JPH0577548A - Reversible thermal recording medium - Google Patents
Reversible thermal recording mediumInfo
- Publication number
- JPH0577548A JPH0577548A JP3241016A JP24101691A JPH0577548A JP H0577548 A JPH0577548 A JP H0577548A JP 3241016 A JP3241016 A JP 3241016A JP 24101691 A JP24101691 A JP 24101691A JP H0577548 A JPH0577548 A JP H0577548A
- Authority
- JP
- Japan
- Prior art keywords
- recording
- recording layer
- particles
- transparent
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、加熱により可逆的に記
録、消去が可能な可逆感熱記録媒体に関するものであ
る。本発明は、定期券、切符、回数券などプリペイドカ
ードとして用いられる書換え可能な表示機能付きメモリ
ーカードや，ＩＣカード、ファクシミリ用記録紙および
光ディスクなどに利用されるとき最もその特徴を発揮す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reversible thermosensitive recording medium capable of reversibly recording and erasing by heating. INDUSTRIAL APPLICABILITY The present invention is most effective when used for a rewritable memory card with a display function used as a prepaid card such as a commuter pass, a ticket, and a coupon ticket, an IC card, a recording paper for facsimile, and an optical disk.
【０００２】[0002]
【従来の技術】従来の可逆感熱記録材料には、ロイコ染
料と顕色剤および消色剤との組合せにより可逆的に発色
・消色させる感熱染料系の記録材料と、マトリクスポリ
マ中の有機結晶粒子の融解・凝固挙動を利用して、その
凝固条件によって粒子の透明性の変化を利用する相変化
形の可逆感熱記録材料、および液晶ポリマ(おもにコレ
ステリック液晶)によりその分子配列の熱的挙動を利用
して透明性を変える方法等がある。2. Description of the Related Art Conventional reversible thermosensitive recording materials include thermosensitive dye recording materials that reversibly develop and decolor by a combination of a leuco dye and a color developer and a decolorizer, and organic crystals in a matrix polymer. Phase change type reversible thermosensitive recording material that utilizes the change of particle transparency depending on the coagulation conditions, and the thermal behavior of its molecular arrangement by using liquid crystal polymer (mainly cholesteric liquid crystal) There is a method to change transparency by using it.
【０００３】本発明は、マトリクスポリマ中の有機結晶
粒子の融解・凝固挙動を利用して、その凝固条件によっ
て粒子の透明性が変化することを利用する相変化形感熱
記録材料に関するもので、熱によって微粒子を融解させ
再び固化しその条件によって凝固形態（多結晶状態、単
結晶状態、無定形状態など）の透明性に違いを生じさせ
記録する。この感熱記録材料は特開昭５４−１１９３７
７に開示されているように、マトリクスポリマと次のよ
うな溶融性有機分子との組合せにより構成され、きわめ
て多様な記録材料を構成できる。ここに開示された溶融
性有機分子としては、脂肪族、芳香族のアルコール、カ
ルボン酸、アミン、アミドおよび、これらのハロゲン化
物、硫化物などがある。また一方、マトリクスポリマと
しては、ポリエステル、ポリアミド、ポリアクリル酸、
スチロール、シリコーン、ポリ塩化ビニル、ポリ塩化ビ
ニリデン、ポリアクリロニトリル等の一般的なポリマが
開示されている。また、これを改良してカーボンブラッ
クや酸化防止剤をさらに加えた記録材料が、特開昭５７
−８２０８７や特開昭５７−８２０８８に開示されてい
る。The present invention relates to a phase-change type heat-sensitive recording material which utilizes the melting and solidification behavior of organic crystal particles in a matrix polymer and changes in the transparency of the particles depending on the solidification conditions. Fine particles are melted and solidified again by the condition, and the transparency of the solidified morphology (polycrystalline state, single crystalline state, amorphous state, etc.) is changed depending on the condition, and recorded. This heat-sensitive recording material is disclosed in JP-A-54-11937.
