JPS63317385A - Reversible thermal recording material - Google Patents

Reversible thermal recording material

Info

Publication number
JPS63317385A
JPS63317385A JP62152550A JP15255087A JPS63317385A JP S63317385 A JPS63317385 A JP S63317385A JP 62152550 A JP62152550 A JP 62152550A JP 15255087 A JP15255087 A JP 15255087A JP S63317385 A JPS63317385 A JP S63317385A
Authority
JP
Japan
Prior art keywords
temperature
recording material
heat
graft polymer
transparent
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
Application number
JP62152550A
Other languages
Japanese (ja)
Other versions
JP2582784B2 (en
Inventor
Yoshihiko Hotta
吉彦 堀田
Takashi Kubo
久保　敬司
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ricoh Co Ltd
Original Assignee
Ricoh Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ricoh Co Ltd filed Critical Ricoh Co Ltd
Priority to JP62152550A priority Critical patent/JP2582784B2/en
Publication of JPS63317385A publication Critical patent/JPS63317385A/en
Priority to US07/321,854 priority patent/US5017421A/en
Priority to US07/627,329 priority patent/US5108980A/en
Priority to US08/231,751 priority patent/USRE37034E1/en
Application granted granted Critical
Publication of JP2582784B2 publication Critical patent/JP2582784B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B41M5/363—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using materials comprising a polymeric matrix containing a low molecular weight organic compound such as a fatty acid, e.g. for reversible recording
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/405—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by layers cured by radiation

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

PURPOSE:To enhance a thermal sensitivity to form a sharp image and to reduce the deterioration of the image, by a method wherein a thermosensitive layer reversibly varying in transparency according to a temperature is formed, and thereon an overcoat layer mainly composed of a polysiloxane graft polymer is provided. CONSTITUTION:In a reversible thermal recording material, a thermosensitive layer which is mainly composed of a resin base material and an organic low-molecular substance dispersed in the resin base material so as to reversibly vary in transparency according to a temperature is provided on a substrate, and thereon an overcoat layer mainly composed of a polysiloxane graft polymer is provided. The thermosensitive layer is white-opaque at a room temperature of T0 or below, turns to be transparent when being heated to a temperature ranging T1-T2, and keeps transparent if being cooled down to a room temperature of T0 or below. When being heated to a temperature of T3 or above, the thermosensitive layer turns into an intermediate translucent state. It returns to an initial white-opaque state with decreasing temperature. The provision of the overcoat layer mainly composed of the polysiloxane graft polymer enables the reduction of the coefficient of friction of the surface of the material and enhances thermal sensitivity, which is a heat transmission from a thermal head to the recording material.

Description

【発明の詳細な説明】 鼓Ｊした野一 本発明は温度による感熱体の可逆的な透明度変化を利用
して記録及び消去を行なう可逆性感熱記録材料に関する
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a reversible thermosensitive recording material that performs recording and erasing by utilizing the reversible change in transparency of a thermosensitive member depending on temperature.

灸末抜権 可逆的な記録及び消去が可能な感熱記録材料として支持
体上にポリエステル、ポリアミド等の樹脂中に高級アル
コール、高級脂肪酸等の有機低分子物質を分散した感熱
層を設けたものが、例えば特開昭５４−１１９３７７号
、同５５−１５４１９８号等で知られている。この種の
記録材料による記録、即ち画像形成及び消去は感熱層の
温度による透明度変化を利用したものである。As a heat-sensitive recording material capable of reversible recording and erasing, there is a heat-sensitive layer on a support in which organic low-molecular substances such as higher alcohols and higher fatty acids are dispersed in a resin such as polyester or polyamide. , for example, is known from Japanese Patent Application Laid-open Nos. 54-119377 and 55-154198. Recording with this type of recording material, that is, image formation and erasing, utilizes the change in transparency of the heat-sensitive layer depending on the temperature.

しかし従来の可逆性感熱記録材料においては表面をサー
マルヘッド等で加熱して画像形成する際、これら加熱手
段との摩擦が大きいため、充分な密着が得られず、この
ため熱感度が低下したり、表面に凹凸ができたりする結
果、鮮明な画像を形成することは回連であった。However, in conventional reversible thermosensitive recording materials, when forming images by heating the surface with a thermal head, etc., the friction with these heating means is large, so sufficient adhesion cannot be achieved, resulting in a decrease in thermal sensitivity. However, as a result of unevenness on the surface, it was difficult to form clear images.

