JP3868520B2 - Multicolor thermal recording medium - Google Patents

Description

【００１２】
該多色感記録媒体に画像を設けるときは、図８に示すように、低エネルギー印字部１０においては、感熱ヘッドに０．８ｍＪ／ｄｏｔの印字エネルギーを印加し、感熱印字薄膜層４の破壊による破壊印字薄膜層４１で縁取られた印字着色層２３を印字した。
次いで、高エネルギー印字部２０においては、感熱ヘッドに１．０ｍＪ／ｄｏｔの印字エネルギーを印加し、感熱印字薄膜層４を破壊して透明化した破壊印字薄膜層４１を形成するとともに、着色層２を印字着色層２３とし、印字発色層３３との混色した画像を印字した。
すなわち、基材シート１に、破壊印字薄膜層４１の透明部で形成される着色層２による薄赤色の『印字着色層２３』と『印字着色層２３と印字発色層３３との混色』との２画像を鮮明に印字するものである。
【００１３】
（実施例２）
図９に示すように、基材シート１となる王子油化合成紙（株）製ユポＦＰＧ１３０の一方の面に、着色層の機能をも備えた磁気記録層２６全面に塗布量３０ｇ／ｍ² 、及び感熱印字薄膜層４用のポリエステル系ワニスによるプライマー層１６をグラビアコーティングで設けた。次いで着色層の側にプライマー層１６を介して下記組成の「消色層塗布液」を３ｇ／ｍ² 塗布して消色層６を形成した。次いで、上記と同様のプライマー層１７及び低エネルギー発色型の下記組成の赤橙色に発色する「感熱発色層塗布液２」の感熱発色層３を４ｇ／ｍ² 、及び感熱印字薄膜層用の上記と同様のプライマー層１８をグラビアコーティングで設けた。そして、真空蒸着法により錫を５００Åの厚さで設けて感熱印字薄膜層４を形成した。更に、カルボニル基を含む塩化ビニル・酢酸ビニル共重合体系ワニスによるプライマー層１９を介して実施例１と同様の保護層５をグラビアコーティングにより設けて、実施例２の多色感熱記録媒体を設けたカードを形成した。

【００１４】
該多色感記録媒体に画像を設けるときは、図１０に示すように、低エネルギー印字部１０においては、感熱ヘッドに１．０ｍＪ／ｄｏｔの印字エネルギーを印加し感熱印字薄膜層４を破壊して透明部となる破壊印字薄膜層４１を形成すると同時に感熱発色層３の発色による印字発色層３３による画像を印字した。このとき印字発色層３３は、破壊印字薄膜層４１により縁取られた印字磁気記録層２７との混色となるものである。
次いで、高エネルギー印字部２０を設けて、感熱印字薄膜層４を破壊して透明化した破壊印字薄膜層４１を形成するとともに、感熱発色層３が発色する印字発色層は、消色層６が活性化した活性消色層６１で消色され透明化した消色発色層３４となり、結果として透明化した破壊印字薄膜層４１の部分のみで形成される印字磁気記録層２７を印字した。
すなわち、『印字発色層３３と印字磁気記録層２７との混色』による画像と、破壊印字薄膜層４１の透明部に形成される『印字磁気記録層２７』の画像とを２色で鮮明に形成するものである。
そして、 そして、この多色感熱記録媒体に、磁気ヘッドにより磁気記録を行ったところ、記録密度４２０ＦＲＰＩ（flux reversal per inch）で、その再生出力は、印字部で５．９Ｖ、非印字部で６．３Ｖであり、印字が再生出力の出力低下に及ぼす影響は、６％であり実用上問題がない範囲であった。
【００１５】
以下、具体的に構成要件である、基材シート、着色層、感熱印字薄膜層、消色層、感熱発色層及び保護層の材料及び形成方法について記載する。
【００１６】
本発明の基材シートは、ポリアミド、セルローストリアセテート、セルロースジアセテート、ポリスチレン、ポリプロピレン、ポリエステル、ポリイミド、ポリカーボネート、エチレン・酢酸ビニル共重合体ケン化物、ポリ塩化ビニルなどの熱可塑性樹脂の延伸又は無延伸シート、銅、アルミニウムなどの金属、紙、樹脂含浸紙、合成紙などを、単層あるいは積層シートとして使用できる。そして、その厚さは、材料の加工方法、剛性、用途に応じて要求される物性によって決まるが０．０３〜２ｍｍである。そして、必要によっては、無機あるいは有機の顔料や染料による着色を行う。
好ましい材料は、０．０５〜０．４ｍｍの延伸ポリエステルシート又は、印刷コーティング適性に優れた耐熱性のある合成紙である。
また、基材シートには情報記録を行う磁気記録部、ＩＣメモリー、光メモリーをその一部に設けることができる。磁気記録部は、基材シートに直接形成して更に、本発明の多色感熱記録媒体を構成することもできる。