As disclosed in No. 7, it is constituted by a combination of a matrix polymer and the following fusible organic molecules, so that a great variety of recording materials can be constituted. The fusible organic molecules disclosed herein include aliphatic and aromatic alcohols, carboxylic acids, amines, amides and their halides, sulfides, and the like. On the other hand, as the matrix polymer, polyester, polyamide, polyacrylic acid,
Common polymers such as styrene, silicone, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile are disclosed. Further, a recording material obtained by improving this and further adding carbon black and an antioxidant is disclosed in JP-A-57 / 57.
-82087 and JP-A-57-82088.
【０００４】[0004]
【発明が解決しようとする課題】しかし、このマトリク
スポリマ中の有機結晶粒子の融解・凝固挙動を利用し
て、透明性を変化させることを利用する相変化形感熱記
録材料においては、記録・消去時に有機結晶粒子を繰り
返し融解・凝固させるため、感熱記録ヘッドの圧力によ
って融解時に記録層の変形が生じ、耐久性が向上しない
という大きな課題があった。これはこの記録の原理上避
けられない大きな問題点であった。However, in the phase-change type heat-sensitive recording material which utilizes the melting and solidification behavior of the organic crystal particles in the matrix polymer to change the transparency, recording and erasing are performed. Since the organic crystal particles are repeatedly melted and solidified at times, the pressure of the thermal recording head causes deformation of the recording layer at the time of melting, which poses a serious problem that durability is not improved. This is a big problem that cannot be avoided on the principle of this recording.
【０００５】そこで、本発明は新規な構成の記録材料を
用いることによって、耐久性に優れる新規な可逆感熱媒
体を提供することを目的としている。Therefore, an object of the present invention is to provide a novel reversible thermosensitive medium having excellent durability by using a recording material having a novel constitution.
【０００６】[0006]
【課題を解決するための手段】本発明の可逆感熱記録媒
体は、基板上に結晶性有機分子、透明マトリクスポリマ
および透明粒子を含む記録層を形成し、透明粒子が記録
層の厚さに近い大きさを有する高強度粒子で、記録層中
に１０％以下含有した可逆感熱記録媒体で、上記課題を
解決した。In the reversible thermosensitive recording medium of the present invention, a recording layer containing crystalline organic molecules, a transparent matrix polymer and transparent particles is formed on a substrate, and the transparent particles are close to the thickness of the recording layer. The above problems were solved by a reversible thermosensitive recording medium containing high strength particles having a size of 10% or less in the recording layer.
【０００７】[0007]
【作用】本発明の可逆感熱記録媒体は、記録層中に前記
記録層の厚みに近いサイズの高強度の透明粒子を１０％
以下含んでなることを特徴とするもので、この透明粒子
は硬質球状粒子よりおもに構成される。そのため、マト
リクスポリマ中の有機結晶粒子の融解・凝固挙動を利用
して、透明性を変化させる熱変形しやすい記録材料であ
っても、本発明の粒子が記録層の柱の役目を果たし感熱
記録ヘッドの圧力に抗する。よって記録融解時にも記録
層の変形が生ぜず、耐久性が大きく向上する。本発明は
このように、記録の原理上避けられない、記録層の溶融
による変形という大きな問題点を簡単な方法で解決する
ものである。The reversible thermosensitive recording medium of the present invention contains 10% of high-strength transparent particles having a size close to the thickness of the recording layer in the recording layer.
The transparent particles are mainly composed of hard spherical particles. Therefore, the particles of the present invention function as pillars of the recording layer even if the recording material is susceptible to thermal deformation that changes transparency by utilizing the melting / solidifying behavior of organic crystal particles in the matrix polymer. Withstands head pressure. Therefore, the recording layer is not deformed even when the recording is melted, and the durability is greatly improved. The present invention thus solves a major problem of deformation due to melting of the recording layer, which is unavoidable in principle of recording, by a simple method.
