JP3412122B2 - Initialized reversible thermosensitive recording medium and initialization method - Google Patents
Initialized reversible thermosensitive recording medium and initialization methodInfo
- Publication number
- JP3412122B2 JP3412122B2 JP18930594A JP18930594A JP3412122B2 JP 3412122 B2 JP3412122 B2 JP 3412122B2 JP 18930594 A JP18930594 A JP 18930594A JP 18930594 A JP18930594 A JP 18930594A JP 3412122 B2 JP3412122 B2 JP 3412122B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- thermosensitive recording
- reversible thermosensitive
- recording medium
- upper limit
- 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.)
- Expired - Fee Related
Links
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、温度の変化により透明
度を変化させることで所望の文字、数字、記号、パター
ン等を可逆的に書き込む（以下「印字」と記す）ことが
可能な可逆性感熱記録媒体に対して、その印字性能を向
上させるために初期化を行う方法に関する。また本発明
は、この方法で初期化された可逆性感熱記録媒体に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reversible feeling in which desired characters, numbers, symbols, patterns and the like can be reversibly written (hereinafter referred to as "printing") by changing the transparency by changing the temperature. The present invention relates to a method of initializing a thermal recording medium in order to improve its printing performance. The present invention also relates to a reversible thermosensitive recording medium initialized by this method.
【０００２】[0002]
【従来の技術】可逆性感熱記録媒体において、可逆性感
熱記録塗料を用いて形成された可逆性感熱記録層は、外
部から熱を加えられたときに、その温度に応じて、透明
な状態から白濁状態までの範囲でその光透過性を変え、
冷却後にはその状態を保持する性質をもつので、文字等
を書換え可能に書き込むことができ、通常は透明状態の
背景に白濁させた文字等を書き込んでいる。このような
可逆性感熱記録材料として、たとえば特開昭６３−３９
３７８号、特開昭６３−１３０３８０号、特開平２−１
３６３号公報等に記載されたものが知られている。2. Description of the Related Art In a reversible thermosensitive recording medium, a reversible thermosensitive recording layer formed by using a reversible thermosensitive recording coating material is transparent from a transparent state depending on the temperature when external heat is applied. Change its light transmittance in the range up to the cloudy state,
Since it has the property of retaining its state after cooling, it is possible to rewrite the characters and the like, and normally, the opaque characters and the like are written on the transparent background. As such a reversible thermosensitive recording material, for example, JP-A-63-39
378, JP-A-63-130380, JP-A 2-1
Those described in Japanese Patent No. 363, etc. are known.
【０００３】これら公知の可逆性感熱記録塗料は、基本
的には、
(1) 樹脂母材
(2) 高級脂肪酸
(3) 有機溶媒
の３成分からなっている。樹脂母材としては、一般に塩
化ビニル・酢酸ビニル共重合体が使用されている。また
高級脂肪酸としては、炭素数１６〜２４程度の脂肪酸、
たとえばステアリン酸あるいはベヘン酸が多く用いられ
ている。有機溶媒は、樹脂母材、高級脂肪酸を溶解し得
るもので、一般的にはテトラヒドロフラン（ＴＨＦ）が
使用される。These known reversible thermosensitive recording paints basically consist of three components: (1) resin base material (2) higher fatty acid (3) organic solvent. A vinyl chloride / vinyl acetate copolymer is generally used as the resin base material. As the higher fatty acid, a fatty acid having about 16 to 24 carbon atoms,
For example, stearic acid or behenic acid is often used. The organic solvent is capable of dissolving the resin base material and the higher fatty acid, and tetrahydrofuran (THF) is generally used.
【０００４】前述のような可逆性感熱記録媒体は通常、
ＰＥＴのような材料からなる支持体の少なくとも片面
に、磁性粉を含有する磁気記録層、平滑層、光反射層、
可逆性感熱記録層、および保護層をこの順序で順次に積
層した構造を有し、そして通常、所望の視覚的情報を付
与するために、可逆性感熱記録層と保護層との間に印刷
層が設けられることが多い。Reversible thermosensitive recording media such as those mentioned above are usually
A magnetic recording layer containing a magnetic powder, a smoothing layer, a light reflecting layer, on at least one surface of a support made of a material such as PET,
It has a structure in which a reversible thermosensitive recording layer and a protective layer are sequentially laminated in this order, and usually a printing layer is provided between the reversible thermosensitive recording layer and the protective layer in order to impart desired visual information. Are often provided.
【０００５】従来、可逆性感熱記録層の形成は、あらか
じめ基材の上に磁性層、平滑層および光反射層を形成し
た後、光反射層の上に、前述のような組成を有する塗料
を所定の厚さで塗布し、ついで加熱乾燥、放冷すること
により行われている。Conventionally, a reversible thermosensitive recording layer is formed by forming a magnetic layer, a smooth layer and a light reflecting layer on a substrate in advance, and then applying a paint having the above-mentioned composition on the light reflecting layer. It is carried out by applying a predetermined thickness, followed by heating, drying, and cooling.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら前述のよ
うな一般的な方法で製造された可逆性感熱記録媒体は、
製造後、使用中にこの可逆性感熱記録媒体が受けた熱履
歴によって印字特性、とくに印字濃度が大きく変化し、
品質が一定しないという共通の欠点を有している。した
がって新品の可逆性感熱記録媒体でも、印字明瞭度が大
幅に異なり、製品の信頼性を低下させている。However, the reversible thermosensitive recording medium manufactured by the general method as described above is
After manufacturing, the printing characteristics, especially the printing density, change significantly depending on the heat history received by the reversible thermosensitive recording medium during use.
They have the common drawback of inconsistent quality. Therefore, even in the case of a new reversible thermosensitive recording medium, the printing clarity is significantly different, and the reliability of the product is lowered.