そこで本発明者らは特願昭６２−５５６５０号において
シリコーン樹脂、シリコーンゴム等のオーバーコート層
を設けて表面の摩擦を小さくした可逆性感熱記録材料を
提案したが、このオーバーコート層の場合は感熱層との
接着性が未だ不充分で、機械的な刺激を繰返し与えると
、剥れてしまい、画像劣化を生じるという問題があった
。Therefore, the present inventors proposed a reversible thermosensitive recording material in which surface friction was reduced by providing an overcoat layer of silicone resin, silicone rubber, etc. in Japanese Patent Application No. 62-55650. The adhesion with the heat-sensitive layer is still insufficient, and repeated mechanical stimulation causes the film to peel off, resulting in image deterioration.

１的 本発明の目的はサーマルヘッド等の加熱により画像形成
する際にこれら加熱手段との密着性。One object of the present invention is to improve the adhesion with heating means when forming an image by heating a thermal head or the like.

従って熱感度を向上させて鮮明な画像を形成でき、且つ
繰返し使用しても画像劣化の少ない可逆性感熱記録材料
を堤供することができる。Therefore, it is possible to provide a reversible thermosensitive recording material that can improve thermal sensitivity, form clear images, and exhibit little image deterioration even after repeated use.

構　　　成 本発明の可逆性感熱記録材料は支持体上に樹脂母材とこ
の樹脂母材中に分散された有機低分子物質を主成分とし
てなり、温度に依存して透明度が可逆的に変化する感熱
層と更にその上にポリシロキサングラフトポリマーを主
成分とするオーバーコート層を設けたことを特徴とする
ものである。Structure The reversible heat-sensitive recording material of the present invention is a heat-sensitive material whose main components are a resin base material on a support and an organic low-molecular substance dispersed in the resin base material, and whose transparency changes reversibly depending on the temperature. This layer is characterized by further providing an overcoat layer containing a polysiloxane graft polymer as a main component thereon.

本発明記録材料の記録原理は感熱層の温度による透明度
変化を利用したもので、これを図面によって説明する。The recording principle of the recording material of the present invention utilizes the change in transparency of the heat-sensitive layer depending on the temperature, and this will be explained with reference to the drawings.

第１図において感熱層は例えばＴ。以下の常温では白濁
不透明状態にある。In FIG. 1, the heat-sensitive layer is, for example, T. At room temperature below, it is cloudy and opaque.

これをＴ１−Ｔ２間の温度に加熱すると透明になり、こ
の状態でＴ。以下の常温に戻しても透明のままである。When this is heated to a temperature between T1 and T2, it becomes transparent, and in this state it becomes T. It remains transparent even after returning to room temperature below.

更にＴ１以上の温度に加熱すると、最大透明度と最大不
透明度との中間の半透明状態になる。次にこの温度を下
げて行くと、再び透明状態をとることなく、最初の白濁
不透明状態に戻る。なおこの不透明状態のものをＴ。Further heating to a temperature of T1 or higher results in a translucent state intermediate between maximum transparency and maximum opacity. Next, when this temperature is lowered, the liquid returns to its initial cloudy and opaque state without becoming transparent again. Note that this opaque state is T.

〜Ｔ０間の温度に加熱した後、常温、即ち、Ｔ０以上の
温度に冷却した場合には透明と不透明との間の状態をと
ることができる。また前記、常温で透明になったものも
再び１３以上の温度に加熱し、常温に戻せば、再び白濁
不透明状態に戻る。When heated to a temperature between ~T0 and then cooled to room temperature, that is, a temperature higher than T0, a state between transparent and opaque can be taken. Moreover, if the above-mentioned material that becomes transparent at room temperature is heated again to a temperature of 13 or more and returned to room temperature, it will return to a cloudy, opaque state.

即ち常温で不透明及び透明の両形態並びにその中間状態
をとることができる。That is, it can take both opaque and transparent forms, as well as intermediate states, at room temperature.

なお透明部が透明に見えるのはこの部分の樹脂母材中に
分散された有機低分子物質が大きな結晶粒子で構成され
ているため、一方の側から入射した光は散乱されること
なく、他方の側に透過するからであると考えられる。ま
た不透明部が白く見えるのはこの部分の樹脂母材中に分
散された有機低分子物質が微細結晶が集合した多結晶粒
子で構成され、個々の結晶の結晶軸が種々の方向に向い
ているため、一方の側から入射した光は各結晶の界面で
何度も屈折し散乱されるからであると考えられる。The reason why the transparent part looks transparent is because the organic low-molecular substance dispersed in the resin base material in this part is composed of large crystal particles, so light that enters from one side is not scattered and is transmitted to the other side. This is thought to be due to the fact that it is transmitted to the . The reason why the opaque area appears white is because the organic low-molecular substance dispersed in the resin base material in this area is composed of polycrystalline particles, which are aggregates of microcrystals, and the crystal axes of the individual crystals are oriented in various directions. This is thought to be because light incident from one side is refracted and scattered many times at the interface of each crystal.

