感熱記録媒体において、一部の記録層又はマイクロカプセルが不可逆性の場合も、全層又は全部のマイクロカプセルが可逆性の場合と同一装置を使用して効率的な画像の形成及び消去が可能であるが、この場合は当然のことながら全層又は全部のマイクロカプセルを初期状態にすることはできず、その不可逆性組成物の発色が残る。なお、不可逆性組成物が存在する場合の画像形成及び消去の状況は可逆性組成物のみを対象として考えれば良い。
【００６７】
本発明において、効率の良い表示を行うのに好ましい表示装置の基本構成を図７に示す。（ａ）はシート状の表示媒体に、全体消色用の発熱体Ｌ_１’、Ｌ_２’、Ｌ_３’と画像形成用の発熱体Ｈ_１’、Ｈ_２’、Ｈ_３’が接しており、移動する表示媒体に熱を印加し、画像の形成と消去を行う。この場合、固定された表示媒体に対し発熱体が移動してもよい。（ｂ）はエンドレスベルト状の表示媒体に対し、同様に画像形成用と消去用の発熱体が設置されている。
表示媒体の各画像形成層の消色温度領域が図４と同じである場合、全体消色用の発熱体Ｌ_１’、Ｌ_２’、Ｌ_３’は、それぞれ記録層を温度Ｔ_２、Ｔ_３、Ｔ_４に順次加熱されるように設置されており、表示媒体が既に多色画像を形成していても、この部分を通過すれば記録層が消色されて初期状態にすることができる。
【００６８】
その後、表示媒体は画像状に熱を印加できる発熱体Ｈ_１’、Ｈ_２’、Ｈ_３’からなる記録部分を通過する。このうちＨ_１’の発熱体は発色用であり、必要に応じて画像状に温度Ｔ_１、Ｔ_２又はＴ_３に一時的に加熱できるように発熱する。続くＨ_２’、Ｈ_３’はそれぞれ温度Ｔ_３及びＴ_４に記録層を加熱できるように必要に応じて画像状に発熱し、Ｈ_１’で発色した記録層のうち所要の色を消去させる。具体的には、例えば図４のＣ層の色のみ必要な画像部分であれば、Ｈ_１’はＴ_１に加熱できるように、Ｈ_２’及びＨ_３’はそれぞれＴ_３、Ｔ_４に加熱できるように設定される。Ｈ_１’通過でＡ、Ｂ、Ｃの全層が発色するが、Ｈ_２’通過でＢ層が消色し、Ｈ_３’通過でＡ層が消色するので、その画像部分はＣ層のみの色となる。なお、具体的な画像印加用及び全体消色用発熱体は記録媒体の場合と同一で良い。一部の記録層が不可逆層より成る場合についても、記録媒体の場合と同様に可逆層による画像形成及び消去を行えば良い。また、複数種のマイクロカプセルで標示媒体が形成されている場合も、図７の装置で効率良く多色画像を形成させることができる。
【００６９】
【実施例】
以下、実施例により本発明を更に詳細に説明するが、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。
【００７０】
実施例１
下記の顕色剤と発色剤をモル比２：１の割合に混合し、良く粉砕・混合した組成物Ａ、Ｂを作製した。
組成物Ａ
テトラデシルホスホン酸
２−（ｏ−クロルアニリノ）−６−ジブチルアミノフルオラン
組成物Ｂ
オクタデシルホスホン酸
２−クロル−６−ジエチルアミノフルオラン
厚さ約１ｍｍのガラス板を用意し、ホットプレート上で表面が１７０℃になるように加熱した。そのガラス板上に組成物Ｂの粉末を少量のせて溶融させた後、その融液上に厚さ０．１ｍｍのガラス板をかぶせて融液を均一な厚さに広げた。次に、そのガラス板上に組成物Ａの粉末を少量のせて溶融させ、前と同様に厚さ０．１ｍｍのガラス板をかぶせて融液を均一な厚さに広げた。
【００７１】
次に、全体をホットプレートからはずして氷水に接触させて急冷した。このようにして得られた記録媒体は、ガラス基板上に発色した記録層Ｂを持ち、その上にガラスからなる中間層を挾んで発色した記録層Ａがあり、最上部にガラスからなる保護層を持った構成となっている。なお、発色した記録層Ａの単独色は黒であり、記録層Ｂの単独色は赤である。
この記録媒体を、まず記録層Ｂの消色温度領域である７２℃に一時的に加熱・冷却して、記録層Ｂを消色した。７２℃は記録層Ａの発色温度以上となっているため、記録層Ａは発色状態のままである。続いて、記録層Ａの消色温度領域である５６℃に一時的に加熱・冷却して記録層Ａも消色した。これで記録層Ａ、Ｂの両方が消色した未記録の初期状態が得られた。
このようにして得られた記録媒体に対して、表３に示す記録操作と消色操作の組合せを、▲１▼→▲２▼→▲３▼→▲１▼→▲２▼→▲３▼……のように１０回繰り返して行った。
【００７２】
【表３】

表３に示すように▲１▼、▲２▼、▲３▼のそれぞれの記録操作により、３種類の色調が得られた。また、記録、消色の繰り返しを安定して行うことができた。
【００７３】
実施例２
下記の組合せの組成物Ａ及びＢを用い、混合比をモル比で４／１（顕色剤／発色剤）とした以外は、実施例１と同様にして記録媒体を作成した。
組成物Ａ
ヘキサデシルホスホン酸
２−（ｏ−クロルアニリノ）−６−ジブチルアミノフルオラン
組成物Ｂ
エイコシルホスホン酸
１，２−ベンゾ−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン
記録媒体を無色の初期状態とするため、まず記録層Ｂの消色温度領域である８０℃に加熱・冷却して、記録層Ｂを消色した。８０℃は記録層Ａにとっては発色温度以上となっているため、記録層Ａは発色状態のままである。続いて記録層Ａの消色温度領域である６４℃に加熱・冷却して記録層Ａも消色した。これで記録層Ａ、Ｂの両方が消色した未記録の初期状態が得られた。
【００７４】
このようにして得られた記録媒体に対して、表４に示す記録操作と消色操作の組合せを実施例１と同様に１０回繰り返して行った。
【表４】

表４に示すように▲１▼、▲２▼、▲３▼のそれぞれの記録操作により、３種類の色調が得られた。また、記録、消色の繰り返しを安定して行うことができた。
【００７５】
実施例３
下記の組合せの組成物Ａ及びＢを用いた以外は、実施例２と同様にして記録媒体を作成した。
組成物Ａ
オクタデシルチオリンゴ酸
２−アニリノ−３−メチル−６−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）フルオラン
組成物Ｂ
エイコシルチオリンゴ酸
１，２−ベンゾ−６−（Ｎ−イソペンチル−Ｎ−エチルアミノ）フルオラン記録媒体を無色の初期状態とするため、記録層Ｂの消色温度領域であり、かつ記録層Ａの消色温度領域でもある温度６５℃に加熱して、両記録層を消色した。
【００７６】
このようにして得られた記録媒体に対して、表５に示す記録操作と消色操作の組合せ▲１▼、▲２▼を実施例１と同様に１０回繰り返して行った。
【表５】

表５に示すように▲１▼、▲２▼のそれぞれの記録操作により、２種類の色調が得られた。また、記録、消色の繰り返しを安定して行うことができた。
【００７７】
実施例４
下記の組合せの組成物Ａ及びＢを用いた以外は、実施例２と同様にして記録媒体を作製した。
組成物Ａ
ヘキサデシルホスホン酸
２−（Ｎ−メチル−アニリノ）−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン
組成物Ｂ
ドコシルホスホン酸
１，２−ベンゾ−６−（Ｎ−イソアミル−Ｎ−エチルアミノ）フルオラン
記録媒体を無色の初期状態にするため、まず記録層Ｂの消色温度領域である８４℃に加熱・冷却して記録層Ｂを消色した。８４℃は、記録層Ａにとっては発色温度以上であるため、記録層Ａは発色状態のままである。続いて、記録層Ａの消色温度領域である６４℃に加熱・冷却して記録層Ａも消色した。これで、記録層Ａ、Ｂの両方が消色した未記録の初期状態が得られた。
【００７８】
このようにして得られた記録媒体に対して、表６に示す記録操作と消色操作の組合せを実施例１と同様に１０回繰り返して行った。
【表６】

表６に示すように▲１▼、▲２▼、▲３▼のそれぞれの記録操作により、３種類の色調が得られた。また、記録と記録消去の繰り返しを安定に行うことができた。
【００７９】
実施例５
下記の顕色剤及び発色剤を含む組成物Ａ及びＢを、それぞれボールミルで粒径１μｍ程度になるまで十分に粉砕・分散して記録層形成用塗布液を作製した。

【００８０】
厚さ１００μｍのポリエステルフィルム上に、塗布液Ａを塗布・乾燥して膜厚約５μｍの記録層Ａを設けた。次に、記録層Ａの上に、ポリビニルアルコールの１０ｗｔ％水溶液を塗布・乾燥して厚さ約２μｍの中間層を設けた。更に、中間層の上に、塗布液Ｂを塗布・乾燥して膜厚約５μｍの記録層Ｂを設けた。
一方、厚さ４．５μｍのポリエステルフィルムの片面に、接着剤層として飽和ポリエステル樹脂〔東洋紡（株）製：バイロン３００〕のトルエン／メチルエチルケトン溶液を塗布・乾燥した。この層の厚さは約０．５μｍであった。次に、記録層Ｂの上に、このフィルムを接着剤層と接するように重ね、圧力２ｋｇ（線圧）で温度１２５℃のヒートローラーを通して圧着した。
以上のようにして、中間層を挾んで記録層ＡとＢを持ち、更に表面に保護層を持った記録媒体を得た。この記録媒体を１２５℃のホットプレート上に約１０秒間のせて急冷した後、温度８２℃のオーブン中に３分間入れて記録層Ａを消色し、続いて温度６３℃のオーブン中に３分間入れて記録層Ｂを消色した。この操作によって該記録媒体は両記録層が消色した初期状態となった。
【００８１】
記録媒体の発色特性を調べるために次の操作▲１▼及び▲２▼を順次行い、それぞれの段階での発色色調を調べた。それぞれの加熱及び冷却操作は、ホットプレート上に１０秒間のせてから直ちに裏面を１℃の冷却板に接触させる方法で行った。
▲１▼　加熱温度　１２５℃・急冷→色調：あずき色（赤と緑の混合色）…Ａ、Ｂ両方とも発色
▲２▼　加熱温度　６５℃・急冷→色調：緑…Ａは発色、Ｂは消色
同様に下記の操作▲１▼及び▲２▼を順次行った。
▲１▼　加熱温度　１２５℃・急冷→色調：あずき色（赤と緑の混合色）…Ａ、Ｂ両方とも発色
▲２▼　加熱温度　８５℃・急冷→色調：赤…Ａは消色、Ｂは発色
以上の結果から、この記録媒体は１又は２段階の加熱・冷却操作によって３色の画像形成が可能なことが分った。これらは、いずれも次の操作▲１▼及び▲２▼を順次行うことで初期状態に戻すことができた。
▲１▼　加熱温度　８５℃・急冷
▲２▼　加熱温度　６５℃・急冷
以上の発色・消色は安定して繰り返すことができた。
【００８２】
実施例６
下記組成物Ａ及びＢを使った以外は実施例５と同様にして記録媒体を得た。

【００８３】
この記録媒体を実施例５と同様にして初期状態とした後、次の操作▲１▼及び▲２▼を順次行い、発色特性を調べた。
▲１▼　加熱温度　１２５℃・急冷→色調：あずき色（赤と緑の混合色）…Ａ、Ｂ両方とも発色
▲２▼　加熱温度　６５℃・急冷→色調：緑…Ａは発色、Ｂは消色
同様に下記の操作▲１▼及び▲２▼を順次行った。
▲１▼　加熱温度　１２５℃・急冷→色調：あずき色（赤と緑の混合色）…Ａ、Ｂ両方とも発色
▲２▼　加熱温度　８５℃・急冷→色調：赤…Ａは消色、Ｂは発色
以上の結果から、この記録媒体は３色の画像形成が可能なことが分った。これらの色は、実施例５と同様にして初期状態とすることができ、発色及び消色は安定して繰り返すことができた。
次に、該記録媒体を初期状態として、サーマルヘッドを使って下記▲１▼、▲２▼の条件で画像状に熱を印加して発色色調を調べた。
▲１▼　印加電圧１３．３Ｖ、パルス幅１．８ｍｓｅｃ→色調：あずき色…Ａ、Ｂ発色
▲２▼　印加電圧１３．３Ｖ、パルス幅０．５ｍｓｅｃ→色調：赤…Ｂのみ発色
このように、熱の印加条件によって発色色調の異なる画像が形成できた。
【００８４】
実施例７
下記組成物Ａ及びＢを使った以外は実施例５と同様にして記録媒体を得た。

【００８５】
この記録媒体を実施例５と同様にして初期状態とした後、次の操作▲１▼及び▲２▼を順次行って発色特性を調べた。
▲１▼　加熱温度　１２５℃・急冷→色調：あずき色（赤と緑の混合色）…Ａ、Ｂ両方とも発色
▲２▼　加熱温度　６５℃・急冷→色調：緑…Ａは発色、Ｂは消色
同様に下記の操作▲１▼及び▲２▼を順次行った。▲１▼　加熱温度　１２５℃・急冷→色調：あずき色（赤と緑の混合色）…Ａ、Ｂ両方とも発色
▲２▼　加熱温度　８５℃・急冷→色調：赤…Ａは消色、Ｂは発色
以上の結果から、この記録媒体は３色の画像形成が可能なことが分った。これらの色は、実施例５と同様にして初期状態とすることができ、発色・消色は安定して繰り返すことができた。
次に、記録媒体を初期状態として、サーマルヘッドを使って下記▲１▼、▲２▼の条件で画像状に熱を印加して発色色調を調べた。
▲１▼　印加電圧１３．３Ｖ、パルス幅１．８ｍｓｅｃ→色調：あずき色…Ａ、Ｂ発色
▲２▼　印加電圧１３．３Ｖ、パルス幅０．５ｍｓｅｃ→色調：赤…Ｂのみ発色
このように、熱の印加条件によって発色色調の異なる画像が形成できた。
【００８６】
実施例８
下記組成物Ａ及びＢを使った以外は実施例５と同様にして記録媒体を得た。

【００８７】
この記録媒体を実施例５と同様にして初期状態とした後、次の操作▲１▼及び▲２▼を順次行って発色特性を調べた。
▲１▼加熱温度１２５℃・急冷→色調：あずき色（赤と緑の混合色）…Ａ、Ｂ両方とも発色
▲２▼加熱温度　６５℃・急冷→色調：緑…Ａは消色、Ｂは発色
同様に次の操作▲１▼及び▲２▼を順次行った。
▲１▼　加熱温度１２５℃・急冷→色調：あずき色（赤と緑の混合色）…Ａ、Ｂ両方とも発色
▲２▼　加熱温度　８５℃・急冷→色調：赤…Ａは発色、Ｂは消色
以上の結果から、この記録媒体は３色の画像形成が可能なことが分った。これらの色は、実施例５と同様にして初期状態とすることができ、発色及び消色は安定して繰り返すことができた。
【００８８】
実施例９
実施例５と同じ記録媒体をホットプレートで１２５℃に加熱・急冷して、ＡとＢの両記録層が発色した状態にした（あずき色）。この記録媒体を、サーマルヘッドを使って、次の▲１▼、▲２▼の条件で画像状に加熱し、そのときの色調を調べた。▲１▼　印加電圧１３．３Ｖ、パルス幅１．６ｍｓｅｃ→色調：赤…Ａ消色、Ｂ発色
▲２▼　印加電圧８．０Ｖ、パルス幅０．９ｍｓｅｃ→色調：緑…Ａ発色、Ｂ消色
このように、全体があずき色に発色した中に▲１▼及び▲２▼の条件で熱を印加することによって、赤と緑の画像が形成できた。
【００８９】
実施例１０
下記組成物Ａ及びＢを使った以外は実施例５と同様にして記録媒体を得た。