【０００７】このような印字特性のバラツキは、繰り返
して印字・消去を受けることにより、本来の印字特性に
収束していくが、その期間がかなり長い上に、印字条件
によって安定化の程度が異なる。Such variations in the printing characteristics converge to the original printing characteristics by being repeatedly printed and erased, but the period is considerably long and the degree of stabilization varies depending on the printing conditions. .
【０００８】本発明の目的は、従来の可逆性感熱記録媒
体の上記のような欠点を解消して、製造直後の段階か
ら、所定の印字特性を安定して示すように、可逆性感熱
記録媒体を初期化する方法を提供することである。An object of the present invention is to eliminate the above-mentioned drawbacks of the conventional reversible thermosensitive recording medium and to stably exhibit predetermined printing characteristics immediately after the production, so that the reversible thermosensitive recording medium can be stably exhibited. Is to provide a way to initialize.
【０００９】本発明の他の目的は、このような方法で初
期化された可逆性感熱記録媒体を提供することである。Another object of the present invention is to provide a reversible thermosensitive recording medium initialized by such a method.
【００１０】[0010]
【課題を解決するための手段】本発明によれば、透明化
下限温度Ｔ3以上、透明化上限温度Ｔ4以下の温度に加熱
した後、室温まで冷却すると透明状態になり、透明化上
限温度Ｔ4以上で白濁下限温度Ｔ5よりも高い温度に加熱
した後、室温まで冷却すると白濁状態になり、これを可
逆的に繰り返す可逆性感熱記録層を基材上に備えた可逆
性感熱記録媒体を、その使用に先立って初期化する方法
であって、前記可逆性感熱記録媒体を、
(a) 白濁下限温度Ｔ5以上、基材の耐熱温度Ｔ6以下の
温度に加熱する第１の工程、
(b) 前記白濁下限温度Ｔ5以上、基材の耐熱温度Ｔ6以
下の温度から前記可逆性感熱記録媒体への可逆的な記録
が可能な周囲の環境温度の上限温度Ｔ1以下の温度に１
０秒以内で急冷する工程、
(c) 透明化下限温度Ｔ3以上、透明化上限温度Ｔ4以下
の温度に再び加熱する工程、および
(d) 前記透明化下限温度Ｔ3以上、透明化上限温度Ｔ4
以下の温度から前記可逆性感熱記録媒体への可逆的な記
録が可能な周囲の環境温度の上限温度Ｔ1以下の温度に
再び１０秒以内で急冷する工程、を備えていることを特
徴とする可逆性感熱記録媒体の初期化方法が提供され
る。According to the present invention, a transparent state is obtained by heating to a temperature not lower than the lower limit transparent temperature T3 and lower than the upper limit transparent temperature T4 and then cooled to room temperature. When heated to a temperature higher than the lower limit temperature T5 of cloudiness and then cooled to room temperature, a cloudy state is formed, and a reversible thermosensitive recording medium provided with a reversible thermosensitive recording layer on a base material is used. A method of initializing the reversible thermosensitive recording medium prior to the step (a), the first step of heating the reversible thermosensitive recording medium to a temperature not lower than the cloudiness lower limit temperature T5 and not higher than the heat resistant temperature T6 of the substrate, and (b) the cloudiness. Minimum temperature T5 or higher, heat resistant temperature of base material T6 or higher
Reversible recording from the lower temperature to the reversible thermosensitive recording medium
1 to the upper limit temperature T1 below the temperature of the environment temperature around capable
Quenching within 0 seconds ; (c) reheating to a temperature below the clarification lower limit temperature T3 and below the clarification upper limit temperature T4; and (d) above the clarification lower limit temperature T3 and above, the clarification upper limit temperature T4.
Reversible recording on the reversible thermosensitive recording medium from the following temperature
There is provided a method for initializing a reversible thermosensitive recording medium, which comprises a step of rapidly cooling the recording medium to a temperature not higher than an upper limit temperature T1 of an ambient temperature capable of recording within 10 seconds .
【００１１】さらに本発明によれば、上記の方法で初期
化された可逆性感熱記録媒体が提供される。Further according to the present invention, there is provided a reversible thermosensitive recording medium initialized by the above method.
【００１２】具体的に説明すると、通常の組成の可逆性
感熱記録層を通常の方法で塗布することによって得られ
た可逆性感熱記録媒体は、図１に示すような温度履歴を
経て処理される。可逆性感熱記録媒体が製造後に常温に
保持されているとすれば、この可逆性感熱記録媒体の温
度は、その可逆性感熱記録層の動作上限温度Ｔ1以下で
ある。動作上限温度Ｔ1とは、可逆性感熱記録媒体への
可逆的な記録が可能な周囲の環境温度の上限温度のこと
で、周囲の環境温度が動作上限温度Ｔ1以上では白濁化
または透明化が不完全になり、可逆的な記録が不可能と
なる。この可逆性感熱記録媒体は、まず白濁下限温度Ｔ
5以上の温度まで加熱される（パスＡ）。このときの加
熱温度の上限は、可逆性感熱記録媒体の層の基材の耐熱
温度によって定まる。基材の耐熱温度とは、基材が常時
使用可能である限界の温度で、たとえば厚さ１８８μｍ
のポリエチレンテレフタレート（ＰＥＴ）では約１５０
℃である。More specifically, a reversible thermosensitive recording medium obtained by applying a reversible thermosensitive recording layer having a usual composition by a usual method is processed through a temperature history as shown in FIG. . If the reversible thermosensitive recording medium is kept at room temperature after being manufactured, the temperature of the reversible thermosensitive recording medium is equal to or lower than the operation upper limit temperature T1 of the reversible thermosensitive recording layer. The operation upper limit temperature T1 is the upper limit temperature of the ambient environmental temperature at which reversible recording on the reversible thermosensitive recording medium is possible. When the ambient environmental temperature is the operation upper limit temperature T1 or higher, clouding or transparency does not occur. It becomes perfect and reversible recording becomes impossible. This reversible thermosensitive recording medium has a cloudiness lower limit temperature T
Heated to a temperature above 5 (pass A). The upper limit of the heating temperature at this time is determined by the heat resistant temperature of the base material of the layer of the reversible thermosensitive recording medium. The heat resistant temperature of the base material is a limit temperature at which the base material can be used at all times, for example, a thickness of 188 μm.