【０００８】[0008]
【実施例】本発明の代表的な実施例を図１に示す。図１
は、アルミ蒸着反射層２を形成した高分子シート基板１
上に、本発明の記録層３を形成している。その記録層３
の上にさらに表面コート層５が形成されている。記録層
３には、記録層の厚みにほぼ近いサイズの硬質の透明粒
子４が含まれている。記録層３の中の有機結晶粒子の部
分を拡大して示すと、図２のようにマトリクスポリマ中
に有機結晶粒子６が分散されており、加熱・放冷過程に
よってマトリクスポリマ中の有機結晶粒子６は透明な単
結晶粒子６Ａ状態と不透明な多結晶粒子６Ｂ状態（光散
乱状態）の二状態をとる。これがそれぞれ消去・記録に
相当する。EXAMPLE A typical example of the present invention is shown in FIG. Figure 1
Is a polymer sheet substrate 1 on which an aluminum vapor deposition reflective layer 2 is formed.
The recording layer 3 of the present invention is formed thereon. The recording layer 3
A surface coat layer 5 is further formed on the above. The recording layer 3 contains hard transparent particles 4 having a size substantially close to the thickness of the recording layer. When the organic crystal particles in the recording layer 3 are enlarged and shown, the organic crystal particles 6 are dispersed in the matrix polymer as shown in FIG. 2, and the organic crystal particles in the matrix polymer are heated and cooled. 6 has two states, a transparent single crystal particle 6A state and an opaque polycrystalline particle 6B state (light scattering state). This corresponds to erasing / recording.
【０００９】本発明の記録層は、記録層の厚みに近いサ
イズの高強度の透明粒子を記録層中に１０％以下含む構
成を特徴としている。１０％以上の粒子は熱変形の防止
には必要でない。粒径および添加量は、記録・表示の画
質に影響を与えない工夫が必要である。この透明粒子
は、強度の点でガラスあるいは高分子製で、大きさとし
ては記録層の厚さで変わるが一般には平均粒径１〜１０
０μｍの範囲が好ましく、粒度分布が狭い方が望まし
い。また、粒子の大きさと記録層の厚みとの関係は、同
一が望ましいが、粒子の平均の大きさが記録層の±２０
％以内であれば本発明の効果が充分に現れ、±１０％以
内が好ましい。したがって、上記範囲内に粒度分布が入
る粒子を用いることが望ましい。高分子粒子としては、
メラミン樹脂、アクリル樹脂、ナイロン樹脂、ポリカー
ボネートなど多くのものが使用できる。本発明の透明粒
子形状としては、作製の面から球形粒子が好ましいが、
本発明の根本思想は記録層に近い大きさを有する高硬度
の粒子であるため球形粒子に限定されるものではない。The recording layer of the present invention is characterized in that the recording layer contains 10% or less of high-strength transparent particles having a size close to the thickness of the recording layer. 10% or more of particles are not necessary to prevent thermal deformation. It is necessary to devise the particle size and the addition amount so as not to affect the image quality of recording and display. The transparent particles are made of glass or a polymer in terms of strength, and the size varies depending on the thickness of the recording layer, but generally the average particle size is 1 to 10
A range of 0 μm is preferable, and a narrow particle size distribution is desirable. The relationship between the size of the particles and the thickness of the recording layer is preferably the same, but the average size of the particles is ± 20 of the recording layer.
If it is within%, the effect of the present invention is sufficiently exhibited, and it is preferably within ± 10%. Therefore, it is desirable to use particles having a particle size distribution within the above range. As polymer particles,
Many materials such as melamine resin, acrylic resin, nylon resin and polycarbonate can be used. The shape of the transparent particles of the present invention is preferably spherical particles from the viewpoint of production,
The basic idea of the present invention is not limited to spherical particles because it is a high hardness particle having a size close to that of the recording layer.
【００１０】本発明における有機結晶粒子とマトリクス
ポリマには、従来例にあるようないずれの材料でも良い
が、特に水素結合性基を有する分子より構成するのが、
結晶性の面から望ましい。有機結晶粒子としては、水素
結合性基としてカルボキシル基、ヒドロキシキシル基の
うちの少なくとも一つをもつ６０〜１２０℃に融点を有
する分子が適す。これらの分子を、さらに別個の高級ア
ルコール、脂肪酸、アルキルアミン、オキシカルボン
酸、ジカルボン酸、ジアミン、アルキレングリコール、
などと共晶あるいは錯体を形成させて、６０〜１２０℃
に融点を有する有機分子結晶粒子を構成させることもで
きる。The organic crystal particles and the matrix polymer in the present invention may be any materials as in the prior art, but in particular, they are composed of molecules having a hydrogen-bonding group.