【００１７】
着色層は、通常の無機あるいは有機の顔料を単体又は適宜に混合して所望の色相とし、エチルセルロースなどの繊維素誘導体、ロジン誘導体、アクリル樹脂、ポリエステル樹脂とワックス、可塑剤、安定剤などの添加物を加えた樹脂ワニスをバインダーとするものや、アクリル樹脂や、そのオリゴマー、モノマーよりなる電離放射線硬化型樹脂を用いるものがある。
又、絵柄層は、その印刷方法にもよるが、通常の、平版、グラビア版を含む凹版、孔版、凸版の枚葉又は巻取り印刷用の溶剤乾燥型インキや反応硬化型インキにより形成することができる。
着色層は、上記印刷方法の他にロールコート、エアナイフコートなど通常の塗布方法によって基材全面又は一部に形成することができる。
【００１８】
感熱印字薄膜層は、テルル、錫、インジウム、ビスマス、鉛、亜鉛などの金属あるいはこれらの合金、若しくはテルルカーバイドなどの低融点をもつ金属の化合物を、真空蒸着法、スパッタリング法、メッキなどの方法により形成する。そして、感熱印字薄膜層の厚さは、着色層を完全に遮蔽する厚さでよく１００〜２０００Å、好ましくは、５００〜１０００Åである。
【００１９】
感熱発色層は、従来より知られているラクトン環、ラクタム環、スピロピラン環などをもつ無色又は淡色のロイコ染料を発色主剤と、加熱したときにロイコ染料と反応して発色させる発色助剤とを発色剤とし、ポリビニルアルコール、メトキシセルロース、メチルセルロース、ポリアクリル酸ソーダ、アルギン酸ソーダ、デンプン、カゼインなどの天然あるいは合成高分子の水溶液や塩化ビニル・酢酸ビニル共重合体、スチレン・ブタジエン・アクリル樹脂系ラテックスなどの水分散体をバインダーとする塗布液をロールコート、エアナイフコートなど通常の塗布方法によって形成することができる。そして、その塗布量は、所望の発色濃度にもよりが、０．５〜１０ｇ／ｍ² 、好ましくは、２〜５ｇ／ｍ² である。
【００２０】
上記の材料より構成される発色層を消色する消色層は、従来より使用されている消色剤である高級脂肪族アルコール、ポリエーテル、ポリエチレングリコール誘導体や、アセトアミド、ステアリルアミド、フタロニトリルなどの含窒素有機化合物を、上記の発色剤に用いるバインダーに溶解、又は分散して同様の方法で塗布して形成する。そして、その塗布量は、感熱発色層の塗布量にもよるが、０．５〜１０ｇ／ｍ² 、好ましくは、２〜５ｇ／ｍ² である。
【００２１】
保護層は、上記の各種塗布層、又は形成した画像を、摩擦などの物理的損傷や、油などの化学的汚染を防ぐために設けるものである。
アクリル系、ウレタン系、ポリエステル系、塩化ビニル・酢酸ビニル共重合体を主とする熱可塑性樹脂のワニスに、必要によっては、ワックス、シリコーン樹脂などの滑剤や静電防止剤を加えて構成する。
また、官能基をもつ、ポリウレタン、ポリエステルやポリエーテル系樹脂を、ポリイソシアネートにより硬化するものや、アミノアルキッド、樹脂変性乾性油などの熱、あるいは酸化硬化型ワニスや、電離放射線硬化型樹脂を使用する。
塗布方法は、基材シート又は樹脂ワニスの形状硬化方法に応じた通常の方法で行うことができ、そして、その塗布量は、１〜１０ｇ／ｍ² 、好ましくは、２〜５ｇ／ｍ² である。
磁気記録層はγ-Fe₂0₃、Co被着γ-Fe₂O₃、Fe₃O₄ 、CrO₂、Fe、Fe-Cr 、Fe-Co 、Co-Cr 、Co-Ni 、Mn-Al 、Baフェライトなどの従来から公知の磁性微粒子を適当なインキベヒクルに分散した分散体を、グラビアコート、ロールコート、ナイフコートなどの従来より公知の方法によって形成できる。またFe-Co 、Co-Cr 、Co-Ni などの、金属又は合金あるいはその酸化物を用いて、真空蒸着法、スパッタリング法、メッキ法などによって基材シートに形成することもできる。
塗布による磁気記録層の厚さは、１〜１００μｍ好ましくは５〜２０μｍである。また、真空蒸着法、スパッタリング法、メッキ法などによる磁気記録層の厚さは、１００〜１００００Å、好ましくは５００〜１０００Åである。
γ-Fe₂O₃などを分散するベヒクルは、ポリビニルブチラール、塩化ビニル・酢酸ビニル共重合体、ポリウレタン、ポリエステル、セルロース誘導体、アクリル樹脂、スチレン・マレイン酸共重合体などである。そして、必要に応じてニトリルゴム、ウレタンエラストマーなどのゴムを添加する。また、磁性微粒子を分散する上記のベヒクルには、必要に応じて、界面活性剤、ワックス、シリコーンオイルなどの添加剤やカーボンその他の顔料を添加することもできる。
【００２２】