About 150 for polyethylene terephthalate (PET)
℃.
【００１３】つぎに可逆性感熱記録媒体は、動作上限温
度Ｔ1以下の温度まで急冷される（パスＢ）。この急冷
に要する時間ＱＴ1は短いほどよい。ついで可逆性感熱
記録媒体は、透明化下限温度Ｔ3以上、透明化上限温度
Ｔ4以下の温度に再び加熱され（パスＣ）、最後に再び
動作上限温度Ｔ1以下の温度に急冷される（パスＤ）。Next, the reversible thermosensitive recording medium is rapidly cooled to a temperature below the operation upper limit temperature T1 (pass B). The shorter the time QT1 required for this rapid cooling, the better. Then, the reversible thermosensitive recording medium is heated again to a temperature not lower than the lower limit transparent temperature T3 and lower than the upper limit transparent temperature T4 (pass C) and finally cooled again to a temperature lower than the upper limit operating temperature T1 (pass D). .
【００１４】この加熱急冷処理による可逆性感熱記録層
の白濁度の変化過程を図２に示す。FIG. 2 shows the process of changing the white turbidity of the reversible thermosensitive recording layer by this heating and quenching treatment.
【００１５】パスＢおよびパスＤの急冷は、その前に行
われた加熱により与えられた高温での履歴をそのまま残
すために必要なもので、好ましくは、パスＢおよびパス
Ｄの急冷は１０秒以内で行う。もしパスＢ、パスＤの急
冷が、パスＢ’、パスＤ’に示すように緩慢に行われた
場合には、所望の初期化効果が得られない。The quenching of pass B and pass D is necessary to leave the history at the high temperature given by the heating performed before that, and preferably the quenching of pass B and pass D is 10 seconds. Do it within. If the passes B and D are cooled rapidly as shown in passes B ′ and D ′, the desired initialization effect cannot be obtained.
【００１６】以上のような初期化のための熱処理は、ど
のような方法で行ってもよいが、たとえば図３に示す装
置を用いて初期化を行うことができる。図３において、
前記の各層を設けた長尺の可逆性感熱記録媒体は、巻出
しロール１から一定速度で連続的に巻出された後、赤外
線オーブン２内で白濁下限温度Ｔ5以上、耐熱温度Ｔ6以
下の温度に加熱された、ついで水冷ロール３の表面に接
触させることで動作上限温度Ｔ1以下の温度に急冷され
る。ついでこの冷却された媒体は、赤外線オーブン３を
通過する間に透明化下限温度Ｔ3以上、透明化上限温度
Ｔ4以下の温度に再び加熱され、赤外線オーブン３を出
た媒体は、水冷ロール５の表面に接触することで動作上
限温度Ｔ1以下の温度に再び急冷されたのち、最後に巻
取ロール６に巻取られる。The heat treatment for initialization as described above may be performed by any method, but the initialization can be performed using, for example, the apparatus shown in FIG. In FIG.
The long reversible thermosensitive recording medium provided with each of the layers described above is continuously unwound from the unwinding roll 1 at a constant speed and then, in the infrared oven 2, a temperature of lower than the cloudiness lower limit temperature T5 and lower than the heat resistant temperature T6. By being brought into contact with the surface of the water-cooled roll 3 which has been heated to the above temperature, the water-cooled roll 3 is rapidly cooled to a temperature below the operation upper limit temperature T1. Then, the cooled medium is heated again to a temperature of not less than the lower limit of transparency T3 and not more than upper limit of transparency T4 while passing through the infrared oven 3, and the medium exiting the infrared oven 3 is the surface of the water-cooled roll 5. After being rapidly cooled to a temperature equal to or lower than the operation upper limit temperature T1 by contacting with, the film is finally taken up by the take-up roll 6.
【００１７】上記のような温度履歴を強制的に与えるこ
とにより印字特性が安定化する機構は明らかではない
が、以下に推測できる点を述べる。The mechanism by which the printing characteristics are stabilized by forcibly applying the temperature history as described above is not clear, but the following points can be inferred.
【００１８】可逆性感熱記録媒体が受ける加熱として
は、オーブンや熱板などで可逆性感熱記録媒体全体が加
熱される場合と、サーマルヘッドによる印字・消去など
一部分に短時間加熱される場合とがあり、当然前者の方
が可逆性感熱記録媒体が受ける熱エネルギーが大きい。The reversible heat-sensitive recording medium is heated by heating the whole reversible heat-sensitive recording medium with an oven or a heating plate or by heating a part of the reversible heat-sensitive recording medium for a short time such as printing or erasing with a thermal head. Of course, the former has a larger thermal energy that the reversible thermosensitive recording medium receives.
【００１９】そして実際に情報を記録する際には、可逆
性感熱記録媒体の一部分に短時間しか加熱されないた
め、可逆性感熱記録媒体の脂肪族カルボン酸の状態（分
散状態や粒子の大きさなど）は絶えず記録時の加熱の影
響を受けることになるが、最初に可逆性感熱記録媒体全
体を加熱し、急冷することにより、実際の情報の記録時
にこれ以上の熱エネルギーを受けることはほとんどない
ため、そのときの状態を長く保ち、記録時の加熱の影響
を受けにくくなることが推測される。When actually recording information, since a part of the reversible thermosensitive recording medium is heated for a short time, the state of the aliphatic carboxylic acid in the reversible thermosensitive recording medium (dispersion state, particle size, etc.). ) Will be constantly affected by heating during recording, but by heating the entire reversible thermosensitive recording medium first and then quenching it, it is unlikely that it will receive more thermal energy when recording actual information. Therefore, it is presumed that the state at that time is maintained for a long time and is less likely to be affected by heating during recording.