It is desirable in terms of crystallinity. As the organic crystal particles, molecules having a melting point of 60 to 120 ° C. having at least one of a carboxyl group and a hydroxyxyl group as a hydrogen bonding group are suitable. These molecules are further separated into higher alcohols, fatty acids, alkylamines, oxycarboxylic acids, dicarboxylic acids, diamines, alkylene glycols,
60-120 ° C by forming a eutectic or complex with
It is also possible to form organic molecular crystal particles having a melting point at.
【００１１】一方、一般にマトリクスポリマには、ポリ
エステル、ポリアクリル酸エステル、ポリ塩化ビニル、
塩化ビニル・酢酸ビニル共重合体、酢酸セルロース、ポ
リビニルブチラール、ポリスチレン、スチレン・ブタジ
エン共重合体などがあるが、本発明では、水素結合基含
有透明マトリクスポリマを用いると、より結晶形態変化
に伴う白濁・透明の変化が大きく、コントラストを得易
いため好ましい。具体的な例として、接着性(ＯＨ基含
有)ポリエステル、部分ケン化酢酸ビニル・塩化ビニル
共重合体、ポリアミド、ポリウレタン、熱可塑性フェノ
ール樹脂、ビニルアルコール共重合体、アクリル酸共重
合体、アクリルアミド共重合体、マレイン酸共重合体等
が適している。本発明の記録材料は薄膜であるため、か
なりの透明度が得られる。また、これに可塑剤を適時併
用することも当然である。On the other hand, matrix polymers generally include polyester, polyacrylic acid ester, polyvinyl chloride,
Although there are vinyl chloride / vinyl acetate copolymer, cellulose acetate, polyvinyl butyral, polystyrene, styrene / butadiene copolymer, etc., in the present invention, when a hydrogen bond group-containing transparent matrix polymer is used, it becomes more cloudy due to a change in crystal morphology. -Transparent change is large and contrast is easily obtained, which is preferable. Specific examples include adhesive (OH group-containing) polyester, partially saponified vinyl acetate / vinyl chloride copolymer, polyamide, polyurethane, thermoplastic phenolic resin, vinyl alcohol copolymer, acrylic acid copolymer, acrylamide copolymer. Polymers, maleic acid copolymers and the like are suitable. Since the recording material of the present invention is a thin film, considerable transparency can be obtained. In addition, it is natural to use a plasticizer in combination with this at appropriate times.
【００１２】なお、記録層を構成する有機結晶粒子のマ
トリクスポリマに対する添加量は、５〜５０％の範囲で
加えることができるが、１５〜４０％の添加が望まし
い。有機結晶粒子の比率がこれ以上になると結着力が弱
まり記録層として均質なコーティングも困難になる。逆
に、マトリクスポリマの比率が高くなると、有機結晶性
粒子の量が少なくなるため不透明化が困難になり、記録
のコントラストが悪くなる。The organic crystal particles constituting the recording layer may be added in an amount of 5 to 50% with respect to the matrix polymer, preferably 15 to 40%. When the ratio of the organic crystal particles is higher than this, the binding force is weakened and it becomes difficult to uniformly coat the recording layer. On the other hand, when the ratio of the matrix polymer is high, the amount of organic crystalline particles is small, which makes opacity difficult and deteriorates the contrast of recording.
【００１３】本発明の記録層に、水素結合性表面を有す
る結晶核剤を含有させることは、結晶化特性の信頼性を
向上させる上で大変有効である。また、活性水素を有す
る酸化防止剤を含むことも同様に有効である。したがっ
て、透明粒子が水素結合性基を少なくとも表面に有する
と、結晶性有機分子の結晶化特性を向上できるため好ま
しい。The inclusion of a crystal nucleating agent having a hydrogen-bonding surface in the recording layer of the present invention is very effective in improving the reliability of crystallization characteristics. Further, it is similarly effective to include an antioxidant having active hydrogen. Therefore, it is preferable that the transparent particles have a hydrogen-bonding group on at least the surface because the crystallization characteristics of the crystalline organic molecule can be improved.