上記の各層を形成するとき、層間の接着をより強固に安定する目的で、必要に応じてプライマー層を設けることが好ましい。
プライマー層は、接着剤として使用されているポリエステル・イソシアネート、ポリエーテル・イソシアネート、塩化ビニル・酢酸ビニル共重合体アクリル樹脂などのワニスから各層の特性に応じて選択される。
そして、その塗布量は、塗布ぬけ部がない必要最低限でよく、０．１〜２ｇ／ｍ² を、ロールコーティングやグラビヤコーティングで設ける。
【００２３】
【発明の効果】
本願発明によれば、上記のように、着色層、低エネルギー発色層と高エネルギーで活性化する消色層とを併用することにより低エネルギー印字部では『印字着色層と印字発色層との混色』による画像を、そして、高エネルギー印字部では、消色層を併用することにより『印字着色層』による画像が他の色による縁取りもなく鮮明に形成できるという効果がある。
また、感熱発色層を単層で設けてあるために、温度差により異なる色を生ずることはなく、色相を明確に分離した画像を形成できるという効果がある。
【図面の簡単な説明】
【図１】多色感熱記録媒体の層構成の断面を示す概略図である。
【図２】図１の多色感熱記録媒体より印字形成した画像の断面を示す概略図である。
【図３】多色感熱記録媒体の消色層を用いた層構成の断面を示す概略図である。
【図４】図３の多色感熱記録媒体より印字形成した画像の断面を示す概略図である。
【図５】多色感熱記録媒体の他の層構成の断面を示す概略図である。
【図６】図５の多色感熱記録媒体より印字形成した画像の断面を示す概略図である。
【図７】実施例の多色感熱記録媒体の構成の断面を示す概略図である。
【図８】図７の多色感熱記録媒体より印字形成した画像の断面を示す概略図である。
【図９】他の実施例の多色感熱記録媒体の構成の断面を示す概略図である。
【図１０】図９の多色感熱記録媒体より印字形成した画像の断面を示す概略図である。
【符号の説明】
１ 基材シート
２ 着色層
２１ 絵柄層
２３ 印字着色層
２４ 印字絵柄層
２６ 磁気記録層
２７ 印字磁気記録層
３ 感熱発色層
３３ 印字発色層
３４ 消色発色層
４ 感熱印字薄膜層
４１ 破壊印字薄膜層
５ 保護層
６ 消色層
６１ 活性消色層
１０ 低エネルギー印字部
２０ 高エネルギー印字部
１６、１７、１８、１９ プライマー層[0001]
[Industrial application fields]
The present invention relates to a multi-color thermal recording medium, and more particularly, to easily perform multi-color printing on a magnetic card or the like. By printing the image in the part where the thin film of the thermal printing thin film layer, in which the color layer is partially destroyed by heating, is removed, or by partially erasing the colored image, a multi-colored clear The present invention relates to a multicolor thermosensitive recording medium that enables easy printing.
[0002]
[Prior art]
Conventionally, as a method of performing multicolor printing on a thermal recording medium on a magnetic card or the like, a leuco dye layer and a combination of a developer and a decoloring layer having different color development temperatures or a diazo dye layer and a basic material layer are used. The thing by lamination | stacking with a thermosensitive coloring layer is known.
