JPH0752553A - Thermally reversible heat-sensitive recording material - Google Patents
Thermally reversible heat-sensitive recording materialInfo
- Publication number
- JPH0752553A JPH0752553A JP5207327A JP20732793A JPH0752553A JP H0752553 A JPH0752553 A JP H0752553A JP 5207327 A JP5207327 A JP 5207327A JP 20732793 A JP20732793 A JP 20732793A JP H0752553 A JPH0752553 A JP H0752553A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- recording layer
- erasing
- printing
- recording
- 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
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、可視画像を繰り返し表
示、消去することができる熱可逆性感熱記録材料に関す
る。FIELD OF THE INVENTION The present invention relates to a thermoreversible thermosensitive recording material capable of repeatedly displaying and erasing a visible image.
【０００２】[0002]
【従来の技術】交通機関の定期券、催し会場や建物への
入場許可証などは、毎日繰り返し使用されるが、管理上
不正乗車、不正入場をチエツクする手段がない。近年、
一部で磁気カ−ドによるチエツク法も採用されつつある
が、チエツクの有無が目視できないため、装置上のトラ
ブルによるチエツクもれのおそれがあり、管理者、利用
者とも不便を感じていた。また各種プリペイドカ−ドに
おいても、磁気カ−ドやＩＣカ−ドが使用されている
が、記録内容が直接目視できないため、支払い金額や残
額を簡単にチエツクできず、使用者に対する内容保証の
点で問題があった。2. Description of the Related Art A commuter pass for a transportation facility, an admission permit for an event venue or a building, etc. are used repeatedly every day, but there is no means for checking illegal boarding or entrance due to management. recent years,
Although a check method using a magnetic card is being adopted in some parts, since the presence or absence of a check cannot be visually checked, there is a risk of check leakage due to a trouble on the device, and both the manager and the user feel inconvenient. Magnetic cards and IC cards are also used in various prepaid cards, but since the recorded contents cannot be viewed directly, it is not possible to easily check the amount paid or the balance, which guarantees the contents to the user. There was a problem in terms.
【０００３】そのため従来、記録媒体に目視可能な記録
を行い、またそれを消去する方法が提案されている。例
えば、合成樹脂母材の中に有機低分子物質を分散させ、
温度により透明状態と不透明（白濁）状態に変化する材
料（特開昭５５−１５４１９８）を使用することが提案
されている。この材料は、特定のある温度域から常温に
冷却すると透明になり、またそれよりも高い別の温度域
から常温に冷却されると白濁する性質を有するため、そ
れを利用して可視画像を可逆的に印字・消去することが
できる。Therefore, conventionally, there has been proposed a method of visually recording on a recording medium and erasing it. For example, disperse an organic low molecular weight substance in a synthetic resin matrix,
It has been proposed to use a material (JP-A-55-154198) that changes between a transparent state and an opaque (white turbid) state depending on temperature. This material has the property of becoming transparent when cooled from a certain temperature range to room temperature and becoming cloudy when cooled to room temperature from another higher temperature range. Can be printed / erased manually.
【０００４】[0004]
【発明が解決しようとする課題】この感熱記録材料の印
字・消去の手段としては、各温度に設定された加熱スタ
ンプや加熱ローラーなどが考えられるが、印字・消去の
高速化、および装置の簡易化・コンパクト化などの点か
らサーマルヘツドを用いることが多い。しかしながらサ
ーマルヘツドを用いた場合、印字・消去の際に高温状態
で圧力・せん断力が大きく加わるため物理的に記録層が
つぶれてしまい、印字・消去の繰り返し耐久性が悪いと
いう問題があった。またサーマルヘツドの処理速度の高
速化が進むにつれて記録層にかかる圧力・せん断力も大
きくなり、耐久性が低下する原因となっていた。As a means for printing / erasing the heat-sensitive recording material, a heating stamp or a heating roller set at each temperature is conceivable, but speeding up the printing / erasing and simplifying the apparatus are possible. A thermal head is often used from the standpoints of downsizing and downsizing. However, when the thermal head is used, there is a problem that the recording layer is physically crushed due to the large pressure and shearing force applied at high temperature during printing / erasing, and the durability against repeated printing / erasing is poor. Further, as the processing speed of the thermal head has been increased, the pressure and shearing force applied to the recording layer are also increased, which has been a cause of deterioration in durability.