【００２０】したがって本発明のように可逆性感熱記録
媒体を初期化することにより可逆性感熱記録媒体中の脂
肪族カルボン酸の状態が最良の状態で安定化するので、
印字特性が安定し、印字のコントラストが向上するもの
と推測される。Therefore, by initializing the reversible thermosensitive recording medium as in the present invention, the state of the aliphatic carboxylic acid in the reversible thermosensitive recording medium is stabilized in the optimum state,
It is presumed that the printing characteristics are stable and the printing contrast is improved.
【００２１】なお本発明の初期化方法は、可逆性感熱記
録媒体を製造後、その最初の使用に先立って１度行えば
十分な効果が得られるものである。The initializing method of the present invention has sufficient effect if it is carried out once after the reversible thermosensitive recording medium is manufactured and prior to its first use.
【００２２】本発明の初期化方法は、可逆性感熱記録媒
体を最終使用目的に応じた形状、寸法に裁断した後に適
用することもできるが、処理効率の点から、長尺の基材
に所望の各層を形成した状態で、適当な加熱および冷却
手段を用いて適用することが有利である。適当な加熱手
段は赤外線オーブンであり、冷却手段は水冷ロールであ
る。さらに長尺の場合は、テンションをかけられるの
で、カールを防止することができる。The initialization method of the present invention can be applied after cutting the reversible thermosensitive recording medium into a shape and a size according to the end use purpose, but it is desirable for a long substrate from the viewpoint of processing efficiency. It is advantageous to apply each layer by using appropriate heating and cooling means. Suitable heating means are infrared ovens and cooling means are water cooled rolls. Further, in the case of a long length, tension can be applied, so that curling can be prevented.
【００２３】本発明は、通常の材料を使用して通常の方
法で製造された可逆性感熱記録媒体のほとんど全てに適
用することが可能である。たとえば基材は、ポリエチレ
ンテレフタレート（ＰＥＴ）、ポリカーボネート、ポリ
エチレン、ポリプロピレン、ポリ塩化ビニル、ポリホス
ファゲン、ポリウレタン樹脂、ポリアクリル樹脂、エポ
キシ樹脂、ガラス、金属板、紙、合成紙などであっても
よく、また、これらに磁気記録層、光反射層などを形成
したものであってもよい。The present invention can be applied to almost all reversible thermosensitive recording media manufactured by a conventional method using a conventional material. For example, the substrate may be polyethylene terephthalate (PET), polycarbonate, polyethylene, polypropylene, polyvinyl chloride, polyphosphagen, polyurethane resin, polyacrylic resin, epoxy resin, glass, metal plate, paper, synthetic paper, etc. Alternatively, a magnetic recording layer, a light reflecting layer, or the like may be formed on these.
【００２４】また樹脂母材としては、通常の可逆性感熱
記録塗料に使用されている物質、たとえばポリ塩化ビニ
ル、あるいは塩化ビニルと塩化ビニリデン、酢酸ビニ
ル、ビニルアルコール、マレイン酸、アクリル酸エステ
ル、アクリロニトリルまたはポリエステルの１種または
２種以上との共重合体等を使用することができる。As the resin base material, substances used in ordinary reversible heat-sensitive recording paints such as polyvinyl chloride, or vinyl chloride and vinylidene chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic ester, acrylonitrile. Alternatively, a copolymer with one or more polyesters and the like can be used.
【００２５】透明化温度域の拡大のために、樹脂母材よ
りも低い、好ましくは５０℃以下のガラス転移温度をも
つ有機高分子樹脂（以下「低Ｔｇ樹脂」という）、たと
えばアクリル系樹脂、ポリエステル樹脂、あるいはポリ
アミド樹脂を添加したものもであってもよい。In order to expand the transparent temperature range, an organic polymer resin (hereinafter referred to as "low Tg resin") having a glass transition temperature lower than that of the resin base material, preferably 50 ° C or lower, such as an acrylic resin, What added the polyester resin or the polyamide resin may be used.
【００２６】脂肪族カルボン酸としては、従来の可逆性
感熱記録層を形成するために使用されている、炭素数１
６〜２４程度の脂肪酸、たとえばステアリン酸あるいは
ベヘン酸等の他、これらの高級脂肪酸に代えて、本発明
者らが特願平５−７５０９９号で提案したような、下記
一般式
ＨＯＣＯ−Ｒ−ＣＯＯＨ ・・・ （Ｉ）
（式中、Ｒはアルキル基である）で表わされるジカルボ
ン酸、あるいは特願平４−３４３５５４号で提案したよ
うな、主鎖の任意の位置に−ＯＨ基を２以上有するヒド
ロキシル基置換脂肪族カルボン酸を使用することが、透
明化温度域を広くできるので、本発明の初期化の効果が
顕著に現われる。また可逆性感熱記録層は、紫外線また
は電子線などの放射線により硬化する放射線硬化型樹脂
を含有していてもよい。The aliphatic carboxylic acid has a carbon number of 1 and is used for forming a conventional reversible thermosensitive recording layer.
In place of fatty acids of about 6 to 24, such as stearic acid and behenic acid, and higher fatty acids thereof, the following general formula HOCO-R-as proposed by the present inventors in Japanese Patent Application No. 5-75099 is used. COOH (I) (wherein R is an alkyl group) or a dicarboxylic acid having an -OH group at any position on the main chain, as proposed in Japanese Patent Application No. 4-343554. The use of the above-mentioned hydroxyl group-substituted aliphatic carboxylic acid can broaden the transparentization temperature range, so that the initialization effect of the present invention is remarkably exhibited. The reversible thermosensitive recording layer may contain a radiation curable resin which is cured by radiation such as ultraviolet rays or electron beams.