従って例えば以上のような感熱層を有する層状感熱部材
（支持体上に感熱層を設けたもの、或いは感熱シート）
全体をＴ□〜Ｔ２間の温度に加熱後、Ｔ０以上の常温に
冷却して透明化し。Therefore, for example, a layered heat-sensitive member having a heat-sensitive layer as described above (a heat-sensitive layer provided on a support, or a heat-sensitive sheet)
After heating the whole to a temperature between T□ and T2, it is cooled to room temperature above T0 to become transparent.

ついでこれをサーマルヘッド等で部分的に１３以上の温
度に加熱しその部分を不透明化すれば、白色画像が形成
される。このような白色画像を有する層状感熱部材の裏
面に層状着色部材を配置すれば、この画像は着色部材の
色を背景に白色画像として認識できる。Then, a white image is formed by partially heating this with a thermal head or the like to a temperature of 13 or higher to make the area opaque. If a layered colored member is placed on the back side of a layered heat-sensitive member having such a white image, this image can be recognized as a white image against the background of the color of the colored member.

一方、層状感熱部材全体を１３以上の温度に加熱した後
、Ｔ０以上の常温に戻し白濁、不透明化した後、サーマ
ルヘッド等で部分的に１０〜７２間の温度に加熱してそ
の部分を透明化すれば白色面に透明画像が形成される。On the other hand, after heating the entire layered heat-sensitive member to a temperature of 13 or more, returning it to room temperature of T0 or more and making it cloudy and opaque, heat it partially with a thermal head etc. to a temperature of 10 to 72 to make that part transparent. A transparent image is formed on the white surface.

そしてこのような透明画像を有する層状感熱部材の裏面
に着色部材を配置すれば、この画像は白地を背景に着色
部材の色の画像として認識できる。If a colored member is placed on the back side of a layered heat-sensitive member having such a transparent image, this image can be recognized as an image of the color of the colored member against a white background.

以上のような層状感熱部材への記録及び消去は、少なく
とも１０４回程腐縁り返すことができる。Recording and erasing on the layered heat-sensitive member as described above can be repeated at least 104 times.

本発明では以上のような層状感熱部材の感熱層上に更に
ポリシロキサングラフトポリマーを主成分としたオーバ
ーコート層を設けることにより、こうして得られた可逆
性感熱記録材料表面の摩擦係数を大幅に低下させること
ができる。In the present invention, by further providing an overcoat layer mainly composed of a polysiloxane graft polymer on the heat-sensitive layer of the layered heat-sensitive member as described above, the coefficient of friction on the surface of the reversible heat-sensitive recording material thus obtained is significantly reduced. can be done.

ところでサーマルヘッドの中でも特にラインヘッドで加
熱、画像形成する場合には記録材料はヘッドとプラテン
ローラーとの間に挟まれ、ヘッドに押圧されながらプラ
テンローラーの動きに合せて動き、相対的にヘッドとの
位置が動いて１ライン毎に選択的に加熱され、画像形成
されて行くが、その際本発明の可逆性感熱記録材料は、
前述のように表面の摩擦係数が非常に小さいため、ヘッ
ドに押圧されながら動く際にも非常に滑らかであり、こ
のためヘッドとの間に空気の入る余地は少なく、即ちヘ
ッドとの密着性が良く、その結果、サーマルヘッドから
の記録材料への熱の伝達、即ち熱感度が良好となる。By the way, when heating and forming an image with a line head among thermal heads, the recording material is sandwiched between the head and the platen roller, and is pressed by the head and moves in accordance with the movement of the platen roller, so that the recording material is moved relative to the head. The position of the reversible thermosensitive recording material of the present invention moves and is selectively heated line by line to form an image.
As mentioned above, the friction coefficient of the surface is very small, so it is very smooth even when it moves while being pressed by the head, so there is little room for air to enter between it and the head, which means that it has good adhesion with the head. As a result, the heat transfer from the thermal head to the recording material, that is, the thermal sensitivity is improved.

本発明の可逆性感熱記録材料を作るには一般には下記方
法により支持体上に感熱層を形成後。The reversible heat-sensitive recording material of the present invention is generally prepared after forming a heat-sensitive layer on a support by the following method.

オーバーコート層を形成する方法が採用されるが、（１
）の工程では特に支持体を用いずに、感熱層材料を通常
の成膜法によって自己支持性の感熱シートとしてもよい
。A method of forming an overcoat layer is adopted, but (1
In step ), the heat-sensitive layer material may be formed into a self-supporting heat-sensitive sheet by a normal film-forming method without using any particular support.

（１）　　樹脂母材及び有機低分子物質を溶解した溶液
、又は樹脂母材の溶液（溶剤としては有機低分子物質を
溶解しないものを用いる）に有機低分子物質を微粒子状
に分散してなる分散液を、プラスチックフィルム、ガラ
ス板、金属板等の支持体上に塗布乾燥して感熱層を形成
する。(1) A solution in which a resin base material and an organic low-molecular substance are dissolved, or a solution of a resin base material (use a solvent that does not dissolve the organic low-molecular substance) and an organic low-molecular substance dispersed in the form of fine particles. The dispersion is coated onto a support such as a plastic film, glass plate, metal plate, etc. and dried to form a heat-sensitive layer.