【０００５】[0005]
【課題を解決するための手段】本発明は上記問題点を解
決するために、記録層の高温時での弾性率を向上させる
目的で、有機低分子物質を分散させる樹脂母材として、
紫外線または電子線硬化樹脂と、イソシアネート架橋樹
脂とを併用したことを特徴としている。In order to solve the above problems, the present invention provides a resin base material in which an organic low molecular weight substance is dispersed for the purpose of improving the elastic modulus of a recording layer at high temperature.
It is characterized in that an ultraviolet or electron beam curing resin and an isocyanate cross-linking resin are used in combination.
【０００６】以下本発明を詳しく説明する。図１は、本
発明熱可逆性感熱記録材料を適用した感熱記録シートの
層構成の例を示す断面図である。図１において、１は基
材であり、一般にはポリエチレンテレフタレート（ＰＥ
Ｔ）などの樹脂シートや紙が用いられる。２は感熱記録
層であり、基材１と記録層２との間に記録のコントラス
トを上げるための光反射層４があっても良い。３は保護
層であり、サーマルヘツドに接触する層である。各層間
には必要に応じアンカー剤層や接着剤層を設けても良
い。The present invention will be described in detail below. FIG. 1 is a sectional view showing an example of the layer structure of a thermosensitive recording sheet to which the thermoreversible thermosensitive recording material of the present invention is applied. In FIG. 1, reference numeral 1 is a substrate, which is generally polyethylene terephthalate (PE
A resin sheet such as T) or paper is used. Reference numeral 2 denotes a heat-sensitive recording layer, and a light reflection layer 4 for increasing recording contrast may be provided between the substrate 1 and the recording layer 2. 3 is a protective layer, which is a layer in contact with the thermal head. An anchor agent layer or an adhesive layer may be provided between the layers as necessary.
【０００７】この感熱記録シートの保護層３上からサー
マルヘツドにて印字・消去を行う場合を考えると、記録
層２は樹脂母材に低分子物を分散させたものであり、温
度によって結晶化度などを変えるという媒体自体の特性
上、一般的には高温時の弾性率は低く、圧力、せん断に
弱い。しかし基材１は強度的にしっかりしているため、
保護層３上から高温状態（記録層が軟化した状態）でせ
ん断力をかけると、記録層２に最も負担がかかってつぶ
れてしまう。Considering the case where printing and erasing are performed on the protective layer 3 of the thermosensitive recording sheet with a thermal head, the recording layer 2 is a resin base material in which low molecular weight substances are dispersed, and is crystallized by temperature. Due to the characteristics of the medium itself, such as changing the degree, the elastic modulus at high temperature is generally low, and it is weak against pressure and shear. However, since the base material 1 is strong in strength,
When a shearing force is applied from above the protective layer 3 in a high temperature state (a state where the recording layer is softened), the recording layer 2 is most burdened and is crushed.
【０００８】特に物理的に硬い基材１と軟らかい記録層
２の界面が最もせん断を受けやすく、記録層２の下層部
から歪みが起こる。そのため繰り返し印字・消去におい
て記録層下層部から徐々につぶれ始め、印字白濁度は低
下していく。サーマルヘツドの処理速度が速い場合には
せん断力も大きくなるため、この劣化はさらに著しくな
る。In particular, the interface between the physically hard substrate 1 and the soft recording layer 2 is most susceptible to shearing, and distortion occurs from the lower layer portion of the recording layer 2. Therefore, during repeated printing and erasing, the print layer gradually begins to be crushed from the lower layer portion, and the white turbidity of the print decreases. When the thermal head processing speed is high, the shearing force also becomes large, and this deterioration becomes more remarkable.