【００２７】[0027]
【実施例】以下に本発明の実施例について説明する。EXAMPLES Examples of the present invention will be described below.
【００２８】（実施例１）厚さ１８８μｍのＰＥＴシー
トの一方の表面に、通常の材料を使用し、通常の方法に
したがって、磁気記録層、平滑層および光反射層を順次
に設けて基材を用意した。Example 1 A substrate was prepared by using a usual material on one surface of a PET sheet having a thickness of 188 μm and sequentially providing a magnetic recording layer, a smoothing layer and a light reflecting layer according to a usual method. Prepared.
【００２９】この基材の光反射層上に、下記の組成の塗
料を塗布して可逆性感熱記録層を形成した。A reversible thermosensitive recording layer was formed by coating a paint having the following composition on the light reflecting layer of this substrate.
【００３０】
ドデカン二酸 １重量部
ベヘニルステアレート ５重量部
塩化ビニル／酢酸ビニル共重合体
（ユニオンカーバイド社製商品名「ＶＭＣＨ」） １２重量部
アクリル樹脂（低Ｔｇ樹脂）
（東亜合成化学工業製商品名「Ｓ−２０４０」、
固形分３０％） ２０重量部
アクリロニトリル・スチレンブロックポリマー
（日本油脂製商品名「ＭＳ−１０Ｂ」） ０．２重量部
紫外線硬化型樹脂
（ＢＡＳＦ製商品名「ＬＲ−ＰＯ８３Ｆ」） ４．５重量部
光反応開始剤
（チバガイギー製商品名「イルガキュア１８４」） ０．２重量部
ＴＨＦ ２００重量部
塗料の塗布は、塗料を４０℃に加熱し、同じく４０℃に
加熱された基材の光反射層上に、ワイヤーバーにより塗
布した。Dodecanedioic acid 1 part by weight Behenyl stearate 5 parts by weight Vinyl chloride / vinyl acetate copolymer (trade name “VMCH” manufactured by Union Carbide Co.) 12 parts by weight Acrylic resin (low Tg resin) (manufactured by Toagosei Chemical Industry Co., Ltd.) Product name "S-2040", solid content 30%) 20 parts by weight acrylonitrile / styrene block polymer (NOF product name "MS-10B") 0.2 parts by weight UV curable resin (BASF product name "LR-" PO83F ") 4.5 parts by weight Photoinitiator (trade name" Irgacure 184 "manufactured by Ciba-Geigy) 0.2 parts by weight THF 200 parts by weight To apply the coating material, the coating material is heated to 40 ° C and also to 40 ° C. It coated with the wire bar on the light reflection layer of the base material.
【００３１】このようにして塗布された塗膜は、８０Ｗ
／ｃｍ×２灯、移動速度３０ｍ／分の条件で紫外線を照
射して紫外線硬化型樹脂を硬化させた。得られた可逆性
感熱記録層の厚さは約４〜５μｍであった。The coating film thus applied has a thickness of 80 W.
/ Cm × 2 lights and a moving speed of 30 m / min were irradiated with ultraviolet rays to cure the ultraviolet curable resin. The thickness of the obtained reversible thermosensitive recording layer was about 4 to 5 μm.
【００３２】つぎに可逆性感熱記録層上に、
紫外線硬化型樹脂塗料
（大日本インキ化学工業製商品名「Ｃ３−３７４」） １００重量部
シリコーンオイル
（信越化学工業製商品名「ＫＦ９６」） ３重量部
の組成の保護層用塗料を、乾燥膜厚が約２μｍになるよ
うに塗布し、４０℃のオーブン中で２分間乾燥させた
後、１６０Ｗ／ｃｍ×３灯、移動速度３０ｍ／分の条件
で紫外線を照射して硬化させた。Next, on the reversible thermosensitive recording layer, 100 parts by weight of an ultraviolet curable resin paint (trade name "C3-374" manufactured by Dainippon Ink & Chemicals, Inc.) silicone oil (trade name "KF96" manufactured by Shin-Etsu Chemical Co., Ltd.) 3 A coating material for the protective layer having a composition of 1 part by weight is applied so that the dry film thickness is about 2 μm, and dried in an oven at 40 ° C. for 2 minutes, then 160 W / cm × 3 lights, moving speed 30 m / min It was irradiated with ultraviolet rays under the conditions and cured.
【００３３】この可逆性感熱記録層の温度特性は下記の
とおりであった。The temperature characteristics of this reversible thermosensitive recording layer were as follows.
【００３４】Ｔ1＝４０℃
Ｔ3＝８０℃
Ｔ4＝１１０℃
Ｔ5＝１２０℃
Ｔ6＝１５０℃
このようにして得られた可逆性感熱記録媒体について、
下記の条件で初期化を行った。T1 = 40 ° C. T3 = 80 ° C. T4 = 110 ° C. T5 = 120 ° C. T6 = 150 ° C. For the reversible thermosensitive recording medium thus obtained,
Initialization was performed under the following conditions.
【００３５】(1) 可逆性感熱記録媒体を１３０℃のオー
ブン中に１分間保持後、数秒間以内で約１０℃まで急
冷。(1) After holding the reversible thermosensitive recording medium in an oven at 130 ° C. for 1 minute, it was rapidly cooled to about 10 ° C. within a few seconds.
【００３６】(2) ついで８０℃のオーブン中に２分間保
持後、数秒間以内で約１０℃まで急冷。(2) Then, after holding in an oven at 80 ° C for 2 minutes, it is rapidly cooled to about 10 ° C within a few seconds.