（２）　　その上にポリシロキサングラフトポリマーを
溶解または分散した液を塗布乾燥してオーバーコート層
を形成する。なおこの溶液又は分散液には必要あれば硬
化剤、硬化促進剤、触媒等を混合してもよい。(2) A solution in which a polysiloxane graft polymer is dissolved or dispersed is applied and dried to form an overcoat layer. If necessary, a curing agent, a curing accelerator, a catalyst, etc. may be mixed into this solution or dispersion.

感熱層形成用の溶媒としては、有機低分子物質及び樹脂
母材の種類によって各種のものを用いることが可能であ
る。例えばテトラヒドロフラン、メチルエチルケトン、
メチルイソブチルケトン、クロロホルム、四塩化炭素、
エタノール、トルエン、ベンゼン等の有機溶剤が挙げら
れる。As the solvent for forming the heat-sensitive layer, various solvents can be used depending on the type of organic low-molecular substance and resin base material. For example, tetrahydrofuran, methyl ethyl ketone,
Methyl isobutyl ketone, chloroform, carbon tetrachloride,
Examples include organic solvents such as ethanol, toluene, and benzene.

なお、こうして形成される感熱層においては。In addition, in the heat-sensitive layer formed in this way.

有機低分子物質は樹脂母材中に微粒子として分散状態で
存在する。The organic low-molecular substance exists in a dispersed state as fine particles in the resin matrix.

感熱層に使用される樹脂母材は有機低分子物質を均一に
分散保持した皮膜又はシートを形成すると共に、最大透
明時の透明度に影響を与える材料である。このため樹脂
母材は透明性が良く、機械的に安定で、且つ成膜性の良
い樹脂が好ましい。このような樹脂としてはポリ塩化ビ
ニル；塩化ビニル−酢酸ビニル共重合体、塩化ビニル−
酢酸ビニル〜ビニルアルコール共重合体、塩化ビニル−
酢酸ビニル〜マレイン酸共重合体、塩化ビニルルアクリ
レート共重合体等の塩化ビニリデン−塩化ビニル共重合
体、塩化ビニリデン−アクリロニトリル共重合体等の塩
化ビニリデン系共重合体；ポリエステル；ポリアミド：
ポリアクリレート又はポリメタクリレート或いはアクリ
レ−トルメタクリレート共重合体、シリコン樹脂等が挙
げられる。これらは単独で或いは２種以上混合して使用
される。The resin base material used for the heat-sensitive layer is a material that forms a film or sheet in which a low-molecular-weight organic substance is uniformly dispersed and holds, and also influences the transparency at maximum transparency. Therefore, the resin base material is preferably a resin that has good transparency, is mechanically stable, and has good film-forming properties. Examples of such resins include polyvinyl chloride; vinyl chloride-vinyl acetate copolymer, and vinyl chloride-vinyl acetate copolymer.
Vinyl acetate - vinyl alcohol copolymer, vinyl chloride -
Vinylidene chloride-based copolymers such as vinyl acetate-maleic acid copolymers, vinylidene chloride-vinyl chloride copolymers such as vinyl chloride acrylate copolymers, vinylidene chloride-acrylonitrile copolymers; polyesters; polyamides:
Examples include polyacrylate, polymethacrylate, acrylate-methacrylate copolymer, and silicone resin. These may be used alone or in combination of two or more.

一方、有機低分子物質は第１図の温度Ｔ。〜Ｔ３を選定
することに応じて適宜選択すればよいが、融点３０〜２
００℃、特に５０〜１５０℃程度のものが好ましい。こ
のような有機低分子物質としてはアルカノール；アルカ
ンジオール；ハロゲンアルカノールまたはハロゲンアル
カンジオール；アルキルアミン；アルカン；アルケン；
アルキン；ハロゲンアルカン；ハロゲンアルケン。On the other hand, organic low-molecular substances have a temperature T as shown in FIG. It may be selected as appropriate depending on the selection of ~T3, but the melting point is 30 ~ 2
00°C, particularly preferably about 50 to 150°C. Such organic low-molecular substances include alkanols; alkanediols; halogen alkanols or halogen alkanediols; alkylamines; alkanes; alkenes;
Alkyne; halogen alkane; halogen alkene.