【０００９】以上のように、繰り返し耐久性の低下の直
接的な原因は圧力・せん断による記録層のつぶれによる
ものと考えられる。そこで記録層の高温時での弾性率を
向上させるために鋭意検討を重ね、樹脂母材として紫外
線または電子線を用いて硬化重合させるポリマーと、イ
ソシアネートおよびイソシアネート誘導体からなる架橋
剤により架橋されるポリマーを併用するという本発明に
至った。As described above, it is considered that the direct cause of the deterioration of the repeated durability is crushing of the recording layer due to pressure and shear. Therefore, in order to improve the elastic modulus of the recording layer at high temperature, earnest studies have been made, and a polymer that is cured and polymerized by using ultraviolet rays or electron beams as a resin base material and a polymer that is crosslinked by a crosslinking agent composed of isocyanate and an isocyanate derivative. The present invention has been achieved in which
【００１０】すなわち、紫外線または電子線硬化性樹脂
は弾性率向上の面で有利な材料であるが、溶剤塗工によ
り記録層を形成、製膜する場合、加熱により溶剤を除去
した時には今だ未硬化であるため、樹脂母材が形成され
ておらず低分子物質を分散させる製膜が困難になる。そ
こで通常の溶剤可溶で乾燥すると固化する樹脂を添加し
ていくと加熱乾燥時の記録層製膜を容易にすることがで
きる。ところが溶剤乾燥型樹脂は紫外線または電子線硬
化性樹脂よりも高温時の弾性率が低く記録層の弾性率が
低下するので、それを補うために、溶剤乾燥型樹脂にイ
ソシアネート架橋剤を添加して架橋させる。That is, the ultraviolet ray or electron beam curable resin is an advantageous material in terms of improving the elastic modulus, but when the recording layer is formed and formed by solvent coating and the solvent is removed by heating, it is still unclear. Since it is cured, the resin base material is not formed, and it becomes difficult to form a film in which the low-molecular substance is dispersed. Therefore, by adding a resin that is soluble in a usual solvent and solidifies when dried, it is possible to easily form a recording layer film during heating and drying. However, the solvent-drying type resin has a lower elastic modulus at a high temperature than the ultraviolet ray or electron beam curable resin and the elastic modulus of the recording layer decreases, so in order to compensate for this, an isocyanate crosslinking agent is added to the solvent-drying type resin. Crosslink.
【００１１】本発明における記録層２中の高分子樹脂母
材として用いる紫外線または電子線硬化性樹脂として
は、ウレタンアクリレート系、エポキシアクリレート
系、ポリエステルアクリレート系、ポリエーテルアクリ
レート系、ビニル系、不飽和ポリエステルなどのオリゴ
マーや、各種単官能、多官能のアクリレート、メタクリ
レート、ビニルエステル、スチレン誘導体、アリル化合
物などのモノマーが挙げられる。これらは各種組み合わ
せて配合しても単独で用いても構わない。The ultraviolet ray or electron beam curable resin used as the polymer resin base material in the recording layer 2 in the present invention includes urethane acrylate type, epoxy acrylate type, polyester acrylate type, polyether acrylate type, vinyl type and unsaturated. Examples thereof include oligomers such as polyester, and various monofunctional and polyfunctional acrylates, methacrylates, vinyl esters, styrene derivatives, allyl compounds and other monomers. These may be blended in various combinations or used alone.
【００１２】また紫外線硬化の場合は、ベンゾイン系、
アセトフエノン系、パ−オキシド系などの光重合開始剤
を添加させて紫外線照射により硬化重合させる。なお、
これらの樹脂としては記録層の特性上透明性が良く、黄
変性の少ないものが望ましい。Further, in the case of UV curing, benzoin type,
A photopolymerization initiator such as an acetophenone type or a peroxide type is added and cured and polymerized by ultraviolet irradiation. In addition,
It is desirable that these resins have good transparency and little yellowing due to the characteristics of the recording layer.
【００１３】またこれと併用するイソシアネート架橋性
樹脂としては、透明で製膜性の良い樹脂が望ましく、ポ
リ塩化ビニル、塩化ビニル−酢酸ビニル共重合体などの
塩化ビニル共重合体、ポリ塩化ビニリデン、塩化ビニリ
デン共重合体、ポリエステル、ポリアミド、ポリスチレ
ン、ポリメチル（メタ）アクリレートまたはその共重合
体などが挙げられ、イソシアネート基が反応するための
官能基（ＯＨ基，ＮＨ2 基，ＣＯＯＨ基など）を有して
いるものが望ましい。As the isocyanate crosslinkable resin used in combination therewith, a transparent and film-forming resin is desirable, and polyvinyl chloride, vinyl chloride copolymers such as vinyl chloride-vinyl acetate copolymer, polyvinylidene chloride, Examples thereof include vinylidene chloride copolymers, polyesters, polyamides, polystyrenes, polymethyl (meth) acrylates or copolymers thereof, which have a functional group (OH group, NH 2 group, COOH group, etc.) for reacting an isocyanate group. What you are doing is desirable.