【００９０】

この記録媒体を、実施例９と同様にしてＡとＢの記録層が全面的に発色した状態とした（あずき色）。次に、サーマルヘッドで下記▲１▼、▲２▼の条件で画像状に加熱し、そのときの発色色調を調べた。
▲１▼　印加電圧１３．３Ｖ、パルス幅１．６ｍｓｅｃ→色調：緑…Ａ消色、Ｂ発色
▲２▼　印加電圧８．０Ｖ、パルス幅０．８ｍｓｅｃ→色調：赤…Ａ発色、Ｂ消色
このように、全体があずき色に発色した中に▲１▼及び▲２▼の条件で熱を印加することにより、赤と緑の画像が形成できた。
【００９１】
実施例１１
下記顕色剤及び発色剤を含む組成物Ａ、Ｂを、それぞれボールミルで粒径約１μｍになるまで十分に粉砕・分散して記録層形成用塗布液を調製した。

【００９２】
厚さ１００μｍのポリエステルフィルム上に、塗布液Ｂを塗布・乾燥して膜厚約５μｍの記録層Ｂを設けた。
一方、厚さ４．５μｍのポリエステルフィルムの片面に、接着剤層として飽和ポリエステル樹脂〔東洋紡（株）製バイロン３００〕のトルエン／メチルエチルケトン溶液を塗布・乾燥して、中間層用のフィルムを得た。この場合、樹脂の乾燥付着量は３ｇ／ｍ^２であった。次に、このフィルムの接着剤層を前記で得た記録層Ｂの上に重ね、圧力２ｋｇ（線圧）、温度１２５℃のヒートローラーを通して圧着した。
次に、このようにして形成させた樹脂中間層の上に塗布液Ａを塗布・乾燥して膜厚約５μｍの記録層Ａを設け、本発明の可逆的多色感熱記録媒体を作製した。この記録媒体を温度１２５℃のホットプレート上に２０秒間のせて両方の記録層を発色させた後、温度８２℃のオーブン中に入れて記録層Ａを消色した。次に、温度６３℃のオーブン中に入れて記録層Ｂを消色した。この操作により、記録媒体はほぼ透明な初期状態となった。
【００９３】
該記録媒体の発色特性を調べるため次の操作▲１▼及び▲２▼を順次行い、それぞれの段階での発色色調を調べた。それぞれの加熱・冷却操作は、ホットプレート上に１０秒間のせてから直ちに裏面を１℃の冷却板に接触させる方法で行った。
▲１▼　加熱温度　１２５℃・急冷→色調：赤と緑の混合色…Ａ、Ｂ両方とも発色
▲２▼　加熱温度　６７℃・急冷→色調：赤…Ｂは消色、Ａのみ発色
同様に下記の操作▲１▼及び▲２▼を順次行った。
▲１▼　加熱温度　１２５℃・急冷→色調：赤と緑の混合色…Ａ、Ｂ両方とも発色
▲２▼　加熱温度　８５℃・急冷→色調：緑…Ａは消色、Ｂのみ発色
以上の結果から、この記録媒体は１段又は２段階の加熱及び冷却操作によって３色の画像形成が可能なことが分った。
以上の発色・消色操作は安定して繰り返すことができた。
【００９４】
実施例１２
下記Ｃ，Ｄの組成物を用い、実施例１１と同様にして記録層形成用塗布液を調製した。

【００９５】厚さ１００μｍのポリエステルフィルム上に、実施例１１と同様にして記録層Ｄを設けた。
一方、中間層及び保護層とする厚さ４μｍの芳香族ポリアミドフィルムの片面に、接着剤層として飽和ポリエステル樹脂〔東洋紡（株）製バイロン２００〕を実施例１１と同一手法で塗布し、このフィルムを前記のようにして形成させた記録層Ｄの上に実施例１１と同様にラミネートして貼り合せて中間層とした。
次に、実施例１１と同様にして中間層の上に記録層Ｃを設け、更にその上に中間層の場合と同様にして芳香族ポリアミドフィルムを貼り合せて保護層を形成させた。このようにして作製した本発明の可逆的多色感熱記録媒体を実施例１１と同様に処理し、Ｃ、Ｄの両記録層とも消色されたほぼ透明な初期状態の記録媒体を得た。
【００９６】
記録媒体の発色特性を調べるため次の操作▲１▼及び▲２▼を順次行い、それぞれの段階での発色色調を調べた。加熱及び冷却操作は実施例１１と同じである。
▲１▼　加熱温度　１２５℃・急冷→色調：赤と緑の混合色…Ｃ、Ｄ両方とも発色
▲２▼　加熱温度　６７℃・急冷→色調：緑…Ｄは消色、Ｃのみ発色
同様に下記の操作▲１▼及び▲２▼を順次行った。
▲１▼　加熱温度　１２５℃・急冷→色調：赤と緑の混合色…Ｃ、Ｄ両方とも発色
▲２▼　加熱温度　８５℃・急冷→色調：赤…Ｃは消色、Ｄのみ発色
以上の結果から、この記録媒体は１段又は２段階の加熱で３色の画像形成が可能なことが分った。これらは、いずれも実施例１１と同様に、各記録層を消色温度領域が高温側にある記録層から順に消色する方法で初期状態に戻すことができた。また、これらの発色・消色操作は安定して繰り返すことができた。
【００９７】
実施例１３
中間層のフィルムを厚さ４μｍのポリイミドフィルムに代えた以外は、実施例１１と同様にして本発明の可逆的多色感熱記録媒体を作製した。
この記録媒体について、実施例１１と同様にして発色特性を調べたところ、１段又は２段階の加熱により３色の画像形成が可能であった。また、これらの発色・消色操作は安定して繰り返すことができた。
実施例１４
中間層のフィルムを厚さ５μｍのポリパラバン酸フィルムに代えた以外は、実施例１１と同様にして本発明の可逆的多色感熱記録媒体を作製した。
この記録媒体について、実施例１１と同様にして発色特性を調べたところ、１段又は２段階の加熱により３色の画像形成が可能であった。また、これらの発色・消色操作は安定して繰り返すことができた。
【００９８】
実施例１５
下記Ｅ、Ｆ、Ｇの組成物を用い、実施例１１と同様にして記録層形成用塗布液を調製した。

【００９９】

【０１００】
厚さ１００μｍのポリエステルフィルム上に、実施例１１と同様にして記録層Ｇを設けた。その上に、実施例１１と同様にして中間層となる厚さ４．５μｍのポリエステルフィルムをドライラミネート法で貼り合せた。次に、記録層Ｇの場合と同様にして記録層Ｆを設けた。記録層Ｆの上に、前回と同一手法で中間層となるポリエステルフィルムを貼り合せた。更に、その上に同じ方法によって記録層Ｅを設けた。また、記録層Ｅの上に厚さ４μｍのポリアミドフィルムを実施例１２と同様にして貼り合せて保護層とした。
このようにして得られた３層の記録層を持つ可逆的多色感熱記録媒体を、オーブン加熱によって各層の消色温度に消色温度領域の高い順に処理し、全記録層を消色して初期状態とした。
【０１０１】
該記録媒体の発色特性を調べるため、実施例１１と同様に下記操作▲１▼、▲２▼、▲３▼を順次行った。
〔試験１〕
▲１▼　加熱温度　１２５℃・急冷→色調：赤、緑、黒の混合色…Ｅ，Ｆ，Ｇのすべてが発色
▲２▼　加熱温度　７０℃・急冷→色調：赤、黒の混合色…Ｅ，Ｇ発色、Ｆ消色
▲３▼　加熱温度　５５℃・急冷→色調：赤…Ｅのみ発色、Ｆ，Ｇ消色
〔試験２〕
▲１▼　加熱温度　１２５℃・急冷→色調：赤、緑、黒の混合色…Ｅ，Ｆ，Ｇのすべてが発色
▲２▼　加熱温度　８５℃・急冷→色調：緑、黒の混合色…Ｆ，Ｇ発色、Ｅ消色
▲３▼　加熱温度　５５℃・急冷→色調：緑…Ｆのみ発色、Ｅ，Ｇ消色
〔試験３〕
▲１▼　加熱温度　１２５℃・急冷→色調：赤、緑、黒の混合色…Ｅ，Ｆ，Ｇのすべてが発色
▲２▼　加熱温度　８５℃・急冷→色調：緑、黒の混合色…Ｆ，Ｇ発色、Ｅ消色
▲３▼　加熱温度　７０℃・急冷→色調：黒…Ｇのみ発色、Ｅ，Ｆ消色
以上の結果から、この記録媒体は段階的な加熱によって赤、緑、黒及びそれらの混合色による多色画像の形成が可能なことが分った。また、発色と消色は繰り返し行うことができた。
【０１０２】
実施例１６
以下の方法により、可逆的熱発色性組成物を芯材とするマイクロカプセルを作成した。
芯材としての２−アニリノ−６−（Ｎ−エチル−Ｎ−ｎ−ヘキシルアミノ）フルオランとドコシルホスホン酸のモル比１：４混合物を、塩化ビニル−酢酸ビニル共重合体（ＶＹＨＨ）１．５ｇを塩化メチレン２０ｇに溶解した液に分散し、これを界面活性剤を含む水溶液中に入れて乳化（Ｗ／Ｏ型）した。高速撹拌しながら塩化メチレンを蒸発させてカプセル壁を作り、ろ過・水洗・減圧乾燥してマイクロカプセル粉末Ａを得た。同様にして、芯材として、１，２．ベンゾ−６−（Ｎ−エチル−Ｎ−イソアミルアミノ）フルオランとヘキサデシルホスホン酸のモル比１：４混合物を含むマイクロカプセルＢを得た。
次に下記の組成の記録層形成用塗布液を調製した。
【０１０３】
〔記録層形成用塗布液組成〕
マイクロカプセルＡ　　　　　　　　　　　　　　　　　　　　　５部
マイクロカプセルＢ　　　　　　　　　　　　　　　　　　　　　５部
アイオノマー水性ディスパージョン
（大日本インキ社製；ハイドランＡＰ−４０）　　　　　　　３０部
メラミン系架橋剤
（大日本インキ社製；ＤＥＣＫＡＭＩＮＥ　ＰＭ−Ｎ）　　１．５部
触媒（大日本インキ社製；ＣＡＴＡＬＹＳＴ　ＥＳ−２）　　０．７部
この液を厚さ１００μｍのポリエステルフィルム上に塗布し、１００℃で１０分間乾燥して厚さ約１０μｍの記録層を形成させた。
この記録媒体を実施例５と同様な方法で初期状態とした後、実施例７と同様にして発色特性を調べた。その結果、実施例７と同様な発色特性が得られた。
【０１０４】
実施例１７
下記の顕色剤と発色剤をモル比で５：１に混合・粉砕した混合物を用意した。
オクタデシルホスホン酸
２−（ｏ−クロルアニリノ）−６−ジブチルアミノフルオラン
厚さ約１ｍｍのガラス板を用意し、このガラス板をホットプレート上でその表面が１７０℃になるように加熱した。そのガラス板上に上記混合物の粉末を少量のせて溶融させた後、その融液上に厚さ０．１ｍｍのガラス板をかぶせて融液を均一な厚さに広げた。次に、全体をホットプレートからはずして氷水に接触させて急冷後、上にかぶせた０．１ｍｍのガラス板をはがし取り、発色した記録層（可逆性）の上にポリビニルアルコールの５ｗｔ％水溶液を塗布・乾燥して中間層を設けた。
【０１０５】
続いて、下記組成の不可逆的記録層形成用塗布液を塗布・乾燥して本発明の多色感熱記録媒体を作成した。

この記録媒体を、まず７２℃に一時的に加熱・冷却して可逆的記録層を消色した。この状態が未記録の初期状態であり、両記録層が無色の状態となっている。
【０１０６】
このようにして得られた記録媒体に対して、表７の▲１▼〜▲３▼の記録操作を順次行い、表７に示す３種類の色調の発色を得た。この記録媒体では、一たん不可逆的感熱記録層を発色させると赤色の下地色となり、その上に黒色の画像を可逆的に形成させることができる。
【表７】

【０１０７】
実施例１８
可逆的感熱記録層の顕色剤と発色剤を下記の組合せで作成した以外は、実施例１７と同様にして本発明の可逆的多色感熱記録媒体を作成した。
ヘキサデシルホスホン酸
２−アニリノ−３−メチル−６−（Ｎ−エチル−ｐ−トルイジノ）フルオラン
この記録媒体を、実施例１７の場合と同様に処理して該記録媒体を未記録の初期状態とした。
このようにして得られた記録媒体に対して表８の▲１▼〜▲３▼の記録操作を順次行い、表８に示す３種類の色調の発色を得た。この記録媒体の場合も、実施例１７の場合と同様に赤色の下地色形成と、その上への黒色画像の可逆的形成が可能である。
【表８】

【０１０８】
実施例１９
可逆的感熱記録層の顕色剤と発色剤を下記の組合せで作製した以外は、実施例１７と同様にして本発明の可逆的多色感熱記録媒体を作製した。
エイコシルチオリンゴ酸
２−アニリノ−３−メチル−６−ジエチルアミノフルオラン
この記録媒体を、実施例７の場合と同様に処理して、該記録媒体を未記録の初期状態とした。
このようにして得られた記録媒体に対して表９の▲１▼〜▲３▼の記録操作を順次行い、表９に示す３種類の色調の発色を得た。この記録媒体の場合も、実施例１７の場合と同様に赤色の下地色形成と、その上への黒色画像の可逆的形成が可能である。
【表９】