【００１４】本発明の可逆感熱記録媒体は、感熱ヘッド
のみならず熱ローラ等の直接加熱する手段を用いて記録
・消去する方法に供される。The reversible thermosensitive recording medium of the present invention is subjected to a recording / erasing method using not only a thermal head but also a direct heating means such as a heat roller.
【００１５】また、本発明の可逆感熱記録媒体はこのよ
うに直接記録媒体を加熱することによって記録・消去を
行うため、耐摩耗性の表面コート層が耐久性を大きく向
上させる。優れた耐摩耗性の表面コート層を有し、且つ
記録層の熱変形を回避する本発明の可逆感熱記録媒体の
構成では、加熱手段の接触に対しても経時劣化が小さく
繰り返し耐久性の高い記録媒体を構成することができ
る。Since the reversible thermosensitive recording medium of the present invention records and erases by directly heating the recording medium as described above, the abrasion-resistant surface coating layer greatly improves durability. In the constitution of the reversible thermosensitive recording medium of the present invention which has the surface coat layer having excellent abrasion resistance and avoids the thermal deformation of the recording layer, the deterioration with time is small even when contacted by the heating means and the repeated durability is high. A recording medium can be configured.
【００１６】本発明の可逆感熱記録媒体は、図３に示す
ような磁気記録部８を有する表示機能付きメモリーカー
ドとして構成され、キャシュレス用途に広く利用され
る。ＩＣカードとしての応用も大きく期待できる。The reversible thermosensitive recording medium of the present invention is constructed as a memory card with a display function having a magnetic recording section 8 as shown in FIG. 3, and is widely used for cashless applications. The application as an IC card can be expected greatly.
【００１７】次に、実施例を用いて本発明を説明する。 （実施例１）記録材料として、ヒドロキシステアリン酸
２ｇと、フェノール系酸化防止剤０．１ｇと、部分ケン
化し水酸基をもつ塩化ビニル・酢酸ビニル共重合体８ｇ
とを、テトラヒドロフラン１００ｍｌに溶解し、さらに
透明粒子４として平均粒径１５μｍのガラスビーズ０．
８ｇを分散し、図１に示すアルミ蒸着層２を形成した
０．２ｍｍのポリエステル高分子シート基板１上に、記
録層３として１３μｍの厚さで形成した。その記録層３
の上にさらに耐摩耗性の表面コート層５として、紫外線
硬化形アクリル樹脂のプレポリマを２０μｍコーティン
グ後、紫外線照射して硬化させた。こうしてできた可逆
感熱記録シートに感熱ヘッドによって、書き込み・消去
をおこなった。このシートの透明化温度領域は約７０〜
９０℃であった。この条件から感熱ヘッドによってエネ
ルギーを与え１００℃で書き込み８０℃で消去した。書
き込まれた不透明化域と消去された透明化域をそれぞれ
Ｘ線回折により解析したところ、いずれにも回折ピーク
が観測され微結晶であることがわかった。これらは図２
に示したように、それぞれ有機結晶粒子６の不透明な多
結晶粒子６Ｂ状態（光散乱状態）と、透明な単結晶粒子
６Ａ状態とに相当していることがわかった。また、ガラ
スビーズによる記録画質の低下は目視では観察されなか
った。耐久試験を行なったところ、１２００回の繰り返
しが可能となり、ガラスビーズを加えなかったときの約
７倍の高寿命が得られた。Next, the present invention will be described with reference to examples. (Example 1) As a recording material, 2 g of hydroxystearic acid, 0.1 g of a phenolic antioxidant, and 8 g of a vinyl chloride / vinyl acetate copolymer partially saponified and having a hydroxyl group.
Are dissolved in 100 ml of tetrahydrofuran, and further, as transparent particles 4, glass beads having an average particle diameter of 15 μm are added.