【００１４】そしてこれらにイソシアネート基を反応さ
せて三次元網目状に架橋させる。イソシアネートおよび
イソシアネート誘導体からなる架橋剤としてはＴＤＩ
（トルエンジイソシアネート）、ＨＤＩ（ヘキサメチレ
ンジイソシアネート）、ＭＤＩ（メチレンジイソシアネ
ート）、およびそれぞれの誘導体などの架橋剤が挙げら
れるがこれらの限りではない。Then, these are reacted with an isocyanate group to crosslink in a three-dimensional network. TDI as a cross-linking agent consisting of isocyanate and isocyanate derivatives
(Toluene diisocyanate), HDI (hexamethylene diisocyanate), MDI (methylene diisocyanate), and a cross-linking agent such as a derivative thereof, but not limited thereto.
【００１５】またこれらのイソシアネート架橋性ポリマ
ーと上記紫外線または電子線硬化樹脂との配合比につい
ては、それぞれに選択する樹脂により変わるが、記録層
製膜性や、記録特性、屈折率、弾性率、相溶性、生産性
などを考慮して、重量比で９：１〜１：９程度の範囲で
任意に配合できる。The compounding ratio of these isocyanate crosslinkable polymers and the above ultraviolet or electron beam curable resin varies depending on the resin selected, but the recording layer film-forming properties, recording characteristics, refractive index, elastic modulus, In consideration of compatibility, productivity, etc., it can be arbitrarily blended in a weight ratio of about 9: 1 to 1: 9.
【００１６】樹脂母材中に分散させる有機低分子物質と
しては、高級脂肪酸、高級脂肪酸エステル、高級ジカル
ボン酸、高級ケトン、高級エ−テル、高級アルコ−ル、
およびその誘導体などが挙げられる。保護層３として
は、ＰＥＴ、ポリエーテルイミド、ポリエーテルエーテ
ルケトン、ポリサルフオン、ポリフエニレンサルフアイ
ド、ポリアリレート、ポリエーテルサルフオン、ポリカ
ーボネート、ポリエチレンナフタレート、ポリイミド、
アクリル樹脂、紫外線または電子線硬化樹脂などの耐熱
性の高い透明樹脂のフイルムあるいは塗膜を用いること
ができる。Examples of the organic low molecular weight substance dispersed in the resin base material include higher fatty acids, higher fatty acid esters, higher dicarboxylic acids, higher ketones, higher ethers, higher alcohols,
And derivatives thereof. Examples of the protective layer 3 include PET, polyetherimide, polyetheretherketone, polysulfone, polyphenylene sulfide, polyarylate, polyether sulfone, polycarbonate, polyethylene naphthalate, polyimide,
A film or coating film of a transparent resin having high heat resistance such as acrylic resin, ultraviolet ray or electron beam curing resin can be used.
【００１７】このカードは例えば、入場、買物、レンタ
ルなどのプリペイドカードとして使用することができ、
使用の都度、使用金額および残額を磁気記録とともに記
録層２に可視的に表示することにより、常に正確な残額
を知ることができる。また各種感熱記録紙として利用す
ることができる。This card can be used as a prepaid card for entrance, shopping, rental, etc.,
By visually displaying the used amount and the remaining amount together with the magnetic recording on the recording layer 2 each time the device is used, it is possible to always know the accurate remaining amount. Further, it can be used as various thermal recording papers.
【００１８】[0018]
（実施例）基材１として１８８μｍ厚の透明ＰＥＴフイ
ルムを使用し、その表面にアルミ蒸着を施し、光反射層
４を形成し、その上に記録層２を１０μｍ厚に積層し
た。記録層の組成は、 塩化ビニル−アクリル酸エステル共重合体（ＯＨ変性） １００重量部 （積水化学工業社 Ｅ−Ｃ１３０） トルエンジイソシアネート ５重量部 （日本ポリウレタン工業社 コロネートＬ） ポリエチレングリコールジアクリレート（ＰＥＧＤＡ） ５０重量部 １２−トリコサノン ４０重量部 １，１２−テトラデカン二酸 １０重量部 光重合開始剤（１−ヒドロキシシクロヘキシルフェニルケトン） ２重量部 である。(Example) A transparent PET film having a thickness of 188 μm was used as the substrate 1, aluminum was vapor-deposited on the surface thereof to form a light reflecting layer 4, and the recording layer 2 was laminated thereon to a thickness of 10 μm. The composition of the recording layer was as follows: vinyl chloride-acrylic acid ester copolymer (OH modified) 100 parts by weight (Sekisui Chemical Co., Ltd. E-C130) toluene diisocyanate 5 parts by weight (Nippon Polyurethane Industry Co., Ltd. Coronate L) polyethylene glycol diacrylate (PEGDA) ) 50 parts by weight 12-tricosanone 40 parts by weight 1,12-tetradecanedioic acid 10 parts by weight Photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) 2 parts by weight.