【０１０９】
【発明の効果】
本発明の可逆的多色感熱記録媒体及び表示媒体では、熱を印加するだけで容易に多色画像を形成することができ、この画像は常温で安定に保持することができるうえ、その多色画像は消去が可能なので繰り返し使用することができる。形成される多色画像の発色色調は組成物の選択によって自由に変えることができるから、三原色を発色剤とすることによってフルカラー画像も形成可能である。
【図面の簡単な説明】
【図１】本発明で用いる組成物の発色濃度と温度の関係を示すグラフで、発色及び消色原理の説明図である。実線（Ａ→Ｂ→Ｃ）は画像形成過程を、破線（Ｃ→Ｄ→Ａ）は画像消去過程を示す。
【図２】長いアルキル鎖を持つホスホン酸を顕色剤にした組成物について、その光の透過度と温度との関係を示す図である。
【図３】本発明の可逆的多色感熱記録媒体の基本的構成の一例を示す図である。
【図４】本発明の可逆的多色感熱記録層において、該記録層を構成する各層の濃度と温度の関係を表す図である。
【図５】図４と同一の関係を表す別の例を示す図である。
【図６】本発明の記録装置の基本的構成を示す図である。
【図７】本発明の表示装置の基本的構成を示す図である。この図において（ａ）はシート状の表示媒体を使用した場合、（ｂ）はエンドレスベルト状の表示媒体を使用した場合の装置における基本的構成を示している。
【符号の説明】
Ａ，Ｂ，Ｃ　　　　記録層
Ｓ　　　　　　　　支持体
Ｍ　　　　　　　　中間層
Ｐ　　　　　　　　保護層
Ｒ　　　　　　　　可逆的多色感熱記録媒体
Ｈ_１，Ｈ_２，Ｈ_３　　　画像状に熱を印加できる発熱体
Ｌ_１，Ｌ_２，Ｌ_３　　　全体加熱用発熱体
Ｈ_１’，Ｈ_２’，Ｈ_３’　画像状に熱を印加できる発熱体
Ｌ_１’，Ｌ_２’，Ｌ_３’　全体加熱用発熱体
Ｄ　　　　　　　　可逆的多色感熱表示媒体[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a reversible multicolor thermosensitive recording medium and a reversible multicolor thermochromic composition.
Note that the term “recording medium” used in the claims of this specification includes a display medium.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, thermosensitive recording media utilizing a color-forming reaction between an electron-donating color-forming compound (hereinafter, also referred to as a color former) and an electron-accepting compound (hereinafter, also referred to as a color developer) are widely known. , Facsimile, automatic ticket vending machines, scientific measuring machine printers, CRT medical measuring printers, etc. However, all of the conventional products have an irreversible color development and cannot alternately repeat the color development and the decoloration.
On the other hand, according to the patent gazette, some thermal recording media utilizing a color-forming reaction between a color-forming agent and a color-developing agent for reversibly developing and decoloring have been proposed. For example, Japanese Patent Application Laid-Open No. 60-193691 discloses a developer using a combination of gallic acid and phloroglucinol as a color developer. A colored body obtained by thermally coloring this is decolorized with water or water vapor. However, in the case of this heat-sensitive recording medium, there is a problem in that it is difficult to make the recording medium water-resistant, and there is a problem in the recording preservability.
[0003]
JP-A-61-237684 discloses a rewritable optical recording medium using a compound such as phenolphthalene, thymolphthalene, or bisphenol as a color developer. This product forms a colored body by gradually cooling it after heating, and can be decolored by rapidly cooling the heated colored body to a temperature just higher than the coloring temperature. However, in the case of this recording medium, the steps of coloring and decoloring are complicated, and the decolored body obtained by decoloring the colored body still shows some coloring, so that a color image with good contrast can be obtained. Can not. JP-A-62-140881, JP-A-62-138568 and JP-A-62-138556 disclose a homogeneous solution of a color former, a color developer and a carboxylic acid ester. It shows a completely colored state at a low temperature and a completely erased state at a high temperature, and can maintain the colored or erased state at an intermediate temperature between them. By printing on this medium with a thermal head, the colored background White characters (decolorable) can be recorded on (colored). Therefore, in the case of this recording medium, the use of the recorded image is limited because the recorded image is a negative image, and it is necessary to keep the image within a specific temperature range for storing the recorded image.
[0004]
JP-A-2-188294 and JP-A-2-188293 disclose, as color developers, salts of gallic acid and higher aliphatic amines which reversibly develop and reduce the color, and bis (hydroxy). The use of a salt of phenyl) acetic acid or butyric acid with a higher aliphatic amine is shown. It can be colored by heat in a specific temperature range and decolored by heating at a higher temperature.However, since the color developing effect and the color reducing effect occur competitively, these effects are thermally affected. It is difficult to control, and it is difficult to obtain good image contrast.
As described above, the conventional reversible thermosensitive recording medium utilizing the reaction between the color former and the developer contains various problems and is still unsatisfactory.
[0005]
On the other hand, there has been a great demand for multicolor recording, and in recent years, two-color heat-sensitive recording materials used for labels, coupons, tack paper, video printers, and the like have reached the practical use. The gist of this manufacturing method is that high-temperature and low-temperature coloring layers that develop different colors with different coloring heat energies are laminated on a support, and two types of methods have been proposed. One of them is that the image of the low-temperature coloring layer, which is colored when the high-temperature coloring layer is formed, is not erased. It is obtained as an intermediate color of a color tone when color is formed. Another method is to use a suitable decoloring agent to erase the color image of the low-temperature layer, which is simultaneously colored, when the high-temperature color layer is colored. However, in the former case, a two-color image with good contrast cannot be obtained unless the color tone of the high-temperature color layer can sufficiently hide the color tone of the low-temperature color layer. Is impossible. In the latter case, any combination of color developing tones can be used, but it is difficult to achieve both color developing properties and decoloring properties. At the present, it is difficult to achieve three or more colors or full color, and there is no reversible multicolor thermal image forming method.
[0006]
As described above, there is a great demand for multi-color recording, and it is expected that the market needs for highly practical multi-color recording media will be great, but research has only just begun. . The field of thermal display media is further devised in terms of multicoloring, and it is a general idea that colorization is difficult with the current system. For example, in the case of a thermal display using a metal complex salt-based thermochromic material, it has attracted attention as a thermoreversible and free-to-write simple display, but there is a problem with contrast and the like and it is in a stage where it can be sufficiently satisfied. I can not say. A thermal display utilizing the change in the transparency of an organic compound due to temperature has also been proposed. However, in this case, since only a black-and-white image can be obtained, this method cannot be said to be an appropriate display or electronic blackboard that appeals to the visual sense.
[0007]
[Problems to be solved by the invention]
The present invention provides a reversible thermosensitive recording medium utilizing a reaction between a color former and a developer, in which color development and decoloration can be easily performed only by heating, and furthermore, the color development state and the decoloration state are changed. It is an object of the present invention to provide a reversible multicolor thermosensitive recording medium and a reversible multicolor thermochromic composition that can be stably maintained at room temperature and have a decoloring temperature lower than the coloring temperature.
[0008]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.
That is, according to the present invention, the following reversible multicolor thermosensitive recording medium and reversible multicolor thermochromic composition are provided.
[0009]
(1) A reversible multicolor thermosensitive recording medium in which a plurality of types of reversible thermochromic compositions having different color tone and decolorization start temperature are present on a support in a separated and independent state, respectively. Are contained in independent microcapsules.
(2) The reversible multicolor thermosensitive recording medium according to (1), wherein an irreversible thermochromic composition is present on the support in addition to the reversible thermochromic composition.
(3) A reversible multicolor thermochromic composition comprising a mixture of microcapsules independently containing a plurality of types of reversible thermochromic compositions having different color tone and decoloration start temperature.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
In the reversible multicolor thermosensitive recording medium and the display medium (the recording medium described below includes the display medium), the recording layer or the display layer containing the developer and the color former (the recording layer described below has a (Including the display layer), or a recording layer containing a plurality of types of microcapsules containing a developer and a color former, and a plurality of recording layers or a plurality of types of microcapsules. The capsules have different color tone and decoloration start temperature. Therefore, if the image is heated at a temperature equal to or higher than the temperature at which all the recording layers develop, a mixed color image in which all layers or all the microcapsules develop can be obtained. When heat is applied, a mixed color or single color image in which the color of the recording layer or the microcapsule corresponding to the decoloring temperature has disappeared can be obtained. By repeating such an operation, an image of any single color or mixed color constituting the recording layer can be obtained. In the present invention, the coloring of a part of the recording layer or the microcapsule constituting the reversible multicolor heat-sensitive recording layer may be irreversible, but in this case, the irreversible recording layer or the microcapsule is colored once. Since it cannot be erased, it only exists on the recording medium as a background color.
[0011]
The reversible thermochromic composition used in the present invention is composed of an electron-donating color-forming compound and an electron-accepting compound. The color can be instantaneously generated by heating, and the color-forming state is stable even at room temperature. Exists. On the other hand, the composition in the color-developing state can be decolorized by heating to a decoloring temperature lower than the color-developing temperature, and the decolored state exists stably even at room temperature.
The principle of color development and decoloration of the reversible thermochromic composition (hereinafter, also simply referred to as composition) according to the present invention, that is, the principle of image formation and image erasure will be described with reference to the graph shown in FIG.
The vertical axis of the graph represents the color density and the horizontal axis represents the temperature. The solid line 1 shows the image forming process by heating, and the broken line 3 shows the image erasing process by heating. A is the density in the completely erased state, B is T ₁ The density in the saturated coloring state when heated to the above temperature, and C is T in the saturated coloring state. ₀ Where D is T ₀ ~ T ₁ It shows the density when heating and decoloring at temperatures between.
[0012]
The composition is T ₀ At the following temperatures, it is in a colorless state (A). In order to form an image, T ₁ Heating to the above temperature is sufficient, and the color is formed (B) to form an image. This image has a T ₀ Even when the temperature is returned to the following temperature, the state (C) is maintained, and the memory property of the recording is not lost.
Next, in order to erase the image, the color-developed composition is heated to a temperature lower than the color development temperature. ₀ ~ T ₁ It is sufficient to heat to a temperature between the two, and the colorless state (D) is obtained. This state is T ₀ Even when the temperature is returned to the following temperature, the colorless state (A) is maintained as it is. That is, the image formation process reaches C through the path indicated by the solid line ABC, and the image is held. In the image erasing process, the erasing state is reached up to A along the path indicated by the broken line CDA. This image forming and erasing behavior characteristics are reversible and can be repeated many times.
[0013]
The color development of the composition used in the present invention is obtained by cooling a color former composition formed by a eutectic reaction of a color developer and a color former by heating to room temperature. Since the color forming composition has a decoloring temperature region on a lower temperature side than the melting temperature, it is generally preferable to rapidly cool to cool to room temperature while maintaining color development from the molten color forming state. When gradually cooled, decoloring occurs when passing through the decoloring temperature range, and the density often decreases.
It is considered that the color former composition is one in which the molecules of the color former and the developer interact, and the lactone ring of the color former is opened to form a color. The color former composition that has been quenched from the molten state contains color former molecules and color developer molecules and color former molecules that are not directly involved in the formation of the color former. At normal temperature, the color forming composition is in a solidified state due to cohesion between these molecules.
[0014]
The color forming composition is an aggregated solid as described above. The aggregate structure in this state shows regularity, but the degree of this regularity may be very high or not very high, but this depends on the combination of developer and color former, the amount ratio, or cooling. Depends on conditions. The formation of such an aggregated structure is basically based on the alkyl chain structure portion of the color developer molecule forming the color former and the excess alkyl chain structure portion of the color developer molecule not forming the color former. It is presumed that the cohesive force acting between and mainly acts. The formation of such an aggregation structure is related to the decoloring phenomenon of the color forming composition.
Such a color forming composition can be heated to a specific temperature range to be decolorized. In the decoloring process, the aggregate structure of the color former composition changes, and finally the developer molecules are separated and crystallized from the color former to form crystals of the color developer alone, resulting in a stable decolored state. Have been confirmed by X-rays.
[0015]
In the composition used in the present invention, the alkyl group of the color developer plays a large role in the process of forming and decoloring the color forming body. Therefore, the color development and decolorization temperatures can be controlled by the length of the alkyl chain portion of the color developer, and the color development and decolorization temperatures shift to higher temperatures as the chain length increases. This is because the cohesiveness and mobility of the developer molecules change depending on the length of the alkyl chain portion.
Table 1 and FIG. 2 specifically show the relationship between the alkyl chain length of the color developer, the color development start temperature, and the decolorization start temperature.
[Table 1]

[0016]
Table 1 and FIG. 2 show the coloring of reversible thermochromic compositions obtained from phosphonic acids of various chain lengths, which are representative color developers, and 2- (o-chloroanilino) -6-dibutylaminofluorane. It shows the relationship between the decolorization start temperature and the alkyl chain length of the phosphonic acid. The numbers P14 to P20 added to the curve in FIG. 2 indicate the respective alkyl chain lengths.
FIG. 2 shows a result of measuring a change in the amount of light passing through the color body when the temperature of the color body is increased, and the initial light amount is set to 1.0. Therefore, the place where the curve rises is the decolorization start temperature, and the place where the curve descends and becomes the same as the initial is the color development start temperature. From FIG. 2, it is clearly observed that the longer the alkyl chain, the higher the decoloring start temperature shifts to the higher temperature side and the higher the color development start temperature shifts to the higher temperature side.
[0017]
The reversible thermochromic composition used in the present invention is basically a composition in which the developer having an alkyl chain structure is combined with a color former, and a preferred color former is present for each developer. I do. The combination of the color developer and the color forming agent constituting the reversible thermochromic composition occurs when the composition in a colored state obtained by heating both to a temperature higher than the melting temperature is heated to a temperature lower than the melting temperature. It is appropriately selected depending on the easiness of decoloring, that is, the characteristics such as the decoloring property and the color tone of the color development state. Among these, the color erasing property can be determined by the presence or absence of an exothermic peak appearing in a heating process in the differential thermal analysis (DTA) or the differential scanning calorimetry (DSC) of the color-forming composition obtained by the combination. This exothermic peak corresponds to the decoloring phenomenon that characterizes the composition, and serves as a criterion for selecting a good combination of decoloring properties. It should be noted that even if a third substance is present in the composition, no action is taken. For example, even when a polymer compound is present, its reversible decoloring behavior can be maintained.
[0018]
Next, the multicolor image forming mechanism according to the present invention will be described in detail.In the reversible multicolor thermosensitive recording medium of the present invention, a plurality of stacked recording layers or a plurality of types of microcapsules have different color tones and different colors. It has a decoloring start temperature. As described above, in the present invention, after all of the plurality of recording layers or microcapsules are colored, by erasing some of the recording layers or microcapsules, an image consisting of an arbitrary mixed color and a single color can be obtained. Obtainable. This has become possible because the reversible thermochromic composition used in the present invention has its decoloration onset temperature at a lower temperature than the coloration temperature, and the coloration onset temperature and decolorization onset temperature of the composition. The reversible multicolor thermosensitive recording medium of the present invention is a revolutionary reversible thermoreversible recording medium that cannot be considered by analogy with the prior art. Multi-color thermal recording medium.
[0019]
The reversible multicolor heat-sensitive recording medium of the present invention is prepared by preparing a plurality of types of compositions having different coloring tones and decolorization start temperatures, and laminating a plurality of recording layers each independently containing these compositions. Alternatively, a plurality of types of microcapsules each independently containing the composition may be prepared, and a mixture of these microcapsules may be contained in one recording layer. Further, the recording medium of the present invention contains an irreversible thermochromic composition (refers to a thermochromic composition whose erasing temperature is higher than the chromogenic temperature or which has no erasing temperature and is difficult to erase). May be. Further, in the reversible multicolor thermosensitive recording medium of the present invention, a resin intermediate layer may be provided between each recording layer in order to prevent the above-mentioned recording layers from melting and mixing during heating.
[0020]
Next, a multicolor image forming mechanism according to the present invention will be described with reference to FIG.
FIG. 3 shows a basic configuration diagram of a reversible multicolor thermosensitive recording medium having a plurality of recording layers of the present invention. FIG. 3 shows a structure in which reversible thermosensitive recording layers A, B, and C having different color tone and decolorization start temperature are laminated on a support S, M indicates a resin intermediate layer, and P indicates a protective layer. Is shown.
4A, 4B, and 4C show the relationship between the color development start temperature and the color erasure start temperature for each of the reversible thermosensitive recording layers A, B, and C in FIG. In FIG. 4, the horizontal axis represents temperature, and the vertical axis represents color density. In the figure, the solid curve shows the density change when the temperature is increased from the decolored state. ₁ , And a color is formed at a temperature higher than this temperature. This TA ₁ Is the color development start temperature of the recording layer A. Similarly, the coloring start temperature of the recording layers B and C is TB ₁ , TC ₁ It is. The curve shown by the dashed line in the figure shows the density change when the temperature of the recording layer in the colored state is increased from room temperature. ₂ It suddenly drops and loses color. This TA ₂ Is the decoloring start temperature of the recording layer A. Similarly, for the recording layers B and C, TB ₂ , TC ₂ Is the decoloration start temperature.
The color development start temperature and the color erasure start temperature of the recording layers A, B, and C are different from each other, and the area indicated by the arrow between the color development start temperature and the color erasure start temperature, ie, the color erasure temperature area is between It is out of alignment.
[0021]
Next, a recording method using a recording medium including three reversible thermosensitive recording layers having a color development start temperature and a color erasure start temperature shown in FIG. 4 will be described as an example. 4 (a), 4 (b) and 4 (c), it can be seen that the decoloring start temperature of each layer is A at the lowest temperature side, C is at the highest temperature side, and B is between these. Now, this recording medium is used as the coloring start temperature TC of the recording layer C. ₁ Higher temperature T ₁ When the recording medium is temporarily heated and cooled, not only the recording layer C but also the recording layers A and B develop color, so that the color of the recording medium becomes a mixed color of three layers A, B and C.
Next, the recording medium that has developed the mixed color (A, B, C) is subjected to the temperature T in the decolorizing temperature region of the recording layer B. ₃ (TA ₁ <T ₃ <TC ₂ ) Is temporarily heated and cooled, the temperature T ₃ The recording layer B is decolorized by ₃ Is the color development start temperature TA of the recording layer A ₁ The decoloration start temperature TC of the recording layer C is ₂ Because of the following, the recording layers A and C are not erased. Therefore, the recording medium of the mixed color (A, B, C) is set at the temperature T ₃ , A mixed color (A, C) is obtained.
[0022]
The recording medium that has developed the mixed color (A, C) is subjected to the temperature T in the decolorizing temperature region of the recording layer A. ₄ (TA ₂ <T ₄ <TB ₂ If the recording layer A is temporarily heated and cooled, the color of only the recording layer A is erased, and the color of the recording layer C remains unchanged. Similarly, the recording medium in which the entire recording layer is in the decolored state is heated to a temperature T which is equal to or higher than the color development start temperature of the recording layer B and is in the decolorization temperature region of the recording layer C. ₂ To obtain a mixed color (A, B). ₄ When the recording layer B is temporarily heated, the color of the recording layer B is obtained. Also, T ₁ The recording medium of mixed colors (A, B, C) obtained by temporarily heating the recording medium at a temperature T ₄ , Only the recording layer A is erased, and a mixed color (B, C) is obtained. Further, the recording medium in which the entire recording layer is in the decolored state is heated to a temperature ₃ If the recording layer A is temporarily heated, a color in which only the recording layer A has developed can be obtained.
[0023]
Table 2 summarizes the relationship between the heating temperature and the obtained color in the recording medium having the three types of recording layers A, B, and C shown in FIG.
[Table 2]