ハロゲンアルキン；シクロアルカン；シクロアルケン；
シクロアルキン；飽和または不飽和モノまたはジカルボ
ン酸またはこれらのエステル、アミド、またはアンモニ
ウム塩；飽和または不飽和ハロゲン脂肪酸またはこれら
のエステル、アミド、またはアンモニウム塩；アリルカ
ルボン酸またはそれらのエステル、アミドまたはアンモ
ニウム塩；ハロゲンアリルカルボン酸またはそれらのエ
ステル、アミド、またはアンモニウム塩；チオアルコー
ル：チオカルボン酸またはそれらのエステル、アミン、
またはアンモニウム塩１チオアルコールのカルボン酸エ
ステル等が挙げられる。これらは単独で又は２種以上混
合して使用される。これらの化合物の炭素数は１０〜６
０、好ましくは１０〜３８、特に１０〜３０が好ましい
。エステル中のアルコール基部分は飽和していても飽和
していなくてもよく、またハロゲン置換されていてもよ
い。いずれにしても有機低分子物質は分子中に酸素、窒
素、硫黄及びハロゲンの少なくとも１種１例えば−ＯＲ
，−ＣＯＯＨ，−ＣＯＮＨ，−ＣＯＯＲ，−ＮＨ−。Halogenalkyne; cycloalkane; cycloalkene;
cycloalkynes; saturated or unsaturated mono- or dicarboxylic acids or their esters, amides, or ammonium salts; saturated or unsaturated halogenated fatty acids or their esters, amides, or ammonium salts; allylcarboxylic acids or their esters, amides, or ammonium Salts; Halogen allylcarboxylic acids or their esters, amides, or ammonium salts; Thioalcohols: Thiocarboxylic acids or their esters, amines,
Alternatively, carboxylic acid esters of ammonium salts and monothioalcohols may be mentioned. These may be used alone or in a mixture of two or more. The carbon number of these compounds is 10-6
0, preferably 10-38, especially 10-30. The alcohol group moiety in the ester may be saturated or unsaturated, and may be substituted with halogen. In any case, the organic low-molecular substance has at least one of oxygen, nitrogen, sulfur, and halogen in its molecule. For example, -OR
, -COOH, -CONH, -COOR, -NH-.

−ＮＨ２，−８−、−８−３−、−０−、ハロゲン等を
含む化合物であることが好ましい。Preferably, it is a compound containing -NH2, -8-, -8-3-, -0-, halogen, or the like.

更に具体的にはこれら化合物にはラウリン酸。More specifically, these compounds include lauric acid.

ドデカン酸、ミリスチン酸、ペンタデカン酸、パルミチ
ン酸、ステアリン酸、ベヘン酸、ノナデカン酸、アラキ
ン酸、オレイン酸等の高級脂肪酸ニステアリン酸メチル
、ステアリン酸テトラブシル、ステアリン酸オクタデシ
ル、ラウリン酸オクタデシル、パルミチン酸テトラデシ
ル、ベヘン酸トコシル等の高級脂肪酸のエステル；Ｃ１
ａＨ３３−０−Ｃ工ＧＮ３３．ＣニーＨ１ａ−５−Ｃｔ
ｓｌｈａＣＩＪＨ３７−３−Ｃ１−８３７、Ｃｌ２Ｈ２
Ｓ−５−Ｃ１２Ｈ２、Ｃ工、Ｈ３，−５−Ｃ工９Ｈ３！
Ｉｃ工２Ｈ，、−５−３−Ｃ１□１１□。Higher fatty acids such as dodecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, behenic acid, nonadecanoic acid, arachidic acid, oleic acid, etc. Methyl nistearate, tetrabutyl stearate, octadecyl stearate, octadecyl laurate, tetradecyl palmitate , esters of higher fatty acids such as tocosyl behenate; C1
aH33-0-C Engineering GN33. C knee H1a-5-Ct
slhaCIJH37-3-C1-837, Cl2H2
S-5-C12H2, C engineering, H3, -5-C engineering 9H3!
Ic engineering 2H,, -5-3-C1□11□.

ＣＨ。CH.

ＣＨ。CH.

ＣＨ。CH.

ＣＨ。CH.

等のエーテル又はチオエーテル等がある。There are ethers and thioethers such as

なお感熱層中の有機低分子物質と樹脂母材との割合は重
量比で１：０．５〜１：１６程度が好ましい、樹脂母材
の比率がこれ以下になると、有機低分子物質を樹脂母材
中に保持した膜を形成することが困難となり、一方、こ
れ以上になると、有機低分子物質の量が少ないため、不
透明化が困難となる。The ratio of the organic low-molecular substance to the resin base material in the heat-sensitive layer is preferably about 1:0.5 to 1:16 by weight. If the ratio of the resin base material is less than this, the organic low-molecular substance is It becomes difficult to form a film retained in the base material, and on the other hand, if the amount exceeds this, it becomes difficult to make it opaque because the amount of the organic low molecular weight substance is small.