【００１９】この組成物をテトラヒドロフランに溶解し
アルミ蒸着層の上に塗布し、加熱乾燥してイソシアネー
ト架橋させるとともに、エネルギー８０Ｗ／ｃｍ、フイ
ルム速度１０ｍ／分で紫外線照射して硬化重合させて記
録層２を作成した。さらにその上に２μｍのＰＥＴフィ
ルムをラミネ−トして保護層３を形成した。そしてカ−
ド状に打抜き、本発明記録材料を使用したカ−ドを作成
した。This composition was dissolved in tetrahydrofuran, coated on an aluminum vapor-deposited layer, dried by heating to crosslink the isocyanate, and was irradiated with ultraviolet rays at an energy of 80 W / cm and a film speed of 10 m / min to cure and polymerize the recording layer. Created 2. Further, a PET film having a thickness of 2 μm was laminated thereon to form a protective layer 3. And the car
It was punched into a card shape to prepare a card using the recording material of the present invention.
【００２０】このようにして得られたカ−ドは初期状態
で白濁状態であったが、表面を８０℃の加熱スタンプで
加熱するとその部分は透明化され反射層が目視された。
次に８ドツト／ｍｍのサ−マルヘツドにて印加時間１．
１ｍｓｅｃにおいて０．２２ｍＪ／ドツトのエネルギ−
で文字を印字したところ、記録層の印字部は白濁化さ
れ、鮮明な文字が浮かび上がった。The card thus obtained was in an opaque state in the initial state, but when the surface was heated with a heating stamp at 80 ° C., the part was made transparent and the reflective layer was visually observed.
Next, at a thermal head of 8 dots / mm, the application time is 1.
Energy of 0.22 mJ / dot at 1 msec
When a character was printed with, the printed portion of the recording layer became cloudy, and clear characters emerged.
【００２１】これらの印字された記録面に再度、前記条
件において加熱消去、加熱印字を実施すると繰返し５０
０回以上の印字・消去が可能であることが確認され、繰
り返しテスト後の断面写真観察等においてもサーマルヘ
ツド印字における圧力、せん断に対して記録層がつぶれ
にくくなっていることが確認できた。When heat-erasing and heat-printing are again carried out on these printed recording surfaces under the above-mentioned conditions, it is repeated 50 times.
It was confirmed that printing and erasing can be performed 0 times or more, and it was confirmed that the recording layer was less likely to be crushed by the pressure and shear in the thermal head printing even when observing a cross-sectional photograph after the repeated test.
【００２２】（比較例）上記実施例における記録層を構
成する樹脂の中から、アクリレートモノマーであるＰＥ
ＧＤＡと光重合開始剤およびトルエンジイソシアネート
を除いて、紫外線照射による硬化重合および熱架橋を行
わない以外はすべて同様に行った。結果は、繰り返し５
００回の印字・消去において印字部が保護層上から凹ん
だようになっており、白濁度の低下が見られた。断面写
真を撮ってみると記録層がつぶれていることが解り、サ
ーマルヘツド印字においての圧力、せん断によって記録
層に負担がかかってつぶれたことが確認された。(Comparative Example) PE which is an acrylate monomer was selected from the resins constituting the recording layer in the above-mentioned examples.
Except for GDA, a photopolymerization initiator and toluene diisocyanate, the same procedure was carried out except that curing polymerization by ultraviolet irradiation and thermal crosslinking were not performed. The result is repeat 5
After printing and erasing for 00 times, the printed part appeared to be recessed from the protective layer, and the white turbidity was reduced. When a cross-sectional photograph was taken, it was found that the recording layer was crushed, and it was confirmed that the recording layer was crushed due to pressure and shear in the thermal head printing.