[0024]
Here, the heating temperature means to temporarily heat to that temperature, for example, T ₁ → T ₃ This means that temporarily ₁ After heating and cooling to ₃ Means temporarily heating and cooling.
Here, the case where the number of reversible thermosensitive recording layers is three has been described, but multicolor recording can be similarly performed in the case of two or four or more layers. In the case of two layers, an image of three colors can be obtained by combining a mixed color and a single color. An image of seven colors can be obtained with three layers and an image of 15 colors can be obtained with four layers. As can be seen from the above description, if each recording layer that is colored is sequentially decolored from the recording layer whose decoloration start temperature is on the high temperature side to decolorize all the recording layers, the initial state is obtained. can do. In addition, this operation enables the recording medium to repeatedly form a multicolor image.
[0025]
Next, multi-color recording on a recording medium composed of three layers having a decoloration start temperature and a color development start temperature shown in FIGS. 5A, 5B, and 5C will be described.
These three layers have substantially the same color development start temperature and differ only in the color erasure start temperature. Temperature T at which all three layers are colored at first ₁ To obtain a mixed color (A, B, C). When the recording medium in this state is ₄ When the layer is temporarily heated, only the layer A is erased and becomes a mixed color (B, C). Further, the mixed color (A, B, C) or the mixed color (B, C) is temporarily set to T. ₃ , The color of the A, B or B layer is erased, and only the C layer is colored. Therefore, in this case, recording of three colors is possible.
As can be understood from the above description, a multicolor image can be formed even if the color formation start temperatures are the same and there is a difference in the color erasure start temperatures.
[0026]
In the reversible thermosensitive recording medium of the present invention, the color developing agent used in combination with the color forming agent basically has a structure exhibiting a color developing ability capable of forming the color forming agent in the molecule and a cohesive force between the molecules. A compound having an alkyl chain structure portion to be controlled, and is an organic phosphoric acid compound, an aliphatic carboxylic acid compound or a phenol compound having an aliphatic group having 12 or more carbon atoms, or a mercaptoacetic acid having an aliphatic group having 10 to 18 carbon atoms. Or a caffeic acid alkyl ester having an alkyl group having 5 to 8 carbon atoms. The aliphatic group includes a linear or branched alkyl group and alkenyl group, and may have a substituent such as a halogen, an alkoxy group, and an ester group. Hereinafter, the color developer will be specifically exemplified.
[0027]
(A) Organophosphate compound
Those represented by the following general formula (1) are preferably used.
Embedded image
R ₁ -PO (OH) ₂ (1)
(However, R ₁ Represents an aliphatic group having 12 or more carbon atoms)
Specific examples of the organic phosphoric acid compound represented by the general formula (1) include, for example, the following.
Dodecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, octadecylphosphonic acid, eicosylphosphonic acid, docosylphosphonic acid, tetracosylphosphonic acid, hexacosylphosphonic acid, octacosylphosphonic acid and the like.
[0028]
As the organic phosphoric acid compound, α-hydroxyalkylphosphonic acid represented by the following general formula (2) is also preferably used.
Embedded image

(However, R ₂ Is an aliphatic group having 11 to 29 carbon atoms)
Specific examples of the α-hydroxyalkylphosphonic acid represented by the general formula (2) include α-hydroxydodecylphosphonic acid, α-hydroxytetradecylphosphonic acid, α-hydroxyhexadecylphosphonic acid, and α-hydroxyoctadecylphosphonic acid. Acids, α-hydroxyeicosylphosphonic acid, α-hydroxydocosylphosphonic acid, α-hydroxytetracosylphosphonic acid and the like.
[0029]
(B) Aliphatic carboxylic acid compound
Α-Hydroxy fatty acids represented by the following general formula (3) are preferably used.
Embedded image
R ₃ -CH (OH) -COOH (3)
(However, R ₃ Represents an aliphatic group having 12 or more carbon atoms)
Examples of the α-hydroxy aliphatic carboxylic acid compound represented by the general formula (3) include the following.
α-hydroxydodecanoic acid, α-hydroxytetradecanoic acid, α-hydroxyhexadecanoic acid, α-hydroxyoctadecanoic acid, α-hydroxypentadecanoic acid, α-hydroxyeicosanoic acid, α-hydroxydocosanoic acid, α-hydroxytetracosanoic acid , Α-hydroxyhexacosanoic acid, α-hydroxyoctacosanoic acid and the like.
[0030]
As the aliphatic carboxylic acid compound, an aliphatic carboxylic acid compound having an aliphatic group having 12 or more carbon atoms and substituted with a halogen element, and a compound having a halogen element at least in the α-position or β-position carbon is also preferably used. . Specific examples of such compounds include, for example, the following.
2-bromohexadecanoic acid, 2-bromoheptadecanoic acid, 2-bromooctadecanoic acid, 2-bromoeicosanoic acid, 2-bromodocosanoic acid, 2-bromotetracosanoic acid, 3-bromooctadecanoic acid, 3-bromoeicosanoic acid 2,3-dibromooctadecanoic acid, 2-flordodecanoic acid, 2-flortetradecanoic acid, 2-florhexadecanoic acid, 2-floroctadecanoic acid, 2-floreicosanoic acid, 2-flordocosanoic acid, 2-iodohexadecanoic acid, 2-iodooctadecanoic acid, 3-iodohexadecanoic acid, 3-iodooctadecanoic acid, perfluorooctadecanoic acid and the like.
[0031]
As the aliphatic carboxylic acid compound, an aliphatic carboxylic acid compound having an aliphatic group having 12 or more carbon atoms having an oxo group in a carbon chain, and at least the α-position, β-position or γ-position carbon becomes an oxo group Are also preferably used. Specific examples of such compounds include, for example, the following.
2-oxododecanoic acid, 2-oxotetradecanoic acid, 2-oxohexadecanoic acid, 2-oxooctadecanoic acid, 2-oxoeicosanoic acid, 2-oxotetracosanoic acid, 3-oxododecanoic acid, 3-oxotetradecanoic acid, 3-oxohexadecanoic acid, 3-oxooctadecanoic acid, 3-oxoeicosanoic acid, 3-oxotetracosanoic acid, 4-oxohexadecanoic acid, 4-oxooctadecanoic acid, 4-oxodokosanoic acid and the like.
[0032]
As the aliphatic carboxylic acid compound, a dibasic acid represented by the following general formula (4) is also preferably used.
Embedded image

(However, R ₄ Represents an aliphatic group having 12 or more carbon atoms, X represents an oxygen atom or a sulfur atom, n represents 1 or 2, and Xn represents -SO ₂ -May be a group)
Specific examples of the dibasic acid represented by the general formula (4) include the following.
Dodecylmalic acid, tetradecylmalic acid, hexadecylmalic acid, octadecylmalic acid, eicosylmalic acid, docosylmalic acid, detracosylmalic acid, dodecylthiomalic acid, tetradecylthiomalic acid, hexadecylthiomalic acid, octadecyl Thiomalic acid, eicosylthiomalic acid, docosylthiomalic acid, tetracosylthiomalic acid, dodecyldithiomalic acid, tetradecyldithiomalic acid, hexadecyldithiomalic acid, octadecyldithiomalic acid, eicosyldithiomalic acid, Docosyldithiomalic acid, tetracosyldithiomalic acid, dodecylsulfonbutanedioic acid, tetradecylsulfonbutanedioic acid, hexadecylsulfonbutanedioic acid, octadecylsulfonbutanedioic acid, eicosylsulfonbutanedioic acid, docosyls Honbutan such as a two acid.
[0033]
As the aliphatic carboxylic acid compound, a dibasic acid represented by the following general formula (6) is also preferably used.
Embedded image

(However, R ₅ , R ₆ , R ₇ Represents hydrogen or an aliphatic group, at least one of which is an aliphatic group having 12 or more carbon atoms)
Specific examples of the dibasic acid represented by the general formula (5) include the following.
Dodecyl butane diacid, tridecyl butane diacid, tetradecyl butane diacid, pentadecyl butane diacid, octadecyl butane diacid, eicosyl butane diacid, docosyl butane diacid, 2,3-dihexadecyl butane diacid, 2, , 3-Dioctadecylbutanedioic acid, 2-methyl-3-dodecylbutanedioic acid, 2-methyl-3-tetradecylbutanedioic acid, 2-methyl-3-hexadecylbutanedioic acid, 2-ethyl-3- Dodecyl butane diacid, 2-propyl-3-dodecyl butane diacid, 2-octyl-3-hexadecyl butane diacid, 2-tetradecyl-3-octadecyl butane diacid, and the like.
[0034]
As the aliphatic carboxylic acid compound, a dibasic acid represented by the following general formula (6) is also preferably used.
Embedded image

(However, R ₈ , R ₉ Represents hydrogen or an aliphatic group, at least one of which is an aliphatic group having 12 or more carbon atoms)
Specific examples of the dibasic acid represented by the general formula (6) include the following.
Dodecylmalonic acid, tetradecylmalonic acid, hexadecylmalonic acid, octadecylmalonic acid, eicosylmalonic acid, docosylmalonic acid, tetracosylmalonic acid, didodecylmalonic acid, ditetradecylmalonic acid, dihexadecylmalonic acid, di Octadecylmalonic acid, dieicosylmalonic acid, didocosylmalonic acid, methyloctadecylmalonic acid, methyleicosylmalonic acid, methyldocosylmalonic acid, methyltetracosylmalonic acid, ethyloctadecylmalonic acid, ethyleicosylmalonic acid, ethyldoco Silmaronic acid, ethyltetracosylmalonic acid and the like.
[0035]
As the aliphatic carboxylic acid compound, a dibasic acid represented by the following general formula (7) is also preferably used.
Embedded image

(However, R ₁₀ Represents an aliphatic group having 12 or more carbon atoms, n represents 0 or 1, m represents 1, 2 or 3, when n is 0, m is 2 or 3, and when n is 1, m represents 1 or 2)
The following are specific examples of the dibasic acid represented by the general formula (7).
2-dodecyl-pentanedioic acid, 2-hexadecyl-pentanedioic acid, 2-octadecyl-pentanedioic acid, 2-eicosyl-pentanedioic acid, 2-docosyl-pentanedioic acid, 2-dodecyl-hexanedioic acid, 2- Pentadecyl-hexanedioic acid, 2-octadecyl-hexanedioic acid, 2-eicosyl-hexanedioic acid, 2-docosyl-hexanedioic acid and the like.
[0036]
As the aliphatic carboxylic acid compound, a tribasic acid such as citric acid acylated with a long-chain fatty acid is also preferably used. Specific examples thereof include the following.
Embedded image

[0037]
(C) phenolic compound
The compound represented by the following general formula (8) is preferably used.
Embedded image

(Where Y represents -S-, -O-, -CONH- or -COO-, ₁₁ Represents an aliphatic group having 12 or more carbon atoms, and n is an integer of 1, 2 or 3.
Specific examples of the phenol compound represented by the general formula (8) include, for example, the following.
p- (dodecylthio) phenol, p- (tetradecylthio) phenol, p- (hexadecylthio) phenol, p- (octadecylthio) phenol, p- (eicosylthio) phenol, p- (docosylthio) phenol, p- (tetracosylthio) phenol Ruthio) phenol, p- (dodecyloxy) phenol, p- (tetradecyloxy) phenol, p- (hexadecyloxy) phenol, p- (octadecyloxy) phenol, p- (eicosyloxy) phenol, p- ( (Docosyloxy) phenol, p- (tetracosyloxy) phenol, p-dodecylcarbamoylphenol, p-tetradecylcarbamoylphenol, p-hexadecylcarbamoylphenol, p-octadecylcarbamoylphenol, p-eikoshi Carbamoyl phenol, p- de waist carbamoyl phenol, p- tetracosyl carbamoyl phenol, gallic acid hexadecyl ester, gallic acid octadecyl ester, gallic acid eicosyl ester, gallic acid docosyl esters, such as gallic acid tetracosyl esters.
[0038]
As the phenol compound, caffeic acid alkyl esters represented by the following general formula (9) can also be used.
Embedded image

(However, R ₁₂ Is an alkyl group having 5 to 8 carbon atoms)
Specific examples of the caffeic acid alkyl ester represented by the general formula (9) include caffeic acid-N-pentyl, caffeic acid-n-hexyl, caffeic acid-n-heptyl, and caffeic acid-n-octyl. Can be
[0039]
(D) Metal salt of mercaptoacetic acid
A metal salt of an alkyl or alkenyl mercaptoacetic acid represented by the general formula (10) is also preferably used.
Embedded image
(R ₁₃ -S-CH ₂ -COO) ₂ M (10)
(However, R ₁₃ Represents an aliphatic group having 10 to 18 carbon atoms, and M represents tin, magnesium, zinc or copper.
Specific examples of the metal mercaptoacetate represented by the general formula (10) include, for example, the following.
Tin decyl mercaptoacetate, tin dodecyl mercapto acetate, tin tetradecyl mercapto acetate, tin hexadecyl mercapto acetate, tin octadecyl mercapto acetate, magnesium decyl mercapto acetate, magnesium dodecyl mercapto acetate, magnesium tetradecyl mercapto acetate , Magnesium hexadecylmercaptoacetate, magnesium octadecylmercaptoacetate, zinc decylmercaptoacetate, zinc dodecylmercaptoacetate, zinc tetradecylmercaptoacetate, zinc hexadecylmercaptoacetate, zinc octadecylmercaptoacetate, copper decylmercaptoacetate Salt, copper dodecylmercaptoacetate, copper tetradecylmercaptoacetate, copper hexadecylmercaptoacetate, copper octadecylmercaptoacetate Etc..
[0040]
The color forming composition used in the present invention is basically formed by combining the color developer and the color forming agent. The color former used in the present invention exhibits an electron donating property, and is itself a colorless or light-colored dye precursor, and is not particularly limited, and conventionally known ones such as a triphenylmethanephthalide-based compound and a fluoran-based compound Phenothiazine compounds, leuco auramine compounds, indolinophthalide compounds, and the like. Specific examples of the coloring agent are shown below.
As a preferred color former used in the present invention, there is a fluoran compound represented by the following general formula (11).
Embedded image