[0003]
[Problems to be solved by the invention]
However, in the combination of the leuco dye layer and the developer and the color erasing layer having different color development temperatures, the developer or the color erasing agent acts on the leuco dye layer or the diazo dye layer to cause the base fog phenomenon or color development. Phenomenon that the storage stability of the ink is deteriorated, or the desired color development by high energy printing becomes an image where the periphery of the printing area is bordered by the hue due to the coloring of the printing temperature corresponding to low energy, and the desired two colors There was a problem that it could not be completely separated.
The heat-sensitive color developing layer formed by laminating the diazo dye layer and the basic material layer requires a fixing step by irradiating the image with ultraviolet rays after printing, and there is a problem that the apparatus becomes complicated.
Further, when a multicolor thermosensitive recording medium is provided on the magnetic layer, there is a problem that the layer thickness is increased and it is difficult to read the magnetism.
According to the present invention, multicolor printing can be easily and clearly obtained without changing the periphery of the printing portion due to change in printing energy, and can be printed on the magnetic recording layer easily and clearly. An object of the present invention is to provide a multicolor thermal recording medium such as a card that can be used.
[0004]
[Means for Solving the Problems]
In the present invention, the above object is achieved by the following configuration.
That is, the first invention of the present application has at least a colored layer (2), a decoloring layer (6), a thermosensitive coloring layer (3) , a thermosensitive printing thin film layer (4 ) on one surface of the substrate sheet (1). ) , A multicolor thermal recording medium in which are sequentially laminated,
The thermal printing thin film layer (4) is made of a metal or a compound having a low melting point, and is destroyed and made transparent by the printing energy of the print head ,
The thermosensitive coloring layer (3) comprises a coloring aid that reacts with the leuco dye when heated using a leuco dye as a color developing agent, and develops color by the printing energy of the print head,
The decoloring layer (6) is made of a higher aliphatic alcohol, a polyether, a polyethylene glycol derivative, or a nitrogen-containing organic compound such as acetamide, stearylamide, or phthalonitrile, and has a higher energy than the printing energy that the thermosensitive coloring layer develops. A multicolor thermosensitive recording medium, wherein the thermosensitive coloring layer is decolorized and transparent .
A second invention of the present application is the multicolor thermal recording medium according to the first invention, wherein a magnetic recording layer is provided between the base sheet and the colored layer .
The third invention of the present application is, in the second invention, a multicolor heat-sensitive recording medium where the upper Ki磁 vapor recording layer is characterized Rukoto serves as a colored layer.
A fourth invention of the present application is the multicolor thermal recording medium according to the first or second invention, wherein a picture layer is provided in place of the colored layer .
[0005]
As shown in FIG. 1, the multicolor thermosensitive recording medium of the present invention is provided with a colored layer 2 and a thermosensitive coloring layer 3 on one surface of a substrate sheet 1, and further comprises a thermosensitive printing thin film layer 4 and a protective layer 5. They are laminated in order.
[0006]
When printing an image on the multicolor recording medium, as shown in FIG. 2, the low-energy printing unit 10 has the colored layer 2 because the thermal printing thin film layer 4 becomes the destructive printing thin film layer 41 and becomes transparent. Then, an image is formed only by the “printing colored layer 23” bordered by the destructive printing thin film layer 41. With this printing energy, the thermosensitive coloring layer 3 is not colored and is kept transparent.
In the high energy printing section 20, the thermal printing thin film layer 4 becomes a destructive printing thin film layer 41 and becomes transparent. At the same time, the thermal coloring layer 3 develops a color to form a printing coloring layer 33. An image by “color mixing with the layer 33” is formed.
That is, on the base sheet 1, the image by the print coloring layer 23 is clearly displayed at the low temperature energy 10, and the image by the color mixture of the print coloring layer 33 and the print coloring layer 23 by the heat sensitive coloring layer is clearly displayed at the high temperature printing unit 20. It is for printing.
[0007]
As shown in FIG. 3, the second invention has a decoloring layer 6, a thermosensitive coloring layer 3, a thermosensitive printing thin film that acts on one surface of the base sheet 1 with higher energy than the colored layer 2 and the thermosensitive coloring layer 3. The layer 4 and the protective layer 5 are laminated in order.
And the magnetic recording layer 26 of 3rd invention and / or the pattern layer 21 which is 4th invention are formed in the surface of the base material sheet 1. FIG.
The picture layer 21 can be provided together with the colored layer or can be provided with only the picture layer. The magnetic recording layer can also serve two functions as a colored layer.