【００２３】[0023]
【発明の効果】本発明の熱可逆性感熱記録材料は、サー
マルヘツドなどによる圧力・せん断力の大きな記録印字
・消去手段においても良好な繰り返し耐久性をもつと同
時に、記録層製膜性が良好なものである。これにより印
字・消去の高速化や装置のコンパクト化による繰り返し
耐久性の低下を軽減でき、可逆性感熱記録シートなどの
リサイクル性向上ができる。INDUSTRIAL APPLICABILITY The thermoreversible thermosensitive recording material of the present invention has good repetitive durability even in recording / printing / erasing means having a large pressure / shearing force due to thermal head and the like, and at the same time has good recording layer film forming property. It is something. As a result, it is possible to reduce the deterioration of repeated durability due to the speeding up of printing and erasing and the downsizing of the device, and it is possible to improve the recyclability of the reversible thermosensitive recording sheet.
【図１】本発明の熱可逆性感熱記録材料を適用した感熱
記録シートの層構成の例を示す断面図。FIG. 1 is a sectional view showing an example of the layer structure of a thermosensitive recording sheet to which the thermoreversible thermosensitive recording material of the present invention is applied.
１ 基材 ２ 記録層 ３ 保護層 1 base material 2 recording layer 3 protective layer
Claims (1)
てなり、温度により透明状態と不透明状態との可逆変化
を生じる熱可逆性感熱記録材料において、樹脂母材が、
紫外線または電子線硬化樹脂と、イソシアネート架橋樹
脂との混合樹脂からなることを特徴とする熱可逆性感熱
記録材料。1. A thermoreversible thermosensitive recording material comprising an organic low-molecular substance dispersed in a resin base material, which causes a reversible change between a transparent state and an opaque state depending on temperature, wherein the resin base material comprises:
A thermoreversible thermosensitive recording material comprising a resin mixture of an ultraviolet or electron beam curing resin and an isocyanate cross-linking resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5207327A JP2942689B2 (en) | 1993-08-23 | 1993-08-23 | Thermoreversible thermosensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5207327A JP2942689B2 (en) | 1993-08-23 | 1993-08-23 | Thermoreversible thermosensitive recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0752553A true JPH0752553A (en) | 1995-02-28 |
| JP2942689B2 JP2942689B2 (en) | 1999-08-30 |
Family
ID=16537927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5207327A Expired - Lifetime JP2942689B2 (en) | 1993-08-23 | 1993-08-23 | Thermoreversible thermosensitive recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2942689B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2320582A (en) * | 1996-12-20 | 1998-06-24 | Ricoh Kk | Reversible thermosensitive recording material |
| JPH10509644A (en) * | 1994-12-02 | 1998-09-22 | ウェスコーン クラッシャーズ プロプライエタリー リミテッド | Improved gyrate crusher |
| GB2326726A (en) * | 1997-06-26 | 1998-12-30 | Ricoh Kk | Reversible thermosensitive recording material |
-
1993
- 1993-08-23 JP JP5207327A patent/JP2942689B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10509644A (en) * | 1994-12-02 | 1998-09-22 | ウェスコーン クラッシャーズ プロプライエタリー リミテッド | Improved gyrate crusher |
| GB2320582A (en) * | 1996-12-20 | 1998-06-24 | Ricoh Kk | Reversible thermosensitive recording material |
| US5981115A (en) * | 1996-12-20 | 1999-11-09 | Ricoh Company, Ltd. | Reversible thermosensitive recording material |
| GB2320582B (en) * | 1996-12-20 | 2001-10-03 | Ricoh Kk | Reversible thermosensitive recording material |
| DE19756888B4 (en) * | 1996-12-20 | 2007-12-13 | Ricoh Co., Ltd. | Reversible thermosensitive recording material, method of production, recording method and coating liquid |
| GB2326726A (en) * | 1997-06-26 | 1998-12-30 | Ricoh Kk | Reversible thermosensitive recording material |
| US6090748A (en) * | 1997-06-26 | 2000-07-18 | Ricoh Company, Ltd. | Reversible thermosensitive recording material and recording method and recording apparatus therefor |
| GB2326726B (en) * | 1997-06-26 | 2002-06-12 | Ricoh Kk | Reversible thermosensitive recording material and recording method and recording apparatus therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2942689B2 (en) | 1999-08-30 |
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