8 g was dispersed and formed as a recording layer 3 with a thickness of 13 μm on the 0.2 mm polyester polymer sheet substrate 1 on which the aluminum vapor deposition layer 2 shown in FIG. 1 was formed. The recording layer 3
Further, as a wear-resistant surface coating layer 5, a prepolymer of an ultraviolet curable acrylic resin was coated to 20 μm and then irradiated with ultraviolet rays to be cured. Writing and erasing were performed on the reversible thermosensitive recording sheet thus formed by a thermosensitive head. The transparency temperature range of this sheet is about 70-
It was 90 ° C. Under this condition, energy was applied by a thermal head to write at 100 ° C. and erase at 80 ° C. When the written opaque region and the erased transparent region were analyzed by X-ray diffraction, diffraction peaks were observed in both and it was found that they were fine crystals. These are shown in Figure 2.
As shown in, it was found that the organic crystal particles 6 corresponded to the opaque polycrystalline particle 6B state (light scattering state) and the transparent single crystal particle 6A state, respectively. Further, the deterioration of the recording image quality due to the glass beads was not visually observed. When a durability test was performed, it was possible to repeat 1200 times, and a long life of about 7 times that obtained when glass beads were not added was obtained.
【００１８】（実施例２）記録材料として、ベヘン酸２
ｇと、フェノール系酸化防止剤０．１ｇと、接着性ポリ
エステル（東洋紡(株)バイロン）２ｇと、ポリウレタン
５ｇとを、テトラヒドロフラン１００ｍｌに溶解し、さ
らに透明粒子４として平均粒径２０μｍのメラミン樹脂
製球形粒子を０．３ｇ分散し、図１に示すアルミ蒸着層
２を形成した０．２ｍｍのポリエステル高分子シート基
板１上に、記録層３として２０μｍの厚さで形成した。
その記録層３の上にさらに耐摩耗性の表面コート層５と
して紫外線硬化形アクリル樹脂のプレポリマを２５μｍ
コーティング後、紫外線照射して硬化させた。こうして
できた可逆感熱記録シートに感熱ヘッドによって、書き
込み・消去をおこなった。このシートの透明化温度領域
は約９０〜１１０℃であった。この条件から感熱ヘッド
によってエネルギーを与え１２０℃で書き込み１００℃
で消去したところ、鮮明な記録特性が得られた。さらに
繰り返して寿命特性を測定したところ１８６０回の繰り
返しに耐えた。Example 2 Behenic acid 2 was used as a recording material.
g, 0.1 g of a phenolic antioxidant, 2 g of adhesive polyester (Toyobo Co., Ltd. Byron), and 5 g of polyurethane were dissolved in 100 ml of tetrahydrofuran, and the transparent particles 4 were made of a melamine resin having an average particle size of 20 μm. 0.3 g of spherical particles were dispersed to form a recording layer 3 with a thickness of 20 μm on a 0.2 mm polyester polymer sheet substrate 1 on which the aluminum vapor deposition layer 2 shown in FIG. 1 was formed.
On the recording layer 3, as a wear-resistant surface coating layer 5, a prepolymer of an ultraviolet curable acrylic resin is 25 μm.
After coating, it was irradiated with ultraviolet rays and cured. Writing and erasing were performed on the reversible thermosensitive recording sheet thus formed by a thermosensitive head. The clearing temperature range of this sheet was about 90 to 110 ° C. Under this condition, energy is applied by the thermal head to write at 120 ° C and write at 100 ° C.
When erased with, clear recording characteristics were obtained. When the life characteristics were measured again and again, it could withstand 1860 repetitions.