本発明のオーバーコート層に用いられるポリシロキサン
グラフトポリマーとは、ポリシロキサンを幹とし、これ
に任意の重合体の枝をつけたもので、このグラフトポリ
マーはポリシロキサン及び任意の重合体の両方の性質が
ある程度型なった特異な性質を示す、二＼で軸部分のポ
リシロキサンとしては公知のものが全て使用できる。即
ちこのポリシロキサン（オルガノポリシロキサン）は全
体の有機基のうち殆んどがメチル基で極少量ビニル基を
含有させたメチルビニルポリシロキサンが一般的である
。またメチル基の一部を水素原子、フェニル基、アリル
基などで置換することも可能である。一方、核部分の任
意の重合体としては、アクリル酸ブチル、アクリル酸−
２−エチルヘキシル等のアクリル酸エステル類；メタク
リル酸メチル、メタクリル酸ブチル等のメタクリル酸エ
ステル類；酢酸ビニル、プロピオン酸ビニル等のビニル
エステル類；スチレン、ビニルトルエン等の芳香族ビニ
ル類；アクリロニトリル、メタクリロニトリル等の不飽
和ニトリル類；アクリルアミド、Ｎ−メチロールアクリ
ルアミド等の不飽和アミド類；エチレン、プロピレン、
イソブチレン等のα−オレフィン類；メチルビニルエー
テル、エチルビニルエーテル、ｔ−ブチルビニルエーテ
ル等のビニルエーテル類；塩化ビニル、塩化ビニリデン
、弗化ビニル、弗化ビニリデン等の含ハロゲンα、β−
不飽和単量体類；（メタ）アクリル酸トリフルオロエチ
ル、２，２，３．３−テトラフルオロプロピルアクリレ
ート、ＬＨ，ＬＨ，２Ｈ，２Ｈ−へブタデカフルオロデ
シルアクリレート、ＩＨ，ＬＨ。The polysiloxane graft polymer used in the overcoat layer of the present invention has polysiloxane as its backbone and branches of an arbitrary polymer attached to it, and this graft polymer contains both polysiloxane and an arbitrary polymer. All known polysiloxanes can be used as the polysiloxane for the shaft portion, which exhibits unique properties with a certain degree of pattern. That is, this polysiloxane (organopolysiloxane) is generally methylvinylpolysiloxane in which most of the organic groups are methyl groups and a very small amount of vinyl groups are contained. It is also possible to partially substitute a methyl group with a hydrogen atom, a phenyl group, an allyl group, or the like. On the other hand, as the arbitrary polymer of the core part, butyl acrylate, acrylic acid-
Acrylic esters such as 2-ethylhexyl; Methacrylic esters such as methyl methacrylate and butyl methacrylate; Vinyl esters such as vinyl acetate and vinyl propionate; Aromatic vinyls such as styrene and vinyltoluene; Acrylonitrile and methacrylate Unsaturated nitriles such as lonitrile; unsaturated amides such as acrylamide and N-methylolacrylamide; ethylene, propylene,
α-olefins such as isobutylene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether; halogen-containing α-, β- such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, etc.
Unsaturated monomers; trifluoroethyl (meth)acrylate, 2,2,3.3-tetrafluoropropyl acrylate, LH, LH, 2H, 2H-hebutadecafluorodecyl acrylate, IH, LH.

５Ｈ−オクタフルオロペンチルアクリレート等の含弗素
（メタ）アクリル酸エステル類；　２，３，５．６−チ
トラフルオロフエニルアクリル酸エステル、２．３，４
，５，６−ペンタフルオロフェニルメタクリル酸エステ
ル等の芳香族弗素含有（メタ）アクリル酸エステル等の
単量体の重合体が挙げられる。Fluorine-containing (meth)acrylic acid esters such as 5H-octafluoropentyl acrylate; 2,3,5.6-titrafluorophenyl acrylic ester, 2.3,4
Examples include polymers of monomers such as aromatic fluorine-containing (meth)acrylic esters such as , 5,6-pentafluorophenyl methacrylic esters.

なおポリシロキサンと任意の重合体の割合を適宜変化さ
せることにより、ポリシロキサンの滑り性を維持したま
ま下層との密着性を向上させることが可能である。Note that by appropriately changing the proportion of polysiloxane and any polymer, it is possible to improve the adhesion with the lower layer while maintaining the slipperiness of polysiloxane.

オーバーコート層の厚さは、摩擦係数に影響を与える要
因が表面物性に限られるところから最低１分子あればよ
く、多くとも５μｍ程度、好ましくは３μｍ程度が適当
である。５μｍ以上になると、熱感度が低下する傾向が
ある。The thickness of the overcoat layer should be at least one molecule since the factors that influence the coefficient of friction are limited to surface properties, and the appropriate thickness is about 5 μm at most, preferably about 3 μm. If the thickness exceeds 5 μm, thermal sensitivity tends to decrease.