[0008]
When printing an image on the multicolor thermal recording medium, as shown in FIG. 4, in the low energy printing unit 10, the thermal printing thin film layer 4 becomes a transparent destructive printing thin film layer 41, and at the same time, the print coloring layer 33 is formed. The printed image is printed by mixing colors of the print coloring layer 23 and the print coloring layer 33. At this low printing energy, the decoloring layer 6 is not activated and is maintained as a transparent layer.
Further, in the high energy printing unit 20, the thermal printing thin film layer 4 becomes a destructive printing thin film layer 41 and becomes transparent, and at the same time, the printing color developing layer 33 is decolored by the activated active decoloring layer 61 and decoloring color development. The layer 34 is formed, and an image is formed on the print portion by the print coloring layer 23 bordered by the destructive print thin film layer 41.
That is, an image formed by color mixing of the print coloring layer 23 and the print coloring layer 33 is formed on the base sheet 1 at low temperature energy 10, and the image formed by the print coloring layer 23 is clearly printed at the high temperature printing unit 20. It is.
[0009]
Further, as shown in FIG. 5, a multicolor thermosensitive recording medium in which a heat-sensitive coloring layer 3 and a fine pattern color pattern are provided as a picture layer 21 on a base sheet 1, and a thermal printing thin film layer 4 and a protective layer 5 are provided in this order. Can also be configured. Then, as shown in FIG. 6, in the low energy printing unit 10, the color pattern, which is the printed pattern layer 24 bordered by the destructive printing thin film layer 41 of the thermal printing thin film layer 4, is directly expressed on the base sheet 1. Further, in the high energy printing unit 20, the print picture layer 24 can be expressed on the print coloring layer 33.
[0010]
[Action]
As described above, the present invention includes a coloring layer, a heat-sensitive coloring layer that develops color by high-energy printing, a low-energy-breaking heat-sensitive printing thin film layer provided in a layer near the heating printing portion, and a protective layer. Consists of Therefore, in low energy printing, the image by the “printing colored layer” bordered by the destructive printing thin film layer is formed clearly, and in high energy printing, the image by the “color mixture of the printing coloring layer and the printing coloring layer” is clearly formed. is there.
Further, the second invention is a combination of a colored layer, a low energy coloring layer, and a decoloring layer activated with high energy, so that in a low energy printing portion, a “printing colored layer and "Color mixing with printing color layer", and in the high energy printing part, the combined printing layer has the effect of making the printing color layer transparent, and the image by "print coloring layer" has no border by other colors It can be clearly formed.
Since the thermosensitive coloring layer is provided as a single layer, there is no difference in hue due to temperature difference, and an effect of forming an image in which the hue is clearly separated is produced.
And in order to use in combination with different printing effects such as thermosensitive coloring layer, thermal printing thin film layer, colored layer, and decoloring layer, there is no color development in different hues, and the mutual coloring in the printing process does not affect, A clear image can be formed.
In addition, the layer thickness for expressing multiple colors can be reduced, and magnetic reading can be performed accurately and easily even when stacked on a magnetic card provided with a magnetic recording layer.
Then, an image rich in changes by not only the colored layer but also the pattern layer can be expressed on the printing portion.
[0011]
【Example】
Hereinafter, embodiments of the present invention will be described in more detail with reference to the drawings.
Example 1
As shown in FIG. 7, a primer layer 16 (acrylic varnish) is applied to one surface of a biaxially stretched polyester sheet having a thickness of 188 μm as a base sheet 1 by a gravure printing method at a coating amount of 0.3 g / m ² (solid In the following description, the coating amount in this specification is described as a solid content), 2 g / m ^{2 of} the red colored layer ² , and a primer layer 17 similar to the above for the thermal printing thin film layer with acrylic varnish. Next, the primer layer 17 was provided with 5 g / m ^{2 of} the high-energy color-sensitive heat-sensitive color developing layer 3 made of “thermo-sensitive color developing layer coating solution 1” which develops a black color having the following composition, and the same primer layer 18 as described above. Then, a thermal printing thin film layer 4 was formed by providing tin with a thickness of 500 mm by vacuum deposition. Furthermore, a varnish composed of a two-component reactive linear polyester-isocyanate, an antistatic agent and a lubricant is provided as a protective layer 5 through a primer layer 19 made of a vinyl chloride / vinyl acetate copolymer varnish containing a carbonyl group. A card provided with the multicolor thermosensitive recording medium of Example 1 was formed by the m ² gravure coating method.