【００３７】（実施例２）
実施例１において、オーブン内での加熱時間を１０分と
した以外は同様に操作して初期化を行った。Example 2 Initialization was performed in the same manner as in Example 1 except that the heating time in the oven was changed to 10 minutes.
【００３８】（実施例３）
実施例１において、オーブン内での加熱時間を４時間と
した以外は同様に操作して初期化を行った。Example 3 Initialization was performed in the same manner as in Example 1, except that the heating time in the oven was changed to 4 hours.
【００３９】（比較例１）実施例１で用いたものと同じ
可逆性感熱記録媒体において、初期化を行わなかった。Comparative Example 1 The same reversible thermosensitive recording medium as that used in Example 1 was not initialized.
【００４０】（比較例２）実施例１において、初期化工
程(1)の冷却を１０℃／ｍｉｎで４０℃まで行った以外
は同様に操作した。Comparative Example 2 The same operation as in Example 1 was carried out except that the cooling in the initialization step (1) was performed at 40 ° C. at 10 ° C./min.
【００４１】（比較例３）
実施例１において、初期化工程(2)の冷却を１０℃／ｍ
ｉｎで４０℃まで行った以外は同様に操作した。(Comparative Example 3) In Example 1, cooling in the initialization step (2) was performed at 10 ° C / m.
The same operation was performed except that the temperature was changed to 40 ° C. in.
【００４２】実施例１〜３、および比較例１〜３で得た
可逆性感熱記録媒体について、通常のサーマルプリンタ
ーを用いて印字を行った結果を下記の表１に示す。使用
したサーマルプリンターのドット密度は８ドット／ｍ
ｍ、印字エネルギーは０．３５ｍＪ／ドットであった。
得られた印字部分の地肌濃度、印字濃度、およびコント
ラスト（地肌濃度−印字濃度）を、マクベス反射濃度計
を用いて測定した。The reversible thermosensitive recording media obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were printed using a conventional thermal printer, and the results are shown in Table 1 below. The dot density of the thermal printer used is 8 dots / m
m, the printing energy was 0.35 mJ / dot.
The background density, the printing density, and the contrast (background density-printing density) of the obtained printed portion were measured using a Macbeth reflection densitometer.
【００４３】[0043]
【表１】
（実施例４）厚さ１８８μｍのＰＥＴシートの一方の表
面に、通常の材料を使用し、通常の方法にしたがって、
磁気記録層、平滑層および光反射層を順次に設けて基材
を用意した。[Table 1] (Example 4) An ordinary material was used for one surface of a PET sheet having a thickness of 188 μm, and according to an ordinary method,
A magnetic recording layer, a smoothing layer and a light reflecting layer were sequentially provided to prepare a base material.
【００４４】この基材の光反射層上に、下記の組成の塗
料を塗布して可逆性感熱記録層を形成した。A reversible thermosensitive recording layer was formed by coating a coating material having the following composition on the light reflecting layer of this substrate.
【００４５】
ドデカン二酸 １重量部
ステアリルステアレート ５重量部
塩化ビニル／酢酸ビニル共重合体
（ユニオンカーバイド社製商品名「ＶＭＣＨ」） １２重量部
アクリル樹脂（低Ｔｇ樹脂）
（東亜合成化学工業製商品名「Ｓ−２０４０」、
固形分３０％） ４重量部
紫外線硬化型樹脂
（ＢＡＳＦ製商品名「ＬＲ−ＰＯ８３Ｆ」） ２重量部
光反応開始剤
（チバガイギー製商品名「イルガキュア１８４」） ０．１重量部
ＴＨＦ １００重量部
このようにして塗布された塗膜は、８０Ｗ／ｃｍ×２
灯、移動速度３０ｍ／分の条件で紫外線を照射して紫外
線硬化型樹脂を硬化された。得られた可逆性感熱記録層
の厚さは約４μｍであった。Dodecanedioic acid 1 part by weight Stearyl stearate 5 parts by weight Vinyl chloride / vinyl acetate copolymer (trade name “VMCH” manufactured by Union Carbide Co.) 12 parts by weight Acrylic resin (low Tg resin) (manufactured by Toagosei Chemical Industry Co., Ltd.) Product name “S-2040”, solid content 30%) 4 parts by weight UV curable resin (BASF product name “LR-PO83F”) 2 parts by weight Photoinitiator (Ciba Geigy product name “Irgacure 184”) 1 part by weight THF 100 parts by weight The coating film thus applied has a thickness of 80 W / cm × 2.
The UV curable resin was cured by irradiating with UV light under the conditions of a lamp and a moving speed of 30 m / min. The resulting reversible thermosensitive recording layer had a thickness of about 4 μm.
【００４６】つぎに可逆性感熱記録層上に、
紫外線硬化型樹脂塗料
（大日本インキ化学工業製商品名「Ｃ３−３７４」） １００重量部
シリコーンオイル
（信越化学工業製商品名「ＫＦ９６」） ３重量部
の組成の保護層用塗料を、乾燥膜厚が約２μｍになるよ
うに塗布し、４０℃のオーブン中で２分間乾燥させた
後、１６０Ｗ／ｃｍ×３灯、移動速度３０ｍ／分の条件
で紫外線を照射して硬化させた。Next, on the reversible thermosensitive recording layer, 100 parts by weight of an ultraviolet curable resin paint (trade name "C3-374" manufactured by Dainippon Ink and Chemicals, Inc.) silicone oil (trade name "KF96" manufactured by Shin-Etsu Chemical Co., Ltd.) 3 A coating material for the protective layer having a composition of 1 part by weight is applied so that the dry film thickness is about 2 μm, and dried in an oven at 40 ° C. for 2 minutes, then 160 W / cm × 3 lights, moving speed 30 m / min It was irradiated with ultraviolet rays under the conditions and cured.