(Where R ₁₄ Represents a hydrogen atom, an alkyl group, an allyl group, a cyclic alkyl group or an alkoxyalkyl group, _Fifteen Represents an alkyl group, a cyclic alkyl group, an allyl group, an alkoxyalkyl group or an optionally substituted phenyl group. X represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an alkoxyalkyl group or a halogen atom, and Y represents a lower alkyl group, an amino group, a substituted amino group, a cyano group or a halogen atom. )
[0041]
Specific examples of the compound of the general formula (11) include the following compounds.
2-anilino-3-methyl-6- (Nn-hexyl-N-iso-amylamino) fluoran,
2-anilino-3-methyl-6- (di-n-hexylamino) fluoran,
2-anilino-3-methyl-6- (di-n-amylamino) fluoran,
2-anilino-3-methyl-6- (di-n-octylamino) fluoran,
2-anilino-3-methyl-6- (di-n-butylamino) fluoran,
2-anilino-3-methyl-6- (N-isopropyl-N-methylamino) fluoran,
2-anilino-3-methyl-6- (Nn-octyl-N-ethylamino) fluoran,
2-anilino-3-methyl-6- (Nn-octyl-N-iso-propylamino) fluoran,
2-anilino-3-methyl-6- (Nn-amyl-Nn-propylamino) fluoran,
2-anilino-3-methyl-6- (Nn-amyl-Nn-butylamino) fluoran,
2-anilino-3-methyl-6- (Nn-amyl-N-ethylamino) fluoran,
2-anilino-3-methyl-6- (Nn-amyl-N-methylamino) fluoran,
2-anilino-3-methyl-6- (N-iso-amyl-N-ethylamino) fluoran,
2-anilino-3-methyl-6- (Nn-propyl-N-isopropylamino) fluoran,
2-anilino-3-methyl-6- (Nn-butyl-Nn-propylamino) fluoran,
2-anilino-3-methyl-6- (N-ethyl-N-sec-butylamino
) Fluoran,
2-anilino-3-methyl-6- (Nn-butyl-N-iso-propylamino) fluoran,
2-anilino-3-methyl-6- (Nn-butyl-N-ethylamino) fluoran,
2-anilino-3-methyl-6- (N-isobutyl-N-methylamino) fluoran.
[0042]
2-anilino-3-methyl-6- (N-cyclohexyl-Nn-tetradecylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexyl-Nn-dodecylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexyl-Nn-decylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexyl-Nn-octylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexyl-Nn-hexylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexyl-Nn-amylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexyl-N-iso-amylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexyl-Nn-butylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexyl-Nn-propylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexyl-N-ethylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexyl-N-methylamino) fluoran,
2-anilino-3-methyl-6- (dicyclohexylethylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexylethyl-Nn-hexylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexylethyl-Nn-amylamino) fluoran,
2-anilino-3-methyl-6- (dicyclohexylmethylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexylmethyl-Nn-hexylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexylmethyl-Nn-amylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexylmethyl-Nn-butylamino) fluoran,
2-anilino-3-methyl-6- (N-cyclohexylmethyl-N-cyclohexylamino) fluoran.
[0043]
2-anilino-3-methyl-6- (diallylamino) fluoran,
2-anilino-3-methyl-6- (Nn-octyl-N-allylamino) fluoran,
2-anilino-3-methyl-6- (Nn-hexyl-N-allylamino) fluoran,
2-anilino-3-methyl-6- (Nn-amyl-N-allylamino) fluoran,
2-anilino-3-methyl-6- (N-ethyl-N-allylamino) fluoran,
2-anilino-3-methyl-6- (N-2-ethoxypropyl-N-ethylamino) fluoran,
2-anilino-3-methyl-6- (diethoxyethylamino) fluoran,
2-anilino-3-methyl-6- (N-ethoxyethyl-Nn-hexylamino) fluoran,
2-anilino-3-methyl-6- (N-ethoxyethyl-Nn-amylamino) fluoran,
2-anilino-3-methyl-6- (N-ethoxyethyl-N-iso-amylamino) fluoran,
2-anilino-3-methyl-6- (N-ethoxyethyl-Nn-butylamino) fluoran,
2-anilino-3-methyl-6- (N-ethoxyethyl-N-ethylamino) fluoran,
2-anilino-3-methyl-6- (N-ethoxymethyl-Nn-hexylamino) fluoran,
2-anilino-3-methyl-6- (N-ethoxymethyl-Nn-amylamino) fluoran,
2-anilino-3-methyl-6- (N-ethoxymethyl-N-iso-amylamino) fluoran,
2-anilino-3-methyl-6- (Nn-hexadecylamino) fluoran,
2-anilino-3-methyl-6- (Nn-octylamino) fluoran,
2-anilino-3-methyl-6- (Nn-hexylamino) fluoran,
2-anilino-3-methyl-6- (N-ethyl-p-toluidino) fluoran,
2-anilino-3-methyl-6- (N-methyl-p-toluidino) fluoran,
[0044]
2-anilino-3-methoxy-6- (di-n-hexylamino) fluoran,
2-anilino-3-methoxy-6- (di-n-amylamino) fluoran,
2-anilino-3-methoxy-6- (Nn-hexyl-N-iso-amylamino) fluoran,
2-anilino-3-methoxy-6- (N-cyclohexyl-Nn-hexylamino) fluoran,
2-anilino-3-ethoxy-6- (di-n-amylamino) fluoran,
2-anilino-3-ethoxy-6- (di-n-butylamino) fluoran,
2-anilino-3-ethoxy-6-diethylaminofluoran,
2-anilino-3-ethoxy-6- (N-cyclohexyl-Nn-hexylamino) fluoran,
2-anilino-3-ethoxy-6- (N-cyclohexyl-Nn-amylamino) fluoran,
2-anilino-3-ethoxyethyl-6- (di-n-amylamino) fluoran,
2-anilino-3-ethoxyethyl-6- (di-n-butylamino) fluoran,
2-anilino-3-ethoxyethyl-6-diethylaminofluoran,
2-anilino-3-ethoxymethyl-6- (di-n-butylamino) fluoran,
2-anilino-3-ethoxymethyl-6- (N-cyclohexyl-Nn-hexylamino) fluoran,
2-anilino-3-ethoxymethyl-6- (di-n-amylamino) fluoran,
2-anilino-3-methoxymethyl-6- (N-cyclohexyl-Nn-hexylamino) fluoran,
2-benzylamino-3-methyl-6- (di-n-butylamino) fluoran, 2-benzylamino-3-methyl-6- (di-n-amylamino) fluoran
,
2-benzylamino-3-methyl-6- (N-cyclohexyl-Nn-hexylamino) fluoran,
2- (m-trichloromethylanilino) -3-methyl-6-diethylaminofluoran,
2- (m-trifluoromethylanilino) -3-methyl-6-diethylaminofluoran,
2- (m-trifluoromethylanilino) -3-methyl-6- (N-cyclohexyl-N-methylamino) fluoran,
2- (2,4-dimethylanilino) -3-methyl-6- (Nn-hexyl-N-iso-amylamino) fluoran,
2- (2,4-dimethylanilino) -3-methyl-6- (di-n-hexylamino) fluoran,
2- (2,4-dimethylanilino) -3-methyl-6- (di-n-amylamino) fluoran,
2- (2,4-dimethylanilino) -3-methyl-6- (di-n-butylamino) fluoran,
2- (2,4-dimethylanilino) -3-methyl-6-diethylaminofluoran,
2- (N-ethyl-p-toluidino) -3-methyl-6- (N-ethylanilino) fluoran,
2- (N-methyl-p-toluidino) -3-methyl-6- (N-propyl-p-toluidino) fluoran,
[0045]
2-anilino-6- (di-n-hexylamino) fluoran,
2-anilino-6- (Nn-hexyl-N-iso-amylamino) fluoran,
2-anilino-6- (di-n-amylamino) fluoran,
2-anilino-6-diethylaminofluoran,
2-anilino-6- (Nn-hexyl-N-ethylamino) fluoran,
2-anilino-6- (N-cyclohexyl-Nn-hexylamino) fluoran,
2-anilino-6- (N-cyclohexyl-Nn-amylamino) fluoran,
2-anilino-6- (N-cyclohexyl-N-methylamino) fluoran,
2-anilino-6- (diethoxyethylamino) fluoran,
2-anilino-6- (N-ethoxyethyl-N-iso-amylamino) fluoran,
2-anilino-6- (N-ethoxyethyl-Nn-amylamino) fluoran,
2-anilino-6- (N-ethoxyethyl-Nn-butylamino) fluoran,
2-anilino-6- (Nn-octylamino) fluoran,
2-anilino-6- (Nn-hexylamino) fluoran,
2-anilino-6- (Nn-amylamino) fluoran,
2- (N-methylanilino) -6- (N-ethyl-p-toluidino) fluoran,
2- (o-chloroanilino) -6-diethylaminofluoran,
2- (o-bromoanilino) -6-diethylaminofluoran,
2- (o-chloroanilino) -6-dibutylaminofluoran,
2- (o-floranilino) -6-dibutylaminofluoran,
2- (p-chloroanilino) -6- (Nn-octylamino) fluoran,
2- (p-chloroanilino) -6- (Nn-palmitylamino) fluoran,
2- (p-chloroanilino) -6- (di-n-octylamino) fluoran,
2- (m-trifluoromethylanilino) -6-diethylaminofluoran,
2- (p-acetylanilino) -6-diethylaminofluoran,
2- (p-acetylanilino) -6- (Nn-hexyl-N-iso-hexylamino) fluoran,
2- (p-acetylanilino) -6- (di-n-hexylamino) fluoran,
2- (p-acetylanilino) -6- (Nn-hexyl-Nn-amylamino) fluoran,
2- (p-acetylanilino) -6- (di-n-amylamino) fluoran,
2- (p-acetylanilino) -6- (Nn-amyl-Nn-butylamino) fluoran,
2- (p-acetylanilino) -6- (N-cyclohexyl-Nn-hexylamino) fluoran,
2- (p-acetylanilino) -6- (N-ethoxyethyl-N-iso-amylamino) fluoran,
2- (p-acetylanilino) -6- (N-ethoxyethyl-Nn-amylamino) fluoran,
[0046]
2-benzylamino-6- (N-ethyl-p-toluidino) fluoran,
2-benzylamino-6- (N-methyl-2,4-dimethylanilino) fluoran,
2-benzylamino-6- (N-ethyl-2,4-dimethylanilino) fluoran,
2-benzoylamino-6- (N-ethyl-p-toluidino) fluoran,
2- (o-methoxybenzoylamino) -6- (N-methyl-p-toluidino) fluoran,
2-dibenzylamino-6- (di-n-butylamino) fluoran,
2-dibenzylamino-6- (di-n-amylamino) fluoran,
2-dibenzylamino-6- (di-n-hexylamino) fluoran,
2-dibenzylamino-6- (Nn-hexyl-N-iso-amylamino) fluoran,
2-dibenzylamino-6- (di-n-propylamino) fluoran,
2-dibenzylamino-6- (N-cyclohexyl-Nn-amylamino) fluoran,
2-dibenzylamino-6- (N-cyclohexyl-Nn-hexylamino) fluoran,
2-dibenzylamino-6- (N-methyl-p-toluidino) fluoran,
2-dibenzylamino-6- (N-ethyl-p-toluidino) fluoran,
2- (di-p-methylbenzylamino) -6- (N-ethyl-p-toluidino) fluoran,
2-dibenzylamino-4-methyl-6-diethylaminofluoran,
2-dibenzylamino-4-methyl-6- (di-n-propylamino) fluoran,
2-dibenzylamino-4-methyl-6- (di-n-butylamino) fluoran,
2-dibenzylamino-4-methyl-6- (di-n-amylamino) fluoran,
2-dibenzylamino-4-methoxy-6- (N-methyl-P-toluidino) fluoran,
2-benzylamino-4-methyl-6- (N-ethyl-P-toluidino) fluoran,
2- (α-phenylethylamino) -4-methyl-6-diethylaminofluoran,
2- (p-toluidino) -3- (t-butyl) -6- (N-methyl-p-toluidino) fluoran,
2- (α-phenylethylamino) -6- (N-ethyl-p-toluidino) fluoran,
2- (o-methoxycarbonylanilino) -6-diethylaminofluoran,
[0047]
2-methylamino-6- (N-methylanilino) fluoran,
2-methylamino-6- (N-ethylanilino) fluoran,
2-methylamino-6- (N-propylanilino) fluoran,
2-ethylamino-6- (N-methyl-p-toluidino) fluoran,
2-ethylamino-6- (N-ethyl-p-toluidino) fluoran,
2-methylamino-6- (N-methyl-2,4, -dimethylanilino) fluoran,
2-ethylamino-6- (N-ethyl-2,4, -dimethylanilino) fluoran,
2-dimethylamino-6- (N-methylanilino) fluoran,
2-dimethylamino-6- (N-ethylanilino) fluoran,
2-diethylamino-6- (N-methyl-p-toluidino) fluoran,
2-diethylamino-6- (N-ethyl-p-toluidino) fluoran,
2-dipropylamino-6- (N-methylanilino) fluoran,
2-dipropylamino-6- (N-ethylanilino) fluoran,
2-acetylamino-3-methyl-6-diethylaminofluoran,
2-acetylamino-3-methyl-6- (di-n-butylamino) fluoran,
2-acetylamino-3-methyl-6- (di-n-amylamino) fluoran,
2-acetylamino-3-methyl-6- (di-n-hexylamino) fluoran,
2-acetylamino-6- (N-methyl-p-toluidino) fluoran,
[0048]
2-amino-6-diethylaminofluoran,
2-amino-6- (di-n-butylamino) fluoran,
2-amino-6- (di-n-amylamino) fluoran,
2-amino-6- (di-n-hexylamino) fluoran,
2-amino-6- (N-cyclohexyl-Nn-amylamino) fluoran,
2-amino-6- (N-methylanilino) fluoran,
2-amino-6- (N-ethylanilino) fluoran,
2-amino-6- (N-propylanilino) fluoran,
2-amino-6- (N-methyl-p-toluidino) fluoran,
2-amino-6- (N-ethyl-p-toluidino) fluoran,
2-amino-6- (N-propyl-p-toluidino) fluoran,
2-amino-6- (N-methyl-p-ethylanilino) fluoran,
2-amino-6- (N-ethyl-p-ethylanilino) fluoran,
2-amino-6- (N-propyl-p-ethylanilino) fluoran,
2-amino-6- (N-methyl-2,4-dimethylanilino) fluoran,
2-amino-6- (N-ethyl-2,4-dimethylanilino) fluoran,
2-amino-6- (N-propyl-2,4-dimethylanilino) fluoran,
2-amino-6- (N-methyl-p-chloroanilino) fluoran,
2-amino-6- (N-ethyl-p-chloroanilino) fluoran,
2-amino-6- (N-propyl-p-chloroanilino) fluoran,
2-amino-3-methyl-6-diethylaminofluoran,
2-amino-3-methyl-6- (di-n-butylamino) fluoran,
2-amino-3-methyl-6- (di-n-amylamino) fluoran,
2-amino-3-methyl-6- (di-n-hexylamino) fluoran,
2-amino-3-methoxy-6- (di-n-butylamino) fluoran,
2-amino-3-methoxy-6- (di-n-amylamino) fluoran,
2-amino-3-methoxy-6- (di-n-hexylamino) fluoran,
[0049]
1,3-dimethyl-6-diethylaminofluoran,
1,3-dimethyl-6- (di-n-butylamino) fluoran,
1,3-dimethyl-6- (di-n-amylamino) fluoran,
1,3-dimethyl-6- (di-n-hexylamino) fluoran,
1,3-dimethyl-6- (N-cyclohexyl-Nn-butylamino) fluoran,
2,3-dimethyl-6-dimethylaminofluoran,
2-methyl-6-dimethylaminofluoran,
2-methyl-6-diethylaminofluoran,
2-methyl-6- (di-n-propylamino) fluoran,
2-methyl-6- (di-n-butylamino) fluoran,
2-methyl-6- (di-n-amylamino) fluoran,
2-methyl-6- (di-n-hexylamino) fluoran,
2-methyl-6- (N-cyclohexyl-Nn-amylamino) fluoran,
2-methyl-6- (N-cyclohexyl-N-methylamino) fluoran,
3-diethylamino-6- (m-trifluoromethylanilino) fluoran,
3-methyl-6- (N-ethyl-p-toluidino) fluoran,
2-methyl-6- (N-ethyl-p-toluidino) fluoran,
4-methoxy-6- (N-ethyl-p-toluidino) fluoran,
2-cyano-6-diethylaminofluoran,
2-cyano-6- (di-n-butylamino) fluoran,
2-cyano-6- (di-n-amylamino) fluoran,
2-cyano-6- (di-n-hexylamino) fluoran,
2-cyano-6- (N-cyclohexyl-Nn-hexylamino) fluoran,
2-cyano-6- (N-cyclohexyl-Nn-decylamino) fluoran.
[0050]
2-chloro-6-diethylaminofluoran,
2-bromo-6-diethylaminofluoran,
2-chloro-6-dipropylaminofluoran,
2-chloro-6-dibutylaminofluoran,
3-chloro-6-cyclohexylaminofluoran,
3-bromo-6-cyclohexylaminofluoran,
2-chloro-6- (N-ethyl-N-isoamylamino) fluoran,
2-chloro-3-methyl-6-diethylaminofluoran,
2-anilino-3-chloro-6-diethylaminofluoran,
2- (o-chloroanilino) -3-chloro-6-cyclohexylaminofluoran,
2- (m-trifluoromethylanilino) -3-chloro-6-diethylaminofluoran,
2- (2,3-dichloroanilino) -3-chloro-6-diethylaminofluoran,
2-ethoxyethylamino-3-chloro-6-dibutylaminofluoran,
2-benzylamino-4-chloro-6- (N-ethyl-p-toluidino) fluoran,
2-dibenzylamino-4-chloro-6- (N-ethyl-p-toluidino) fluoran,
2- (α-phenylethylamino) -4-chloro-6-diethylaminofluoran,
2- (N-benzyl-p-trifluoromethylanilino) -4-chloro-6-diethylaminofluoran and the like.
[0051]
In addition to the general formula (10), there are many fluoran compounds which are preferable as the color former used in the present invention, and specific examples include the following compounds.
2-anilino-3-methyl-6-pyrrolidinofluoran,
2-anilino-3-chloro-6-pyrrolidinofluoran,
2-anilino-3-methyl-6- (N-ethyl-N-tetrahydrofurfurylamino) fluoran,
2-mesidino-3-methyl-4 ', 5'-benzo-6-diethylaminofluoran,
2- (m-trifluoromethylanilino) -3-methyl-6-pyrrolidinofluoran,
2- (α-naphthylamino) -3,4-benzo-4′-bromo-6- (N-benzyl-N-cyclohexylamino) fluoran,
2-piperidino-6-diethylaminofluoran,
2- (Nn-propyl-p-trifluoromethylanilino) -6-morpholinofluoran,
2- (di-N-p-chlorophenyl-methylamino) -6-pyrrolidinofluoran,
2- (Nn-propyl-m-trifluoromethylanilino) -6-morpholinofluoran,
1,2-benzo-6-diethylaminofluoran,
1,2-benzo-6- (N-ethyl-N-isoamylamino) fluoran,
1,2-benzo-6-dibutylaminofluoran,
1,2-benzo-6- (di-n-amylamino) fluoran,
1,2-benzo-6- (di-n-hexylamino) fluoran,
1,2-benzo-6- (N-methyl-N-cyclohexylamino) fluoran,
1,2-benzo-6- (N-ethyl-Nn-octylamino) fluoran,
1,2-benzo-6- (N-ethyl-p-toluidino) fluoran,
1,2-benzo-6-diallylaminofluoran,
1,2-benzo-6- (N-ethoxyethyl-N-ethylamino) fluoran and the like.
[0052]
Many compounds other than the fluoran compound are preferable as the color former used in the present invention, and specific examples thereof include the following compounds.
Benzolecomethylene blue,
Lactam 2- [3,6-bis (diethylamino)]-6- (0-chloroanilino) xanthylbenzoate,
Lactam 2- [3,6-bis (diethylamino)]-9- (0-chloroanilino) xanthylbenzoate,
3,3-bis (p-dimethylaminophenyl) -phthalide,
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone),
3,3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide,
3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide,
3,3-bis (p-dibutylaminophenyl) phthalide,
3- (2-methoxy-4-dimethylaminophenyl) -3- (2-hydroxy-4,5-dichlorophenyl) phthalide,
3- (2-hydroxy-4-dimethylaminophenyl) -3- (2-methoxy-5-chlorophenyl) phthalide,
3- (2-hydroxy-4-dimethoxyaminophenyl) -3- (2-methoxy-5-chlorophenyl) phthalide,
3- (2-hydroxy-4-dimethylaminophenyl) -3- (2-methoxy-5-nitrophenyl) phthalide,
3- (2-hydroxy-4-diethylaminophenyl) -3- (2-methoxy-5-methylphenyl) phthalide,
3- (2-methoxy-4-dimethylaminophenyl) -3- (2-hydroxy-4-chloro-5-methoxyphenyl) phthalide,
3,6-bis (dimethylamino) fluorenespiro (9,3 ')-6'-dimethylaminophthalide,
6'-chloro-8'-methoxy-benzoindolino-spiropyran,
6'-bromo-2'-methoxy-benzoindolino-spiropyran and the like.
[0053]
The ratio of the color former and the developer contained in the composition used in the present invention needs to be selected appropriately according to the physical properties of the compound to be used, and the range is the molar ratio of the color former to the developer. Is in the range of 1 to 20, preferably 2 to 10. The color developer and the color former may be used alone or as a mixture of two or more kinds. However, the color erasing characteristics change depending on the ratio of the color developer and the color developer, and the color erasing starts when the color developer is relatively large. When the temperature is low, and when the temperature is relatively low, the decolorization becomes sharp with respect to the temperature. Therefore, this ratio may be appropriately selected according to the application and purpose.
The thermochromic composition used in the present invention is basically composed of the color developer and the color former. However, for the purpose of improving various properties, for example, decolorability and storage stability, the color developer is An additive or the like having an effect of controlling crystallization of the compound can be contained.
[0054]
In the present invention, when the recording medium is multicolored by providing a plurality of reversible thermosensitive recording layers, a plurality of reversible thermosensitive recording layers containing only one thermochromic composition are laminated on a support. However, it is more desirable to provide a resin intermediate layer between the recording layers to be laminated. The resin intermediate layer used here is for preventing the recording layers from mixing with each other during heating, and is preferably formed of a heat-resistant resin. The support is paper, synthetic paper, a plastic film or a composite thereof, a glass plate, or the like, as long as it can hold the recording layer.
The reversible thermosensitive recording layer may be in any form as long as the above-mentioned thermochromic composition is present.For example, a developer and a color former are mixed and melted to form a film, which is cooled to be reversible. It may be a heat-sensitive recording layer. However, in general, a reversible thermosensitive recording layer is preferably prepared by sufficiently dispersing a color developer and a color former in a binder resin, and a long-life reversible multicolor thermosensitive recording medium can be obtained by this method.
[0055]
Examples of the binder resin include hydroxyethyl cellulose, hydroxypropyl cellulose, methoxy cellulose, carboxymethyl cellulose, methyl cellulose, cellulose acetate, gelatin, casein, starch, sodium polyacrylate, polyvinyl pyrrolidone, polyacrylamide, polyvinyl chloride, polyvinyl acetate, and chloride. Vinyl-vinyl acetate copolymer, polystyrene, styrene copolymer, phenoxy resin, polyester, aromatic polyester, polyurethane, polycarbonate, polyacrylate, polymethacrylate, acrylic acid copolymer, maleic acid copolymer Polymers, polyvinyl alcohol, chlorinated vinyl chloride resins, mixtures of these resins, and the like are used.
[0056]
The developer and the color former can be used as they are or in a microcapsule. Microencapsulation of a color developer and a color former may be performed by a known method such as a coacervation method, an interfacial polymerization method, or an in-situ polymerization method.
The reversible heat-sensitive recording layer is formed by uniformly dispersing or dissolving a color former and a developer together with a binder resin with water or an organic solvent according to a conventionally known method, and applying this on a support or an intermediate layer. -It can be performed by drying.