[0012]
When an image is provided on the multicolor recording medium, as shown in FIG. 8, in the low energy printing unit 10, a printing energy of 0.8 mJ / dot is applied to the thermal head to destroy the thermal printing thin film layer 4. The printing colored layer 23 bordered by the destructive printing thin film layer 41 was printed.
Next, in the high energy printing unit 20, a printing energy of 1.0 mJ / dot is applied to the thermal head to break the thermal printing thin film layer 4 to form a transparent printing thin film layer 41, and the colored layer 2 Was used as the print coloring layer 23, and a mixed color image with the print coloring layer 33 was printed.
That is, a light red “printing color layer 23” and “a color mixture of the print coloring layer 23 and the print coloring layer 33” by the colored layer 2 formed of the transparent portion of the destructive printing thin film layer 41 on the base sheet 1 Two images are printed clearly.
[0013]
(Example 2)
As shown in FIG. 9, the coating amount is 30 g / m ^{2 on the} entire surface of the magnetic recording layer 26 having the function of a colored layer on one surface of Yupo FPG 130 manufactured by Oji Oil Synthetic Paper Co. The primer layer 16 made of polyester varnish for the thermal printing thin film layer 4 was provided by gravure coating. Next, 3 g / m ² of the “decoloring layer coating solution” having the following composition was applied to the colored layer side through the primer layer 16 to form the decoloring layer 6. Next, 4 g / m ² of the above-described primer layer 17 and the low-energy coloring type thermal coloring layer 3 of “thermal coloring layer coating solution 2” of the following composition of red / orange color and the above for the thermal printing thin film layer. The same primer layer 18 as in Example 1 was provided by gravure coating. Then, a thermal printing thin film layer 4 was formed by providing tin with a thickness of 500 mm by vacuum deposition. Further, a protective layer 5 similar to that of Example 1 was provided by gravure coating through a primer layer 19 made of a vinyl chloride / vinyl acetate copolymer varnish containing a carbonyl group to provide the multicolor thermosensitive recording medium of Example 2. A card was formed.

[0014]
When an image is provided on the multicolor recording medium, as shown in FIG. 10, in the low energy printing unit 10, a printing energy of 1.0 mJ / dot is applied to the thermal head to destroy the thermal printing thin film layer 4. In addition, the destructive printing thin film layer 41 to be a transparent portion was formed, and at the same time, an image was printed by the printing color developing layer 33 by color development of the thermosensitive coloring layer 3. At this time, the print coloring layer 33 is mixed with the print magnetic recording layer 27 bordered by the destructive printing thin film layer 41.
Next, the high-energy printing unit 20 is provided to form a destructive printing thin film layer 41 that is made transparent by destroying the thermal printing thin film layer 4. The decolored color developing layer 34 which was decolored by the activated decoloring layer 61 and became transparent, and as a result, the printing magnetic recording layer 27 formed only by the portion of the destructive printing thin film layer 41 which was cleared was printed.
That is, the image of “color mixture of the print coloring layer 33 and the print magnetic recording layer 27” and the image of the “print magnetic recording layer 27” formed on the transparent portion of the destructive print thin film layer 41 are clearly formed in two colors. To do.
Then, when this multicolor thermosensitive recording medium was subjected to magnetic recording with a magnetic head, the reproduction output was 5.9 V at the printing portion and 6 at the non-printing portion at a recording density of 420 FRPI (flux reversal per inch). .3V, and the influence of printing on the output reduction of the reproduction output was 6%, and there was no problem in practical use.
[0015]
Hereinafter, materials and methods for forming the base sheet, colored layer, thermal printing thin film layer, decoloring layer, thermal coloring layer and protective layer, which are specific constituent elements, will be described.
[0016]
The base sheet of the present invention is a stretched or unstretched thermoplastic resin such as polyamide, cellulose triacetate, cellulose diacetate, polystyrene, polypropylene, polyester, polyimide, polycarbonate, saponified ethylene / vinyl acetate copolymer, polyvinyl chloride, etc. Sheets, metals such as copper and aluminum, paper, resin-impregnated paper, synthetic paper, and the like can be used as a single layer or a laminated sheet. The thickness is 0.03 to 2 mm although it depends on the material processing method, rigidity, and physical properties required depending on the application. If necessary, coloring with an inorganic or organic pigment or dye is performed.
A preferred material is a stretched polyester sheet having a thickness of 0.05 to 0.4 mm or a heat-resistant synthetic paper excellent in print coating suitability.