以下に本発明を実施例によって説明する。なお１部」及
び「％」はいずれも重量基準である。The present invention will be explained below by way of examples. Note that both "1 part" and "%" are based on weight.

実施例１ ７５μｍ厚のポリエステルフィルム上にベヘン酸　　　
　　　　　　　　　　４部ステアリルステアレート　　
　　　　１部テトラヒドロフラン　　　　　　　　９２
部よりなる溶液をワイヤーバーで塗布し、加熱乾燥して
１５μｍ厚の感熱層を設けた。Example 1 Behenic acid on a 75 μm thick polyester film
4 parts stearyl stearate
1 part Tetrahydrofuran 92
A solution consisting of 1.5 μm was applied with a wire bar and dried by heating to form a heat-sensitive layer with a thickness of 15 μm.

その上に 硬化剤（同上用）０．２部 ジオキサン　　　　　　　　　　　　１０部よりなる組
成物を均一に溶解した後、ワイヤーバーで塗布し加熱乾
燥して０．５μｍ厚のポリシロキサングラフトポリマー
からなるオーバーコート層を設け、その後６５℃に再加
熱することにより、透明な可逆性感熱記録材料を作った
。After uniformly dissolving a composition consisting of 0.2 parts of a curing agent (for the same as above) and 10 parts of dioxane, it was coated with a wire bar and dried by heating to form an overcoat layer of 0.5 μm thick polysiloxane graft polymer. A transparent reversible heat-sensitive recording material was produced by setting the temperature at 65° C. and then reheating it to 65°C.

実施例２ ステアリルステアレート１部の代りにアジピン酸ジー２
−エチルヘキシル２部を用いた他は実施例１と同様にし
て１０μｍ厚の感熱層を設けた。Example 2 2 parts of adipic acid instead of 1 part of stearyl stearate
- A heat-sensitive layer having a thickness of 10 μm was provided in the same manner as in Example 1 except that 2 parts of ethylhexyl was used.

その上に実施例１と同様にして２μｍ厚のオーバーコー
ト層を設け、その後８５℃に再加熱することにより白濁
不透明な可逆性感熱記録材料を作った。A 2 μm thick overcoat layer was provided thereon in the same manner as in Example 1, and then reheated to 85° C. to produce a cloudy, opaque reversible thermosensitive recording material.

実施例３ 感熱層形成液からステアリルステアレートを除いた他は
実施例１と同様にして透明な可逆性感熱記録材料を作っ
た。Example 3 A transparent reversible heat-sensitive recording material was produced in the same manner as in Example 1, except that stearyl stearate was removed from the heat-sensitive layer forming liquid.

実施例４ 感熱層形成液中のポリシロキサングラフトポリマーとし
て日本触媒化学工業（株）製Ｒ−１８を用いた他は実施
例１と同様にして透明な可逆性感熱記録材料を作った。Example 4 A transparent reversible heat-sensitive recording material was produced in the same manner as in Example 1, except that R-18 manufactured by Nippon Shokubai Chemical Co., Ltd. was used as the polysiloxane graft polymer in the heat-sensitive layer forming liquid.

比較例１ オーバーコート層を設けなかった他は実施例１と同様に
して透明な可逆性感熱記録材料を作った。Comparative Example 1 A transparent reversible thermosensitive recording material was produced in the same manner as in Example 1 except that no overcoat layer was provided.

比較例２ オーバーコート層形成液として、 トルエン　　　　　　　　　　　　４９．９部よりなる
溶液を用いた他は実施例１と同様にして透明な可逆性感
熱記録材料を作成した。Comparative Example 2 A transparent reversible thermosensitive recording material was prepared in the same manner as in Example 1, except that a solution containing 49.9 parts of toluene was used as the overcoat layer forming liquid.

次に以上のようにして作成した可逆性感熱記録材料を６
ドツト／ｍｎの薄膜サーマルヘッドを用いて０．５■／
ドツトで画像形成を行ない、実施例１，３，４、比較例
１，２は透明地に白濁画像、実施例２は白濁地に透明画
像を形成した。Next, the reversible thermosensitive recording material prepared as described above was
0.5μ/m using a dot/mn thin film thermal head
Images were formed using dots, and in Examples 1, 3, and 4 and Comparative Examples 1 and 2, a cloudy image was formed on a transparent background, and in Example 2, a transparent image was formed on a cloudy background.

これを黒色紙上に置きマクベス濃度計ＲＤ５１４で反射
濃度を測定した。さらに画像の形成と消去を５０回繰返
した時の濃度を測定した。This was placed on black paper and the reflection density was measured using a Macbeth densitometer RD514. Furthermore, the density was measured after image formation and erasure were repeated 50 times.

その結果を下表に示す。The results are shown in the table below.