The role of the binder resin in the reversible thermosensitive recording layer is to prevent the thermochromic composition from aggregating due to repetition of coloring and decoloring, and to maintain a state in which the thermochromic composition is uniformly dispersed. In particular, since the thermochromic composition often aggregates and becomes non-uniform due to application of heat at the time of color development, a binder resin having high heat resistance is preferable.
In the reversible multicolor heat-sensitive recording medium of the present invention, various additives used in ordinary heat-sensitive recording paper, for example, a dispersant, a surfactant, for the purpose of improving coating properties or recording properties as necessary. Also, a polymeric cationic conductive agent, a filler, a color image stabilizer, an antioxidant, a light stabilizer, a lubricant, and the like can be added to the recording layer.
[0057]
The resin intermediate layer is a separation layer whose purpose is to prevent the adjacent reversible thermosensitive recording layers from being mixed by heating and pressurizing during decoloring as described above.
The reversible multicolor thermosensitive recording medium of the present invention has a plurality of reversible thermosensitive recording layers for multiple colors, but when the same resin is used as a binder resin of each layer constituting the recording layer, the pressure during heat application is increased. -It is recognized that adjacent recording layers have a tendency to be partially mixed by heating. The resin interlayer solves such a problem.
The resin intermediate layer can be formed by applying a resin that is hardly compatible with or incompatible with the binder resin of the adjacent recording layer, or a resin that does not melt at the recording temperature on the recording layer. When the recording layer is formed of a coating solution containing an organic solvent, the intermediate layer is preferably formed using a water-soluble resin coating solution containing an aqueous solvent. In addition, the resin intermediate layer can be formed by laminating a heat-resistant resin film on the recording layer, and the resin film is formed by a dry lamination method from the viewpoint of the coloring property of the recording medium and the image storability. It is particularly preferable to form them by bonding.
[0058]
As the resin film for forming the intermediate layer, a polyester film such as polyethylene terephthalate is preferably used. Further, a film of polyamide, polyimide, polyamideimide, polyparabanic acid or the like is also preferably used. As the adhesive used for bonding the resin film, any adhesive used in the dry lamination method can be used. For the thermoplastic resin, an ionomer resin, an acrylic resin (including an aqueous emulsion), and a modified ethylene-vinyl acetate are used. Polymer, polybutadiene, phenoxy resin, polyvinyl ether, polyvinyl formal, vinyl acetate resin, polyester and the like are used. As the thermosetting resin, urethane resin, epoxy resin, xylene resin, phenol resin, urea resin and the like are used.
The thickness of the resin intermediate layer may be a thickness that does not cause damage due to application of heat and pressure due to repeated recording and erasing. However, if the thickness of the resin intermediate layer is too large, the heat conductivity deteriorates, so that the resin intermediate layer is preferably as thin as possible, and is usually preferably 10 μm or less.
[0059]
The recording medium of the present invention can be produced by microencapsulating each of the compositions having different color tone and decolorization start temperature, and applying a mixture of these to a support.
That is, a plurality of types of microcapsule mixtures each independently containing a composition having a different color tone and decoloring temperature may be prepared by a conventional method, and the mixture may be coated on a support in a conventional manner. As the resin for forming the microcapsule wall, a conventionally known thermoplastic resin or thermosetting resin is used.
As the binder resin used for coating the microcapsules on the support, a normal heat-resistant resin for forming a recording layer may be used, and the various binder resins described above are used. In addition, in order to improve the thermal and mechanical strength of the recording layer containing the microcapsules, a method of using a curable resin as a binder resin of the layer and curing the layer after the layering is recommended as a layering method of the layer. Is done.
[0060]
The reversible multicolor heat-sensitive recording medium of the present invention can have a protective layer formed on its surface. The protective layer not only prevents the surface from being deformed or discolored by heat and pressure when applying heat, but also improves the chemical resistance, water resistance, friction resistance, head matching property, and the like. Things. As the material for forming the protective layer, it is desirable to use a heat-resistant and high-strength resin film, and a polyamide film, a polyimide film, an aromatic polyester film, a polyparabanic acid film, or the like is used. With the formation of such a protective layer, the heat resistance is improved as described above, and the resistance to contact with an organic solvent, a plasticizer, oil, sweat, water, etc. is also increased. It is possible to obtain a recording medium that can be repeated without any problem. In addition, by including a light stabilizer in the protective layer, a recording medium having significantly improved light fastness of an image and a background can be obtained. By adding a polymeric cationic conductive agent, antistatic can be performed. By adding an organic or inorganic filler and a lubricant to the thermal recording medium, it is possible to obtain a heat-sensitive recording medium having excellent reliability and head matching without problems such as sticking caused by contact with a thermal head or the like.
[0061]
In the reversible multicolor thermosensitive recording medium of the present invention, an undercoat layer may be provided between the support and the recording layer, if necessary.
The undercoat layer is used for the purpose of improving heat insulation, improving the adhesion between the support and the recording layer, improving the resistance of the support to a solvent when the recording layer is formed, and preventing the heat-fusible ink from being absorbed by the support when heat is applied. It is installed, and the presence or absence of the installation may be determined in consideration of the type of the support. One of the important roles of the undercoat layer is to improve the heat insulation. This is to make the applied thermal energy useful for thermal recording formation and heat erasure. Can be performed sharply. The formation of the undercoat layer for the purpose of heat insulation may be achieved by applying fine hollow particles made of an organic or inorganic material on a support, and specifically, a particle size formed of glass, ceramics, plastic, or the like. A fine hollow body of about 10 to 50 μm may be well dispersed in a solvent together with a binder resin, and uniformly coated and dried on a support.
[0062]
The reversible multicolor thermosensitive recording medium of the present invention can be manufactured by various procedures. For example, a recording layer A is coated on a support, a resin film coated with an adhesive is laminated thereon, and then the recording layer is coated. It can be manufactured by applying B and then laminating a resin film. Note that in the laminating method, after bonding, the layers are firmly bonded by pressing and heating with a heat roller or the like. However, the pressing and heating may be performed after all layers including the protective layer are bonded. It may be performed each time two intermediate layers are formed.
Further, as described above, a recording layer can be formed by applying various microencapsulated compositions having different color tone and decoloration start temperature on a support. Furthermore, at least one of the stacked recording layers may be a microcapsule-containing layer, and the other layers may be ordinary thermochromic composition-containing layers.
In the present invention, a transparent recording medium can be obtained by using a transparent film for the support, and this is preferably used for a display medium. In this case, it is needless to say that the films used for the intermediate layer and the protective layer also preferably have higher transparency.
[0063]
In order to bring the reversible multicolor heat-sensitive recording medium of the present invention into an initial state, the recording medium is temporarily heated to a temperature at which all of the reversible thermochromic compositions contained in the recording layer are colored. After all of the reversible thermochromic composition in the color-developing state, the color-decomposition start temperature of the color-developed composition is from the composition on the high-temperature side to the composition on the low-temperature side, in the decolorization temperature range. It is sufficient that all the reversible thermochromic composition present in the recording layer is decolored by heating.
The formation of a recorded image is not particularly limited, such as a hot pen, a thermal head, or laser heating, depending on the intended use. Similarly, the erasing of the recorded image is not particularly limited as long as the erasing temperature conditions are given, such as a heating roller, a sheet heating element, a thermostat, a hot air, a thermal head, and the like.
[0064]
In order to obtain a multicolor image in the present invention, the above-mentioned reversible multicolor heat-sensitive recording medium is used, and after heating and coloring two or more compositions, the composition of a predetermined color is heated to its decoloring temperature. It only has to be heated and erased. By the way, in order to obtain a multicolor image with a multicolor recording layer having a three-layer configuration as shown in Table 2, a plurality of heat applications are required. Therefore, it is preferable to use an apparatus having a plurality of heating elements because a recording apparatus having a single heating element requires a long time to form an image.
The recording apparatus for forming a multicolor image of the present invention includes a heating element capable of applying an image of heat to an arbitrary composition of a plurality of types of compositions so as to have a temperature equal to or higher than its color development temperature, and an extinguisher of the arbitrary composition. It comprises a heating element capable of applying heat in the form of an image so as to reach a color temperature, and a heating element capable of applying heat to the entire composition at its decolorizing temperature. In this case, each heating element can be a heating element group including a plurality of heating elements.
[0065]
FIG. 6 shows a basic configuration of a recording apparatus for a recording medium having three reversible recording layers, ₁ , L ₂ , L ₃ H is a decolorizing heating element for heating all three layers to the decoloring temperature. ₁ , H ₂ , H ₃ Is a heating element for heating each layer imagewise. When the decoloring temperature area of each recording layer of the recording medium is the same as that of FIG. ₁ , L ₂ , L ₃ Indicates that the recording layer has a temperature T ₂ , T ₃ , T ₄ , So that even if the recording medium has already formed a multicolor image, the entire recording layer is erased by passing through this portion. Thereafter, the recording medium is heated by a heating element H capable of applying heat in an image-like manner. ₁ , H ₂ , H ₃ Pass through the image forming section consisting of: H ₁ The heating element is for coloring, and the temperature T ₁ , T ₂ Or T ₃ It generates heat so that it can be heated. Following H ₂ , H ₃ Is the temperature T ₃ And T ₄ In order to heat the recording layer, heat is generated in the form of an image if necessary. ₁ A desired color in the recording layer developed in step is erased. Specifically, for example, if the image portion requires only the color of the C layer in FIG. ₁ Is T ₁ H so that it can be heated to ₂ And H ₃ Is T ₃ , T ₄ Set so that heating can be performed. H ₁ All layers A, B, and C develop color upon passing, but H ₂ When passing through, layer B decolorizes and H ₃ When the image passes through, the layer A is decolored, so that the image portion becomes the color of only the layer C. When the recording medium is composed of a plurality of types of microcapsules, each of the above recording layers may be considered the same as each microcapsule, and a multicolor image can be efficiently formed by the apparatus shown in FIG. .
[0066]
As a heating element, a general thermal head for thermal recording can be used for a recording portion to which heat is applied in an image form, and a heat roller or a thermal head can be used for a heating element of the entire decoloring portion. It should be noted that the entire decoloring of the reversible recording layer or the microcapsule can be performed by the heating element in the recording portion. In this case, the heating element in the entire decoloring portion can be omitted.
In the reversible multicolor thermosensitive recording medium of the present invention, even when some of the recording layers or microcapsules are irreversible, efficient image formation using the same device as when all layers or all microcapsules are reversible is performed. Can be formed and erased, however, in this case, it is needless to say that all layers or all microcapsules cannot be initialized, and the color of the irreversible composition remains. The state of image formation and erasing when the irreversible composition exists may be considered only for the reversible composition.
[0067]
FIG. 7 shows a basic configuration of a display device preferable for performing efficient display in the present invention. (A) shows a sheet-shaped display medium and a heating element L for overall decoloring. ₁ ', L ₂ ', L ₃ 'And the heating element H for image formation ₁ ', H ₂ ', H ₃ 'Is in contact, and heat is applied to the moving display medium to form and erase images. In this case, the heating element may move with respect to the fixed display medium. In (b), a heating element for forming an image and a heating element for erasing are similarly provided for an endless belt-shaped display medium.
When the decoloring temperature area of each image forming layer of the display medium is the same as that of FIG. ₁ ', L ₂ ', L ₃ 'Indicates that the recording layer has a temperature T ₂ , T ₃ , T ₄ In this case, even if the display medium has already formed a multicolor image, the recording layer can be erased by passing through this portion to bring it into an initial state.
[0068]
Thereafter, the display medium is a heating element H capable of applying heat in the form of an image. ₁ ', H ₂ ', H ₃ 'Through the recording part consisting of. H ₁ The heating element is for color development, and the temperature T ₁ , T ₂ Or T ₃ Generate heat so that it can be temporarily heated. Following H ₂ ', H ₃ 'Is the temperature T ₃ And T ₄ In order to heat the recording layer, heat is generated in the form of an image as needed, ₁ The desired color is erased from the recording layer colored by '. Specifically, for example, if the image portion requires only the color of the C layer in FIG. ₁ 'Is T ₁ H so that it can be heated to ₂ 'And H ₃ 'Is T ₃ , T ₄ It is set so that it can be heated. H ₁ 'All layers A, B, and C develop color when passing, but H ₂ 'The B layer is decolorized by passing, ₃ 'Since the layer A is decolored by passing, the image portion has the color of only the layer C. The specific heating elements for applying an image and for decoloring the whole may be the same as those of the recording medium. Even when a part of the recording layer is formed of an irreversible layer, image formation and erasing may be performed by using a reversible layer as in the case of the recording medium. Further, even when the marking medium is formed by a plurality of types of microcapsules, a multicolor image can be efficiently formed by the apparatus shown in FIG.
[0069]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, all the parts shown below are based on weight.
[0070]
Example 1
The following developers and color formers were mixed at a molar ratio of 2: 1 to prepare compositions A and B which were pulverized and mixed well.
Composition A
Tetradecylphosphonic acid
2- (o-chloroanilino) -6-dibutylaminofluoran
Composition B
Octadecylphosphonic acid
2-chloro-6-diethylaminofluoran
A glass plate having a thickness of about 1 mm was prepared and heated on a hot plate so that the surface reached 170 ° C. After a small amount of the powder of the composition B was melted on the glass plate, a glass plate having a thickness of 0.1 mm was placed on the melt to spread the melt to a uniform thickness. Next, a small amount of the powder of the composition A was melted on the glass plate, and a glass plate having a thickness of 0.1 mm was put on the glass plate as before to spread the melt to a uniform thickness.
[0071]
Next, the whole was removed from the hot plate and brought into contact with ice water to be rapidly cooled. The recording medium thus obtained has a colored recording layer B on a glass substrate, a colored recording layer A sandwiched by an intermediate layer made of glass, and a protective layer made of glass on the top. It has a configuration with. The single color of the colored recording layer A is black, and the single color of the recording layer B is red.
First, this recording medium was temporarily heated and cooled to 72 ° C., which is the decoloring temperature range of the recording layer B, to decolor the recording layer B. Since the temperature of 72 ° C. is equal to or higher than the coloring temperature of the recording layer A, the recording layer A remains in a colored state. Subsequently, the recording layer A was temporarily heated and cooled to 56 ° C., which is the decoloring temperature range of the recording layer A, so that the recording layer A was also decolorized. As a result, an unrecorded initial state in which both the recording layers A and B were erased was obtained.
For the recording medium thus obtained, the combination of the recording operation and the decoloring operation shown in Table 3 was performed in (1) → (2) → (3) → (1) → (2) → (3). The test was repeated 10 times, as in.
[0072]
[Table 3]