Further, the base sheet can be provided with a magnetic recording portion for recording information, an IC memory, and an optical memory in a part thereof. The magnetic recording portion can be directly formed on the base sheet to further constitute the multicolor thermosensitive recording medium of the present invention.
[0017]
The colored layer is made of normal inorganic or organic pigments alone or appropriately mixed to obtain a desired hue. Addition of fibrous derivatives such as ethyl cellulose, rosin derivatives, acrylic resins, polyester resins and waxes, plasticizers, stabilizers, etc. There are those using a resin varnish to which a product is added as a binder, and those using an ionizing radiation curable resin made of an acrylic resin, an oligomer or a monomer thereof.
The pattern layer may be formed of a normal, intaglio, including gravure plates, stencils, letterpress plates, or solvent-drying inks for reactive printing or reaction-curable inks, depending on the printing method. Can do.
The colored layer can be formed on the entire surface or a part of the substrate by a normal coating method such as roll coating or air knife coating in addition to the printing method.
[0018]
The thermal printing thin film layer is made of a metal such as tellurium, tin, indium, bismuth, lead, zinc, or an alloy thereof, or a metal compound having a low melting point such as tellurium carbide, a vacuum deposition method, a sputtering method, a plating method, etc. To form. The thickness of the thermal printing thin film layer may be a thickness that completely shields the colored layer, and is 100 to 2000 mm, preferably 500 to 1000 mm.
[0019]
The heat-sensitive coloring layer comprises a conventionally known colorless or light leuco dye having a lactone ring, a lactam ring, a spiropyran ring or the like as a coloring main agent, and a coloring assistant that reacts with the leuco dye when heated to develop a color. As a color former, aqueous solution of natural or synthetic polymers such as polyvinyl alcohol, methoxycellulose, methylcellulose, sodium polyacrylate, sodium alginate, starch, casein, vinyl chloride / vinyl acetate copolymer, styrene / butadiene / acrylic latex A coating solution containing a water dispersion as a binder can be formed by a usual coating method such as roll coating or air knife coating. Then, the coating amount is nearest to the desired color density, 0.5 to 10 g / m ^2, preferably from 2-5 g / m ^2.
[0020]
The color erasing layer for erasing the color developing layer composed of the above-mentioned materials includes higher aliphatic alcohols, polyethers, polyethylene glycol derivatives, acetamide, stearylamide, phthalonitrile, etc., which are conventionally used color erasing agents. These nitrogen-containing organic compounds are dissolved or dispersed in the binder used for the color former and applied by the same method. Then, the coating amount varies depending on the coating amount of the heat-sensitive coloring layer, 0.5 to 10 g / m ^2, preferably from 2-5 g / m ^2.
[0021]
The protective layer is provided in order to prevent physical damage such as friction and chemical contamination such as oil from the above-described various coating layers or formed images.
If necessary, a lubricant such as wax or silicone resin or an antistatic agent may be added to a varnish of a thermoplastic resin mainly composed of an acrylic, urethane, polyester, or vinyl chloride / vinyl acetate copolymer.
Also, polyurethane, polyester or polyether resins with functional groups that are cured with polyisocyanates, heat such as amino alkyds, resin-modified drying oils, or oxidation-curing varnishes or ionizing radiation-curing resins are used. To do.
The coating method can be performed by a usual method according to the shape curing method of the base sheet or the resin varnish, and the coating amount is 1 to 10 g / m ² , preferably ² to 5 g / m ² . is there.
Magnetic recording layer is γ-Fe _{20 3} , Co-coated γ-Fe ₂ O ₃ , Fe ₃ O ₄ , CrO ₂ , Fe, Fe-Cr, Fe-Co, Co-Cr, Co-Ni, Mn-Al A dispersion in which conventionally known magnetic fine particles such as Ba ferrite are dispersed in an appropriate ink vehicle can be formed by a conventionally known method such as gravure coating, roll coating, knife coating or the like. Further, it can be formed on a base sheet by a vacuum deposition method, a sputtering method, a plating method, or the like using a metal, an alloy, or an oxide thereof such as Fe—Co, Co—Cr, and Co—Ni.
The thickness of the magnetic recording layer by coating is 1 to 100 μm, preferably 5 to 20 μm. The thickness of the magnetic recording layer by vacuum deposition, sputtering, plating, or the like is 100 to 10,000 mm, preferably 500 to 1,000 mm.