この表から本発明のようにポリシロキサングラフトポリ
マーのオーバーコート層を設けることにより画像の形成
と消去を繰返しても安定した画像濃度を得られることが
判る。This table shows that by providing an overcoat layer of polysiloxane graft polymer as in the present invention, stable image density can be obtained even if image formation and erasing are repeated.

羞−一果 本発明の可逆性感熱記録材料は以上のようにポリシロキ
サングラフトポリマーのオーバーコート層を設けたので
、サーマルヘッド等との密着が良くなり、従来より熱感
度が向上して鮮明な画像が形成でき、且つ、オーバーコ
ート層の接着性が良いため、繰返し使用しても画像劣化
も殆んどない等の利点を有している。As a result, since the reversible thermosensitive recording material of the present invention is provided with an overcoat layer of polysiloxane graft polymer as described above, it has better adhesion with a thermal head, etc., and has improved thermal sensitivity and clear images compared to conventional ones. Since an image can be formed and the overcoat layer has good adhesion, it has the advantage that there is almost no image deterioration even after repeated use.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明可逆性感熱記録材料の記録及び消去原理
の説明図である。FIG. 1 is an explanatory diagram of the recording and erasing principle of the reversible thermosensitive recording material of the present invention.

Claims (1)

【特許請求の範囲】[Claims] １、支持体上に樹脂母材とこの樹脂母材中に分散された
有機低分子物質を主成分としてなり、温度に依存して透
明度が可逆的に変化する感熱層と更にその上にポリシロ
キサングラフトポリマーを主成分とするオーバーコート
層を設けたことを特徴とする可逆性感熱記録材料。1. A resin base material on a support, a heat-sensitive layer whose main component is an organic low-molecular substance dispersed in the resin base material, and whose transparency changes reversibly depending on the temperature, and a polysiloxane layer on the heat-sensitive layer. A reversible thermosensitive recording material characterized by having an overcoat layer containing a graft polymer as a main component.
JP62152550A 1987-03-10 1987-06-19 Reversible thermosensitive recording material Expired - Lifetime JP2582784B2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP62152550A JP2582784B2 (en) 1987-06-19 1987-06-19 Reversible thermosensitive recording material
US07/321,854 US5017421A (en) 1987-03-10 1989-03-10 Reversible thermosensitive recording material
US07/627,329 US5108980A (en) 1987-03-10 1990-12-14 Reversible thermosensitive recording material
US08/231,751 USRE37034E1 (en) 1987-03-10 1994-04-25 Reversible thermosensitive recording material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62152550A JP2582784B2 (en) 1987-06-19 1987-06-19 Reversible thermosensitive recording material

Publications (2)

Publication Number Publication Date
JPS63317385A true JPS63317385A (en) 1988-12-26
JP2582784B2 JP2582784B2 (en) 1997-02-19

Family

ID=15542916

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62152550A Expired - Lifetime JP2582784B2 (en) 1987-03-10 1987-06-19 Reversible thermosensitive recording material

Country Status (1)

Country Link
JP (1) JP2582784B2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02187389A (en) * 1989-01-17 1990-07-23 Tomoegawa Paper Co Ltd Heat transfer sheet with reversible heat-sensitive recording layer
JPH03227688A (en) * 1990-02-02 1991-10-08 Nitto Denko Corp Reversible thermal recording material
EP1234681A1 (en) 2001-02-26 2002-08-28 Ricoh Company, Ltd. Reversible thermosensitive recording medium and image processing method using the same
US6794334B2 (en) 2000-06-13 2004-09-21 Ricoh Company, Ltd. Thermo reversible recording medium, member having information memorizing part, thermo reversible recording label, method of and apparatus for image processing
US7049268B2 (en) 2002-06-03 2006-05-23 Ricoh Company, Ltd. Heat reversible recording medium, heat reversible recording label, heat reversible recording member, image processor and image processing method

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02187389A (en) * 1989-01-17 1990-07-23 Tomoegawa Paper Co Ltd Heat transfer sheet with reversible heat-sensitive recording layer
JPH0455876B2 (en) * 1989-01-17 1992-09-04 Tomoegawa Paper Co Ltd
JPH03227688A (en) * 1990-02-02 1991-10-08 Nitto Denko Corp Reversible thermal recording material
US6794334B2 (en) 2000-06-13 2004-09-21 Ricoh Company, Ltd. Thermo reversible recording medium, member having information memorizing part, thermo reversible recording label, method of and apparatus for image processing
EP1234681A1 (en) 2001-02-26 2002-08-28 Ricoh Company, Ltd. Reversible thermosensitive recording medium and image processing method using the same
US7049268B2 (en) 2002-06-03 2006-05-23 Ricoh Company, Ltd. Heat reversible recording medium, heat reversible recording label, heat reversible recording member, image processor and image processing method

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