【００１９】（実施例３）記録材料として、ステアリル
アルコール２ｇと、ヒンダードフェノール系酸化防止剤
０．１ｇと、塩化ビニル・酢酸ビニル・アクリルアミド
共重合体８ｇとを、テトラヒドロフラン１００ｍｌに溶
解し、さらに透明粒子として平均粒径２０μｍのメラミ
ン樹脂性球形粒子を０．３ｇ分散し、（図３）に示した
ように表面を金色に着色し反射層を形成した０．２ｍｍ
の硬質ポリ塩化ビニルの１ｍｍ厚の高分子シート１上
に、記録層３として２５μｍの厚さで形成した。その記
録層の上にさらに耐摩耗性の表面コート層４として紫外
線硬化形アクリル樹脂のプレポリマを２０μｍコーティ
ング後、紫外線照射して硬化させた。こうしてできた可
逆感熱記録シートに感熱ヘッドによって、書き込み・消
去をおこなった。このシートの透明化温度領域は約７０
〜９０℃であった。この条件から感熱ヘッドによってエ
ネルギーを与え１００℃で書き込み８０℃で消去した。(Example 3) As a recording material, 2 g of stearyl alcohol, 0.1 g of a hindered phenolic antioxidant, and 8 g of vinyl chloride / vinyl acetate / acrylamide copolymer were dissolved in 100 ml of tetrahydrofuran. 0.3 g of melamine resinous spherical particles having an average particle size of 20 μm were dispersed as transparent particles, and the surface was colored gold as shown in FIG. 3 to form a reflective layer 0.2 mm
A recording layer 3 having a thickness of 25 μm was formed on a 1 mm thick polymer sheet 1 of rigid polyvinyl chloride. On the recording layer, a prepolymer of an ultraviolet-curable acrylic resin was further coated as a wear-resistant surface coating layer 4 to a thickness of 20 μm, and then the coating was irradiated with ultraviolet rays to be cured. Writing and erasing were performed on the reversible thermosensitive recording sheet thus formed by a thermosensitive head. The transparency temperature range of this sheet is about 70
Was ~ 90 ° C. Under this condition, energy was applied by a thermal head to write at 100 ° C. and erase at 80 ° C.
【００２０】この記録シートを切断し可逆感熱記録部７
とし、更に磁気記録層８を形成し、図４のような表示機
能付き記録カードとした。この表示機能付き記録カード
の可逆感熱記録部７も、感熱ヘッドで記録・消去が可能
であり、磁気記録層８と共に書換え可能メモリーカード
の機能を示した。The recording sheet is cut and the reversible thermosensitive recording section 7 is cut.
Further, the magnetic recording layer 8 was further formed to obtain a recording card with a display function as shown in FIG. The reversible thermosensitive recording unit 7 of the recording card with a display function can also be recorded / erased by the thermal head, and the function of a rewritable memory card is shown together with the magnetic recording layer 8.
【００２１】[0021]
【発明の効果】以上のように本発明は、有機結晶粒子が
マトリクスポリマ中に分散された高分子組成物よりなる
記録層を有する可逆感熱記録媒体において、記録層の厚
みに近いサイズの高強度の透明粒子を記録層中に１０％
以下含ませて構成した可逆感熱記録媒体であるため、感
熱記録ヘッドでの書き込み・消去に対して非常に耐久性
の優れる可逆感熱記録媒体を提供できる効果があり、工
業的価値の大なるものである。INDUSTRIAL APPLICABILITY As described above, the present invention provides a reversible thermosensitive recording medium having a recording layer composed of a polymer composition in which organic crystal particles are dispersed in a matrix polymer, and has a high strength of a size close to the thickness of the recording layer. 10% of transparent particles in the recording layer
Since it is a reversible thermosensitive recording medium configured by including the following, it has the effect of providing a reversible thermosensitive recording medium having extremely excellent durability against writing and erasing with a thermosensitive recording head, and is of great industrial value. is there.
【図１】本発明の可逆感熱記録媒体の一実施例を示す概
念断面図FIG. 1 is a conceptual sectional view showing an embodiment of a reversible thermosensitive recording medium of the present invention.
【図２】本発明の可逆感熱記録媒体の記録層中の有機結
晶粒子の二状態を示す概念断面図 （ａ）は有機結晶粒子が透明状態 （ｂ）は有機結晶粒子が不透明状態FIG. 2 is a conceptual cross-sectional view showing two states of organic crystal particles in the recording layer of the reversible thermosensitive recording medium of the present invention. (A) shows the organic crystal particles in a transparent state (b) shows the organic crystal particles in an opaque state
【図３】本発明の可逆感熱記録媒体の別の実施例を示す
概念断面図FIG. 3 is a conceptual sectional view showing another embodiment of the reversible thermosensitive recording medium of the present invention.