Vehicles for dispersing γ-Fe ₂ O _{3 and the} like are polyvinyl butyral, vinyl chloride / vinyl acetate copolymer, polyurethane, polyester, cellulose derivative, acrylic resin, styrene / maleic acid copolymer, and the like. And rubbers, such as a nitrile rubber and a urethane elastomer, are added as needed. In addition, additives such as surfactants, waxes, silicone oils, and carbon and other pigments can be added to the above-described vehicle in which the magnetic fine particles are dispersed.
[0022]
When forming each of the above layers, it is preferable to provide a primer layer as necessary for the purpose of more firmly and stably bonding the layers.
The primer layer is selected from varnishes such as polyester / isocyanate, polyether / isocyanate, vinyl chloride / vinyl acetate copolymer acrylic resin, etc., which are used as an adhesive, according to the characteristics of each layer.
And the application | coating amount may be the minimum required without an application | coating penetration part, and 0.1-2 g / m < ² > is provided by roll coating or gravure coating.
[0023]
【The invention's effect】
According to the present gun invention, as described above, the colored layer, in the low-energy printing unit by the combined use of decolorizing layer to activate at low energy coloring layer and the high-energy as a "print color layer and the printed color layer an image of mixed color ", and, in high-energy printing unit, there is an effect that an image according to" print color layer "the combined use of decolorizing layer border by other colors may not clearly formed.
In addition, since the thermosensitive coloring layer is provided as a single layer, there is an effect that an image having a clearly separated hue can be formed without causing different colors due to a temperature difference.
[Brief description of the drawings]
FIG. 1 is a schematic view showing a cross section of a layer structure of a multicolor thermosensitive recording medium.
2 is a schematic view showing a cross section of an image formed by printing from the multicolor thermosensitive recording medium of FIG. 1. FIG.
FIG. 3 is a schematic view showing a cross section of a layer structure using a decoloring layer of a multicolor thermosensitive recording medium.
4 is a schematic view showing a cross section of an image formed by printing from the multicolor thermosensitive recording medium of FIG. 3;
FIG. 5 is a schematic view showing a cross section of another layer configuration of a multicolor thermosensitive recording medium.
6 is a schematic view showing a cross section of an image formed by printing from the multicolor thermal recording medium of FIG.
FIG. 7 is a schematic view showing a cross section of a configuration of a multicolor thermal recording medium of an example.
8 is a schematic view showing a cross section of an image formed by printing from the multicolor thermal recording medium of FIG.
FIG. 9 is a schematic view showing a cross section of a configuration of a multicolor thermal recording medium of another embodiment.
10 is a schematic view showing a cross section of an image formed by printing from the multicolor thermal recording medium of FIG.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Substrate sheet 2 Colored layer 21 Picture layer 23 Printed color layer 24 Printed picture layer 26 Magnetic recording layer 27 Printed magnetic recording layer 3 Thermal coloring layer 33 Printing coloring layer 34 Decoloring coloring layer 4 Thermal printing thin film layer 41 Destructive printing thin film layer 5 Protective layer 6 Decoloring layer 61 Active decoloring layer 10 Low energy printing part 20 High energy printing part 16, 17, 18, 19 Primer layer

Claims (4)

A multicolor thermosensitive recording medium in which at least a colored layer, a decoloring layer, a thermosensitive coloring layer, and a thermosensitive printing thin film layer are sequentially laminated on one surface of a base sheet,
The thermal printing thin film layer is made of a metal or a compound having a low melting point, and is destroyed by the printing energy of the printing head to be transparent.
The thermosensitive coloring layer comprises a coloring aid that reacts with the leuco dye when heated using a leuco dye as a color developing agent, and develops color by the printing energy of the print head,
The decoloring layer is composed of a higher aliphatic alcohol, a polyether, a polyethylene glycol derivative, or a nitrogen-containing organic compound such as acetamide, stearylamide, phthalonitrile, etc., and the thermosensitive coloring with higher energy than the printing energy that the thermosensitive coloring layer develops. A multicolor thermal recording medium, wherein the layer is decolorized and transparent . Claim 1 Symbol placement of multicolor heat-sensitive recording medium, characterized in that a magnetic recording layer between the substrate sheet and the colored layer. Claim 2 Symbol placement of multicolor heat-sensitive recording medium the magnetic recording layer is equal to or serving as a colored layer. 3. The multicolor thermal recording medium according to claim 1, wherein a pattern layer is provided in place of the colored layer .

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