As shown in Table 3, three types of color tones were obtained by each of the recording operations (1), (2), and (3). Further, recording and decoloring could be repeatedly performed in a stable manner.
[0073]
Example 2
A recording medium was prepared in the same manner as in Example 1 except that the following combinations of compositions A and B were used and the mixing ratio was 4/1 (color developer / color former) in a molar ratio.
Composition A
Hexadecylphosphonic acid
2- (o-chloroanilino) -6-dibutylaminofluoran
Composition B
Eicosylphosphonic acid
1,2-benzo-6- (N-ethyl-p-toluidino) fluoran
In order to bring the recording medium into a colorless initial state, the recording layer B was first heated and cooled to 80 ° C., which is the decoloring temperature range, to decolor the recording layer B. Since 80 ° C. is higher than the coloring temperature for the recording layer A, the recording layer A remains in the color-developed state. Subsequently, the recording layer A was decolored by heating and cooling to 64 ° C., which is the decoloring temperature range of the recording layer A. As a result, an unrecorded initial state in which both the recording layers A and B were erased was obtained.
[0074]
A combination of the recording operation and the decoloring operation shown in Table 4 was repeated 10 times on the thus obtained recording medium in the same manner as in Example 1.
[Table 4]

As shown in Table 4, three types of color tones were obtained by the recording operations of (1), (2), and (3). Further, recording and decoloring could be repeatedly performed in a stable manner.
[0075]
Example 3
A recording medium was prepared in the same manner as in Example 2 except that the following combinations of compositions A and B were used.
Composition A
Octadecylthiomalic acid
2-anilino-3-methyl-6- (N-cyclohexyl-N-methylamino) fluoran
Composition B
Eicosylthiomalic acid
In order to bring the 1,2-benzo-6- (N-isopentyl-N-ethylamino) fluoran recording medium into a colorless initial state, the recording layer B has a decoloring temperature range, and the recording layer A has a decoloring temperature range. However, by heating to a certain temperature of 65 ° C., both recording layers were decolorized.
[0076]
The recording medium thus obtained was repeatedly subjected to the combination of the recording operation and the decoloring operation shown in Table 5 in the same manner as in Example 1 ten times.
[Table 5]

As shown in Table 5, two types of color tones were obtained by each of the recording operations (1) and (2). Further, recording and decoloring could be repeatedly performed in a stable manner.
[0077]
Example 4
A recording medium was prepared in the same manner as in Example 2 except that the following combinations of compositions A and B were used.
Composition A
Hexadecylphosphonic acid
2- (N-methyl-anilino) -6- (N-ethyl-p-toluidino) fluoran
Composition B
Docosylphosphonic acid
1,2-benzo-6- (N-isoamyl-N-ethylamino) fluoran
To bring the recording medium into a colorless initial state, the recording layer B was first decolored by heating and cooling to 84 ° C., which is the decoloring temperature range of the recording layer B. Since 84 ° C. is equal to or higher than the coloring temperature for the recording layer A, the recording layer A remains in a colored state. Subsequently, the recording layer A was decolored by heating and cooling to 64 ° C., which is the decoloring temperature range of the recording layer A. Thus, an unrecorded initial state in which both the recording layers A and B were erased was obtained.
[0078]
A combination of the recording operation and the decoloring operation shown in Table 6 was repeated 10 times on the thus obtained recording medium in the same manner as in Example 1.
[Table 6]

As shown in Table 6, three types of color tones were obtained by the recording operations of (1), (2), and (3). In addition, repetition of recording and recording erasure could be performed stably.
[0079]
Example 5
The following compositions A and B containing a color developer and a color former were sufficiently pulverized and dispersed by a ball mill until the particle diameter became about 1 μm to prepare a coating solution for forming a recording layer.

[0080]
A coating solution A was applied on a 100 μm-thick polyester film and dried to form a recording layer A having a thickness of about 5 μm. Next, on the recording layer A, a 10 wt% aqueous solution of polyvinyl alcohol was applied and dried to form an intermediate layer having a thickness of about 2 μm. Further, on the intermediate layer, a coating liquid B was applied and dried to form a recording layer B having a thickness of about 5 μm.
On the other hand, a toluene / methyl ethyl ketone solution of a saturated polyester resin [manufactured by Toyobo Co., Ltd .: Byron 300] was applied and dried as an adhesive layer on one side of a 4.5 μm-thick polyester film. The thickness of this layer was about 0.5 μm. Next, this film was overlaid on the recording layer B so as to be in contact with the adhesive layer, and was pressed at a pressure of 2 kg (linear pressure) through a heat roller at a temperature of 125 ° C.
As described above, a recording medium having recording layers A and B sandwiching the intermediate layer and further having a protective layer on the surface was obtained. After quenching this recording medium on a hot plate at 125 ° C. for about 10 seconds, the recording medium was placed in an oven at a temperature of 82 ° C. for 3 minutes to decolor the recording layer A, and then placed in an oven at a temperature of 63 ° C. for 3 minutes. Then, the recording layer B was decolorized. By this operation, the recording medium was in an initial state in which both recording layers were erased.
[0081]
The following operations (1) and (2) were sequentially performed in order to examine the coloring characteristics of the recording medium, and the coloring tone at each stage was examined. Each heating and cooling operation was performed by a method in which the back surface was brought into contact with a 1 ° C. cooling plate immediately after being placed on a hot plate for 10 seconds.
(1) Heating temperature 125 ° C, rapid cooling → color tone: reddish (mixed color of red and green) ... Both A and B develop color
(2) Heating temperature 65 ° C, rapid cooling → color tone: green ... A is colored, B is decolorized
Similarly, the following operations (1) and (2) were sequentially performed.
(1) Heating temperature 125 ° C, rapid cooling → color tone: reddish (mixed color of red and green) ... Both A and B develop color
(2) Heating temperature 85 ° C, rapid cooling → color tone: red ... A is decolored, B is colored
From the above results, it was found that this recording medium can form three-color images by one or two-stage heating and cooling operations. These were all returned to the initial state by sequentially performing the following operations (1) and (2).
▲ 1 ▼ Heating temperature 85 ℃ ・ Quick cooling
(2) Heating temperature 65 ° C, rapid cooling
The above coloring and decoloring could be repeated stably.
[0082]
Example 6
A recording medium was obtained in the same manner as in Example 5, except that the following compositions A and B were used.

[0083]
After setting this recording medium in the initial state in the same manner as in Example 5, the following operations (1) and (2) were sequentially performed, and the coloring characteristics were examined.
(1) Heating temperature 125 ° C, rapid cooling → color tone: reddish (mixed color of red and green) ... Both A and B develop color
(2) Heating temperature 65 ° C, rapid cooling → color tone: green ... A is colored, B is decolorized
Similarly, the following operations (1) and (2) were sequentially performed.
(1) Heating temperature 125 ° C, rapid cooling → color tone: reddish (mixed color of red and green) ... Both A and B develop color
(2) Heating temperature 85 ° C, rapid cooling → color tone: red ... A is decolored, B is colored
From the above results, it was found that this recording medium can form images of three colors. These colors can be set to the initial state in the same manner as in Example 5, and coloring and decoloring could be stably repeated.
Next, with the recording medium in an initial state, heat was applied imagewise using a thermal head under the following conditions (1) and (2), and the color tone was examined.
{Circle around (1)} Applied voltage 13.3V, pulse width 1.8msec → color tone: reddish color ... A, B color development
{Circle around (2)} Applied voltage 13.3V, pulse width 0.5msec → color tone: red ... only B color
In this way, images having different color tone were formed depending on the heat application conditions.
[0084]
Example 7
A recording medium was obtained in the same manner as in Example 5, except that the following compositions A and B were used.

[0085]
After setting this recording medium in the initial state in the same manner as in Example 5, the following operations (1) and (2) were sequentially performed to examine the coloring characteristics.
(1) Heating temperature 125 ° C, rapid cooling → color tone: reddish (mixed color of red and green) ... Both A and B develop color
(2) Heating temperature 65 ° C, rapid cooling → color tone: green ... A is colored, B is decolorized
Similarly, the following operations (1) and (2) were sequentially performed. (1) Heating temperature 125 ° C, rapid cooling → color tone: reddish (mixed color of red and green) ... Both A and B develop color
(2) Heating temperature 85 ° C, rapid cooling → color tone: red ... A is decolored, B is colored
From the above results, it was found that this recording medium can form images of three colors. These colors can be set to the initial state in the same manner as in Example 5, and coloring and decoloring could be stably repeated.
Next, with the recording medium in the initial state, heat was applied imagewise using a thermal head under the following conditions (1) and (2) to examine the color tone.
{Circle around (1)} Applied voltage 13.3V, pulse width 1.8msec → color tone: reddish color ... A, B color development
{Circle around (2)} Applied voltage 13.3V, pulse width 0.5msec → color tone: red ... only B color
In this way, images having different color tone were formed depending on the heat application conditions.
[0086]
Example 8
A recording medium was obtained in the same manner as in Example 5, except that the following compositions A and B were used.