【図４】本発明の可逆感熱記録媒体の一実施例である表
示機能付き磁気カードを示す概念断面図FIG. 4 is a conceptual cross-sectional view showing a magnetic card with a display function, which is an embodiment of the reversible thermosensitive recording medium of the present invention.
１ 高分子シート基板 ２ 反射層 ３ 記録層 ４ 透明粒子 ５ 表面コート層 ６ 有機結晶粒子 ６Ａ 透明な単結晶粒子 ６Ｂ 不透明な多結晶粒子 ７ 可逆感熱記録部 ８ 磁気記録部 1 Polymer Sheet Substrate 2 Reflective Layer 3 Recording Layer 4 Transparent Particles 5 Surface Coat Layer 6 Organic Crystal Particles 6A Transparent Single Crystal Particles 6B Opaque Polycrystalline Particles 7 Reversible Thermosensitive Recording Section 8 Magnetic Recording Section
Claims (4)
ポリマおよび透明粒子を含む記録層を形成し、前記透明
粒子が前記記録層の厚さに近い大きさを有する高強度粒
子で、前記記録層中に前記透明粒子を１０％以下含有し
たことを特徴とする可逆感熱記録媒体。1. A recording layer comprising crystalline organic molecules, a transparent matrix polymer and transparent particles is formed on a substrate, and the transparent particles are high-strength particles having a size close to the thickness of the recording layer. A reversible thermosensitive recording medium, characterized in that the layer contains 10% or less of the transparent particles.
る平均粒径１〜１００μｍで粒度分布の球状粒子よりな
ることを特徴とする、請求項１に記載の可逆感熱記録媒
体。2. The reversible thermosensitive recording medium according to claim 1, wherein the transparent particles are spherical particles made of glass or polymer and having an average particle size of 1 to 100 μm and a particle size distribution.
明粒子が水素結合性基を少なくとも表面に有することを
特徴とする、請求項１に記載の可逆感熱記録媒体。3. The reversible thermosensitive recording medium according to claim 1, wherein the crystalline organic molecule has a hydrogen-bonding group, and the transparent particles have a hydrogen-bonding group on at least the surface thereof.
ことを特徴とする、請求項１に記載の可逆感熱記録媒
体。4. The reversible thermosensitive recording medium according to claim 1, wherein a light reflecting film is formed between the substrate and the recording layer.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3241016A JP2701613B2 (en) | 1991-09-20 | 1991-09-20 | Reversible thermosensitive recording medium |
| DE1992629292 DE69229292T2 (en) | 1991-03-28 | 1992-03-27 | Reversible, heat-sensitive recording material and a recording material using this material |
| EP19920105309 EP0506085B1 (en) | 1991-03-28 | 1992-03-27 | A reversible thermosensitive recording material and a recording medium using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3241016A JP2701613B2 (en) | 1991-09-20 | 1991-09-20 | Reversible thermosensitive recording medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0577548A true JPH0577548A (en) | 1993-03-30 |
| JP2701613B2 JP2701613B2 (en) | 1998-01-21 |
Family
ID=17068084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3241016A Expired - Fee Related JP2701613B2 (en) | 1991-03-28 | 1991-09-20 | Reversible thermosensitive recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2701613B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07276813A (en) * | 1994-04-05 | 1995-10-24 | Kyodo Printing Co Ltd | Production of reversible thermal recording medium |
| JP2003136846A (en) * | 2001-11-06 | 2003-05-14 | Mitsubishi Plastics Ind Ltd | Optical recording medium |
| KR100556226B1 (en) * | 2004-12-15 | 2006-03-03 | 주식회사 케이엠티 | Infrared detector |
-
1991
- 1991-09-20 JP JP3241016A patent/JP2701613B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07276813A (en) * | 1994-04-05 | 1995-10-24 | Kyodo Printing Co Ltd | Production of reversible thermal recording medium |
| JP2003136846A (en) * | 2001-11-06 | 2003-05-14 | Mitsubishi Plastics Ind Ltd | Optical recording medium |
| KR100556226B1 (en) * | 2004-12-15 | 2006-03-03 | 주식회사 케이엠티 | Infrared detector |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2701613B2 (en) | 1998-01-21 |
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