【００４７】この可逆性感熱記録層の温度特性は下記の
とおりであった。The temperature characteristics of this reversible thermosensitive recording layer were as follows.
【００４８】Ｔ1＝３３℃
Ｔ3＝５５℃
Ｔ4＝１０５℃
Ｔ5＝１２０℃
Ｔ6＝１５０℃
（実施例５）実施例４において、可逆性感熱記録層の塗
料として下記の組成のものを用いた以外は同様に操作し
て、可逆性感熱記録媒体を調製した。T1 = 33 ° C. T3 = 55 ° C. T4 = 105 ° C. T5 = 120 ° C. T6 = 150 ° C. (Example 5) In Example 4, except that the reversible thermosensitive recording layer coating material having the following composition was used. In the same manner as above, a reversible thermosensitive recording medium was prepared.
【００４９】
ベヘン酸 １重量部
ステアリルステアレート ５重量部
塩化ビニル／酢酸ビニル共重合体
（ユニオンカーバイド社製商品名「ＶＭＣＨ」） １２重量部
紫外線硬化型樹脂
（ＢＡＳＦ製商品名「ＬＲ−ＰＯ８３Ｆ」） ２重量部
光反応開始剤
（チバガイギー製商品名「イルガキュア１８４」） ０．１重量部
ＴＨＦ １００重量部
この可逆性感熱記録層の温度特性は下記のとおりであっ
た。Behenic acid 1 part by weight Stearyl stearate 5 parts by weight Vinyl chloride / vinyl acetate copolymer (trade name "VMCH" manufactured by Union Carbide) 12 parts by weight UV curable resin (BASF trade name "LR-PO83F") 2 parts by weight Photoinitiator (trade name “Irgacure 184” manufactured by Ciba Geigy) 0.1 parts by weight THF 100 parts by weight The temperature characteristics of the reversible thermosensitive recording layer were as follows.
【００５０】Ｔ1＝３３℃
Ｔ3＝７０℃
Ｔ4＝８５℃
Ｔ5＝１１０℃
Ｔ6＝１５０℃
（実施例６）下記の組成からなる塗料を用いて構成した
可逆性感熱記録層を有する可逆性感熱記録媒体を調製し
た。T1 = 33 ° C. T3 = 70 ° C. T4 = 85 ° C. T5 = 110 ° C. T6 = 150 ° C. (Example 6) Reversible thermosensitive recording having a reversible thermosensitive recording layer constituted by using a coating material having the following composition The medium was prepared.
【００５１】
ステアリン酸アミド １重量部
ジヒドロキシベヘン酸 ２重量部
塩化ビニル／酢酸ビニル共重合体
（ユニオンカーバイド社製商品名「ＶＭＣＨ」） １２重量部
ＴＨＦ ２００重量部
形成された塗膜は、紫外線硬化処理を行わなかった以
外、実施例４と同様にして乾燥され、その上に保護層が
設けられた。この可逆性感熱記録媒体の温度特性は下記
のとおりであった。Stearic acid amide 1 part by weight Dihydroxybehenic acid 2 parts by weight Vinyl chloride / vinyl acetate copolymer (trade name “VMCH” manufactured by Union Carbide Co.) 12 parts by weight THF 200 parts by weight The formed coating film is UV cured. It was dried in the same manner as in Example 4 except that no treatment was performed, and a protective layer was provided thereon. The temperature characteristics of this reversible thermosensitive recording medium were as follows.
【００５２】Ｔ1＝３５℃
Ｔ3＝７０℃
Ｔ4＝９０℃
Ｔ5＝１１０℃
Ｔ6＝１５０℃
実施例４〜６で得た可逆性感熱記録媒体について、実施
例１と同じ条件で初期化を行った場合と、行わなかった
場合について、印字特性を測定した。その結果を下記の
表２に示す。T1 = 35 ° C. T3 = 70 ° C. T4 = 90 ° C. T5 = 110 ° C. T6 = 150 ° C. The reversible thermosensitive recording media obtained in Examples 4 to 6 were initialized under the same conditions as in Example 1. The printing characteristics were measured with and without the case. The results are shown in Table 2 below.
【００５３】[0053]
【表２】
表１および表２の結果から、本発明の方法にしたがって
初期化することにより、コントラストが大幅に向上し
て、印字の明瞭度が向上していることが明らかである。[Table 2] From the results of Tables 1 and 2, it is clear that the contrast is significantly improved and the clarity of printing is improved by the initialization according to the method of the present invention.
【００５４】[0054]
【発明の効果】以上のように本発明の方法によれば、製
造されたままの可逆性感熱記録媒体の印字特性が安定化
し、常に一定した印字性能を発揮するので、製品の信頼
性が向上る。As described above, according to the method of the present invention, the printing characteristics of the as-manufactured reversible thermosensitive recording medium are stabilized and consistent printing performance is exhibited, so that the reliability of the product is improved. It
【図１】本発明の初期化方法の温度と時間との関係を示
すグラフ。FIG. 1 is a graph showing the relationship between temperature and time in the initialization method of the present invention.
【図２】本発明の初期化方法における可逆性感熱記録層
の温度と白濁度との関係をすグラフ。FIG. 2 is a graph showing the relationship between the temperature of the reversible thermosensitive recording layer and the white turbidity in the initialization method of the present invention.