[0087]
After setting this recording medium in the initial state in the same manner as in Example 5, the following operations (1) and (2) were sequentially performed to examine the coloring characteristics.
(1) Heating temperature 125 ° C, rapid cooling → color tone: reddish maroon (mixed color of red and green) ... Both A and B develop color
(2) Heating temperature 65 ° C, rapid cooling → color tone: green ... A is decolored, B is colored
Similarly, the following operations (1) and (2) were sequentially performed.
{Circle around (1)} Heating temperature 125 ° C, quenching → color tone: reddish maroon (mixed color of red and green) ... Both A and B develop
(2) Heating temperature 85 ° C, rapid cooling → color tone: red ... A is colored, B is decolorized
From the above results, it was found that this recording medium can form images of three colors. These colors can be set to the initial state in the same manner as in Example 5, and coloring and decoloring could be stably repeated.
[0088]
Example 9
The same recording medium as in Example 5 was heated and quenched to 125 ° C. on a hot plate, so that both recording layers A and B were colored (maroon). This recording medium was heated imagewise using a thermal head under the following conditions (1) and (2), and the color tone at that time was examined. {Circle around (1)} Applied voltage 13.3V, pulse width 1.6msec → color tone: red ... A decolorization, B color development
{Circle around (2)} Applied voltage 8.0 V, pulse width 0.9 msec → color tone: green ... A color development, B color erasure
As described above, red and green images were formed by applying heat under the conditions (1) and (2) while the whole was colored maroon.
[0089]
Example 10
A recording medium was obtained in the same manner as in Example 5, except that the following compositions A and B were used.

[0090]

This recording medium was in a state where the recording layers of A and B were entirely colored in the same manner as in Example 9 (maroon color). Next, an image was heated with a thermal head under the following conditions (1) and (2), and the color tone at that time was examined.
{Circle around (1)} Applied voltage 13.3V, pulse width 1.6msec → color tone: green ... A decolorization, B color development
{Circle around (2)} Applied voltage 8.0 V, pulse width 0.8 msec → color tone: red ... A color development, B color erasure
As described above, red and green images were formed by applying heat under the conditions (1) and (2) while the whole was colored maroon.
[0091]
Example 11
Compositions A and B containing the following color developer and color former were sufficiently pulverized and dispersed by a ball mill until the particle diameter became about 1 μm to prepare a coating solution for forming a recording layer.

[0092]
A coating solution B was applied on a 100 μm-thick polyester film and dried to form a recording layer B having a thickness of about 5 μm.
On the other hand, a toluene / methyl ethyl ketone solution of a saturated polyester resin [Vylon 300 manufactured by Toyobo Co., Ltd.] was applied and dried as an adhesive layer on one side of a 4.5 μm-thick polyester film to obtain a film for an intermediate layer. . In this case, the dry adhesion amount of the resin is 3 g / m ² Met. Next, the adhesive layer of this film was overlaid on the recording layer B obtained above, and pressed by a heat roller having a pressure of 2 kg (linear pressure) and a temperature of 125 ° C.
Next, the coating solution A was applied on the resin intermediate layer thus formed and dried to form a recording layer A having a thickness of about 5 μm, thereby producing a reversible multicolor thermosensitive recording medium of the present invention. The recording medium was placed on a hot plate at a temperature of 125 ° C. for 20 seconds to develop both recording layers, and then placed in an oven at a temperature of 82 ° C. to decolor the recording layer A. Next, the recording layer B was placed in an oven at a temperature of 63 ° C. to erase the color. By this operation, the recording medium was brought into a substantially transparent initial state.
[0093]
The following operations (1) and (2) were sequentially performed in order to examine the coloring characteristics of the recording medium, and the coloring tone at each stage was examined. Each heating / cooling operation was performed by placing the back surface on a hot plate for 10 seconds and then immediately bringing the back surface into contact with a 1 ° C. cooling plate.
(1) Heating temperature 125 ° C, rapid cooling → color tone: mixed color of red and green ... Both A and B develop color
(2) Heating temperature 67 ° C, rapid cooling → color tone: red ... B is decolorized, A only develops color
Similarly, the following operations (1) and (2) were sequentially performed.
(1) Heating temperature 125 ° C, rapid cooling → color tone: mixed color of red and green ... Both A and B develop color
(2) Heating temperature 85 ° C, rapid cooling → color tone: green ... A is decolored, B only
From the above results, it was found that three-color images can be formed on this recording medium by one or two stages of heating and cooling operations.
The above-described coloring and decoloring operations could be repeated stably.
[0094]
Example 12
Using the following compositions C and D, a coating solution for forming a recording layer was prepared in the same manner as in Example 11.

A recording layer D was provided on a 100 μm-thick polyester film in the same manner as in Example 11.
On the other hand, a saturated polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.) was applied as an adhesive layer to one surface of an aromatic polyamide film having a thickness of 4 μm as an intermediate layer and a protective layer by the same method as in Example 11, and Was laminated on the recording layer D formed as described above in the same manner as in Example 11 to obtain an intermediate layer.
Next, a recording layer C was provided on the intermediate layer in the same manner as in Example 11, and an aromatic polyamide film was laminated thereon in the same manner as in the case of the intermediate layer to form a protective layer. The reversible multicolor thermosensitive recording medium of the present invention thus produced was treated in the same manner as in Example 11, to obtain a recording medium in an almost transparent initial state in which both the C and D recording layers were erased.
[0096]
The following operations (1) and (2) were sequentially performed in order to examine the color development characteristics of the recording medium, and the color tone at each stage was examined. The heating and cooling operations are the same as in Example 11.
(1) Heating temperature 125 ° C, rapid cooling → color tone: mixed color of red and green ... Both C and D are colored
(2) Heating temperature 67 ° C, rapid cooling → color tone: green ... D is decolored, C only
Similarly, the following operations (1) and (2) were sequentially performed.
(1) Heating temperature 125 ° C, rapid cooling → color tone: mixed color of red and green ... Both C and D are colored
(2) Heating temperature 85 ° C, rapid cooling → color tone: red ... C decolored, D only
From the above results, it was found that this recording medium can form three-color images by one or two-stage heating. In each of these cases, as in Example 11, each recording layer could be returned to the initial state by a method of erasing the recording layers in order from the recording layer having the decoloring temperature region on the high temperature side. Further, these coloring and decoloring operations could be repeated stably.
[0097]
Example 13
A reversible multicolor heat-sensitive recording medium of the present invention was produced in the same manner as in Example 11, except that the film of the intermediate layer was replaced with a polyimide film having a thickness of 4 μm.
When the coloring properties of this recording medium were examined in the same manner as in Example 11, three-color images could be formed by one or two-stage heating. Further, these coloring and decoloring operations could be repeated stably.
Example 14
A reversible multicolor thermosensitive recording medium of the present invention was produced in the same manner as in Example 11 except that the film of the intermediate layer was replaced with a polyparabanic acid film having a thickness of 5 μm.
When the coloring properties of this recording medium were examined in the same manner as in Example 11, three-color images could be formed by one or two-stage heating. Further, these coloring and decoloring operations could be repeated stably.
[0098]
Example 15
Using the following compositions E, F, and G, a coating solution for forming a recording layer was prepared in the same manner as in Example 11.

[0099]

[0100]
A recording layer G was provided on a 100 μm-thick polyester film in the same manner as in Example 11. A 4.5 μm-thick polyester film serving as an intermediate layer was laminated thereon by a dry lamination method in the same manner as in Example 11. Next, the recording layer F was provided in the same manner as the recording layer G. On the recording layer F, a polyester film to be an intermediate layer was bonded by the same method as the previous one. Further, a recording layer E was provided thereon by the same method. A 4 μm-thick polyamide film was laminated on the recording layer E in the same manner as in Example 12 to form a protective layer.
The reversible multicolor heat-sensitive recording medium having three recording layers obtained in this manner is treated by heating in an oven in order of the decolorization temperature of each layer in descending order of the decolorization temperature range, and all recording layers are decolorized. Initial state.
[0101]
The following operations (1), (2), and (3) were performed sequentially in the same manner as in Example 11 in order to examine the coloring properties of the recording medium.
[Test 1]
(1) Heating temperature 125 ° C · Rapid cooling → Color tone: mixed color of red, green, and black ... E, F, and G all develop color
(2) Heating temperature 70 ° C, rapid cooling → color tone: mixed color of red and black ... E, G color development, F decolorization
(3) Heating temperature 55 ° C, rapid cooling → color tone: Red ... Only E, F, G decolored
[Test 2]
(1) Heating temperature 125 ° C · Rapid cooling → Color tone: mixed color of red, green, and black ... E, F, and G all develop color
(2) Heating temperature 85 ° C, rapid cooling → Color tone: mixed color of green and black ... F, G color development, E decolorization
(3) Heating temperature 55 ° C, rapid cooling → color tone: green ... F only develops color, E, G decolorizes
[Test 3]
(1) Heating temperature 125 ° C · Rapid cooling → Color tone: mixed color of red, green, and black ... E, F, and G all develop color
(2) Heating temperature 85 ° C, rapid cooling → Color tone: mixed color of green and black ... F, G color development, E decolorization
(3) Heating temperature 70 ° C, rapid cooling → Color tone: Black ... G only color, E, F decolorized
From the above results, it has been found that this recording medium can form a multicolor image of red, green, black and a mixed color thereof by stepwise heating. In addition, coloring and decoloring could be repeatedly performed.
[0102]
Example 16
Microcapsules using the reversible thermochromic composition as a core material were prepared by the following method.
A mixture of 2-anilino-6- (N-ethyl-Nn-hexylamino) fluoran and docosylphosphonic acid at a molar ratio of 1: 4 as a core material was used as a vinyl chloride-vinyl acetate copolymer (VYHH). 5 g was dispersed in a solution dissolved in 20 g of methylene chloride, and this was put into an aqueous solution containing a surfactant and emulsified (W / O type). The methylene chloride was evaporated under high-speed stirring to form a capsule wall, which was filtered, washed with water, and dried under reduced pressure to obtain microcapsule powder A. Similarly, as the core material, 1, 2,. Microcapsules B containing a mixture of benzo-6- (N-ethyl-N-isoamylamino) fluoran and hexadecylphosphonic acid at a molar ratio of 1: 4 were obtained.
Next, a coating solution for forming a recording layer having the following composition was prepared.
[0103]
(Coating liquid composition for forming recording layer)
Microcapsule A 5 parts
Microcapsule B 5 parts
Ionomer aqueous dispersion
(Dai Nippon Ink Company; Hydran AP-40) 30 parts
Melamine crosslinking agent
(Dainippon Ink; DECKAMINE PM-N) 1.5 parts
0.7 parts of catalyst (Dainippon Ink Co., Ltd .; CATALYST ES-2)
This solution was applied on a 100 μm-thick polyester film and dried at 100 ° C. for 10 minutes to form a recording layer having a thickness of about 10 μm.
After setting this recording medium in the initial state in the same manner as in Example 5, the coloring properties were examined in the same manner as in Example 7. As a result, the same coloring characteristics as in Example 7 were obtained.
[0104]
Example 17
A mixture was prepared by mixing and pulverizing the following developer and color former at a molar ratio of 5: 1.
Octadecylphosphonic acid
2- (o-chloroanilino) -6-dibutylaminofluoran
A glass plate having a thickness of about 1 mm was prepared, and this glass plate was heated on a hot plate such that the surface thereof was 170 ° C. After a small amount of the powder of the mixture was melted on the glass plate, a 0.1 mm-thick glass plate was placed over the melt to spread the melt to a uniform thickness. Next, the whole was removed from the hot plate, brought into contact with ice water, quenched, the 0.1 mm glass plate overlaid was peeled off, and a 5 wt% aqueous solution of polyvinyl alcohol was put on the colored recording layer (reversible). After coating and drying, an intermediate layer was provided.
[0105]
Subsequently, a coating liquid for forming an irreversible recording layer having the following composition was applied and dried to prepare a multicolor heat-sensitive recording medium of the present invention.

The recording medium was first temporarily heated and cooled to 72 ° C. to erase the color of the reversible recording layer. This state is an unrecorded initial state, and both recording layers are in a colorless state.
[0106]
The recording operations (1) to (3) in Table 7 were sequentially performed on the recording medium thus obtained, and three types of colors shown in Table 7 were obtained. In this recording medium, once the irreversible thermosensitive recording layer is colored, it becomes a red base color, and a black image can be reversibly formed thereon.
[Table 7]

[0107]
Example 18
A reversible multicolor heat-sensitive recording medium of the present invention was prepared in the same manner as in Example 17, except that a developer and a color former of the reversible thermosensitive recording layer were prepared in the following combinations.
Hexadecylphosphonic acid
2-anilino-3-methyl-6- (N-ethyl-p-toluidino) fluoran
This recording medium was processed in the same manner as in Example 17 to set the recording medium in an unrecorded initial state.
The recording operations (1) to (3) in Table 8 were sequentially performed on the recording medium thus obtained, and three types of color tones shown in Table 8 were obtained. In the case of this recording medium as well, the formation of a red base color and the reversible formation of a black image thereon are possible as in the case of the seventeenth embodiment.
[Table 8]

[0108]
Example 19
A reversible multicolor heat-sensitive recording medium of the present invention was prepared in the same manner as in Example 17, except that a developer and a color former of the reversible thermosensitive recording layer were prepared in the following combinations.
Eicosylthiomalic acid
2-anilino-3-methyl-6-diethylaminofluoran
This recording medium was processed in the same manner as in Example 7 to bring the recording medium into an unrecorded initial state.
The recording operations (1) to (3) in Table 9 were sequentially performed on the recording medium thus obtained, and three types of color tones shown in Table 9 were obtained. In the case of this recording medium as well, the formation of a red base color and the reversible formation of a black image thereon are possible as in the case of the seventeenth embodiment.
[Table 9]

[0109]
【The invention's effect】
With the reversible multicolor heat-sensitive recording medium and display medium of the present invention, a multicolor image can be easily formed only by applying heat, and this image can be stably maintained at room temperature, and the multicolor image can be formed. The image can be erased and can be used repeatedly. Since the color tone of the formed multicolor image can be freely changed by selecting the composition, a full-color image can be formed by using the three primary colors as a color former.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the coloring density and the temperature of a composition used in the present invention, and is an explanatory diagram of the principle of coloring and decoloring. A solid line (A → B → C) indicates an image forming process, and a broken line (C → D → A) indicates an image erasing process.
FIG. 2 is a graph showing the relationship between the light transmittance and the temperature of a composition using a phosphonic acid having a long alkyl chain as a color developer.
FIG. 3 is a diagram showing an example of a basic configuration of a reversible multicolor thermal recording medium of the present invention.
FIG. 4 is a diagram showing the relationship between the concentration and the temperature of each layer constituting the reversible multicolor thermosensitive recording layer of the present invention.
FIG. 5 is a diagram showing another example showing the same relationship as FIG.
FIG. 6 is a diagram showing a basic configuration of a recording apparatus of the present invention.
FIG. 7 is a diagram showing a basic configuration of a display device of the present invention. In this figure, (a) shows the basic configuration of the device when a sheet-shaped display medium is used, and (b) shows the basic configuration of the device when an endless belt-shaped display medium is used.
[Explanation of symbols]
A, B, C recording layer
S support
M Intermediate layer
P protective layer
R Reversible multicolor thermal recording medium
H ₁ , H ₂ , H ₃ Heating element that can apply heat in the form of images
L ₁ , L ₂ , L ₃ Heating element for overall heating
H ₁ ', H ₂ ', H ₃ '' Heating element that can apply heat in the form of images
L ₁ ', L ₂ ', L ₃ '' Heating element for overall heating
D Reversible multicolor thermal display medium

Claims (3)

In a reversible multicolor thermosensitive recording medium in which a plurality of types of reversible thermochromic compositions having different coloring color tones and decolorization start temperatures are present on a support in a separated and independent state, each of the compositions is A reversible multicolor heat-sensitive recording medium characterized by being contained in independent microcapsules. 2. The reversible multicolor thermosensitive recording medium according to claim 1, wherein an irreversible thermochromic composition is present on the support in addition to the reversible thermochromic composition. A reversible multicolor thermochromic composition comprising a mixture of microcapsules independently containing a plurality of types of reversible thermochromic compositions having different color tone and decolorization start temperature.

Images