【図３】本発明の初期化方法の実施に適用される装置の
系統図。FIG. 3 is a systematic diagram of an apparatus applied to implement the initialization method of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−24131（ＪＰ，Ａ) 特開 平５−262035（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B41M 5/36 B41J 2/32 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-24131 (JP, A) JP-A-5-262035 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B41M 5/36 B41J 2/32
Claims (2)
度Ｔ4以下の温度に加熱した後、室温まで冷却すると透
明状態になり、透明化上限温度Ｔ4以上で白濁下限温度
Ｔ5よりも高い温度に加熱した後、室温まで冷却すると
白濁状態になり、これを可逆的に繰り返す可逆性感熱記
録層を基材上に備えた可逆性感熱記録媒体を、その使用
に先立って初期化する方法であって、前記可逆性感熱記
録媒体を、 (a) 白濁下限温度Ｔ5以上、基材の耐熱温度Ｔ6以下の
温度に加熱する第１の工程、 (b) 前記白濁下限温度Ｔ5以上、基材の耐熱温度Ｔ6以
下の温度から前記可逆性感熱記録媒体への可逆的な記録
が可能な周囲の環境温度の上限温度Ｔ1以下の温度に１
０秒以内で急冷する工程、 (c) 透明化下限温度Ｔ3以上、透明化上限温度Ｔ4以下
の温度に再び加熱する工程、および (d) 前記透明化下限温度Ｔ3以上、透明化上限温度Ｔ4
以下の温度から前記可逆性感熱記録媒体への可逆的な記
録が可能な周囲の環境温度の上限温度Ｔ1以下の温度に
再び１０秒以内で急冷する工程、 を備えていることを特徴とする可逆性感熱記録媒体の初
期化方法。1. A transparent state is obtained by heating to a temperature not lower than the transparency lowering temperature T3 and not higher than the transparency upper limit temperature T4, and then cooled to room temperature, and becomes a temperature higher than the transparency upper limit temperature T4 and higher than the cloudiness lower limit temperature T5. A method of initializing a reversible thermosensitive recording medium having a reversible thermosensitive recording layer on a substrate, which becomes white turbid when cooled to room temperature after heating, and which is reversibly repeated. A first step of heating the reversible thermosensitive recording medium to a temperature of (a) a minimum white turbidity temperature T5 or higher and a heat resistant temperature T6 of a base material or lower , (b) the minimum cloudiness temperature T5 or higher, a heat resistant temperature of the base material T6 or later
Reversible recording from the lower temperature to the reversible thermosensitive recording medium
1 to the upper limit temperature T1 below the temperature of the environment temperature around capable
Quenching within 0 seconds ; (c) reheating to a temperature below the clarification lower limit temperature T3 and below the clarification upper limit temperature T4; and (d) above the clarification lower limit temperature T3 and above, the clarification upper limit temperature T4.
Reversible recording on the reversible thermosensitive recording medium from the following temperature
A method for initializing a reversible thermosensitive recording medium, further comprising: a step of rapidly cooling the temperature to a temperature not higher than an upper limit temperature T1 of an ambient temperature capable of recording within 10 seconds .
度Ｔ4以下の温度に加熱した後、室温まで冷却すると透
明状態になり、透明化上限温度Ｔ4以上で白濁下限温度
Ｔ5よりも高い温度に加熱した後、室温まで冷却すると
白濁状態になり、これを可逆的に繰り返す可逆性感熱記
録層を基材上に備えた可逆性感熱記録媒体であって、 (a) 白濁下限温度Ｔ5以上、基材の耐熱温度Ｔ6以下の
温度に加熱する第１の工程、 (b) 前記白濁下限温度Ｔ5以上、基材の耐熱温度Ｔ6以
下の温度から前記可逆性感熱記録媒体への可逆的な記録
が可能な周囲の環境温度の上限温度Ｔ1以下の温度に１
０秒以内で急冷する工程、 (c) 透明化下限温度Ｔ3以上、透明化上限温度Ｔ4以下
の温度に再び加熱する工程、および (d) 前記透明化下限温度Ｔ3以上、透明化上限温度Ｔ4
以下の温度から前記可逆性感熱記録媒体への可逆的な記
録が可能な周囲の環境温度の上限温度Ｔ1以下の温度に
再び１０秒以内で急冷する工程、 を経て初期化されていることを特徴とする可逆性感熱記
録媒体。2. A transparent state is obtained by heating to a temperature not lower than the lower limit of transparency T3 and lower than the upper limit temperature of transparency T4 and then cooled to room temperature, and a temperature higher than the upper limit of transparency T4 and higher than the lower limit of cloudiness T5. A reversible thermosensitive recording medium having a reversible thermosensitive recording layer on a substrate, which becomes a cloudy state when heated to room temperature and then reversibly repeated. The first step of heating to a temperature not higher than the heat resistant temperature T6 of the material , (b) above the lower limit temperature of clouding T5, and above the heat resistant temperature of the substrate T6
Reversible recording from the lower temperature to the reversible thermosensitive recording medium
1 to the upper limit temperature T1 below the temperature of the environment temperature around capable
Quenching within 0 seconds ; (c) reheating to a temperature below the clarification lower limit temperature T3 and below the clarification upper limit temperature T4; and (d) above the clarification lower limit temperature T3 and above, the clarification upper limit temperature T4.
Reversible recording on the reversible thermosensitive recording medium from the following temperature
A reversible thermosensitive recording medium, wherein the reversible thermosensitive recording medium is initialized through a step of rapidly cooling again within 10 seconds to a temperature equal to or lower than an upper limit temperature T1 of an environmental temperature capable of recording.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18930594A JP3412122B2 (en) | 1994-08-11 | 1994-08-11 | Initialized reversible thermosensitive recording medium and initialization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18930594A JP3412122B2 (en) | 1994-08-11 | 1994-08-11 | Initialized reversible thermosensitive recording medium and initialization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0852944A JPH0852944A (en) | 1996-02-27 |
| JP3412122B2 true JP3412122B2 (en) | 2003-06-03 |
Family
ID=16239118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18930594A Expired - Fee Related JP3412122B2 (en) | 1994-08-11 | 1994-08-11 | Initialized reversible thermosensitive recording medium and initialization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3412122B2 (en) |
-
1994
- 1994-08-11 JP JP18930594A patent/JP3412122B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0852944A (en) | 1996-02-27 |
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