EP0387264A1 - Inking ribbon. - Google Patents

Inking ribbon.

Info

Publication number
EP0387264A1
EP0387264A1 EP88909286A EP88909286A EP0387264A1 EP 0387264 A1 EP0387264 A1 EP 0387264A1 EP 88909286 A EP88909286 A EP 88909286A EP 88909286 A EP88909286 A EP 88909286A EP 0387264 A1 EP0387264 A1 EP 0387264A1
Authority
EP
European Patent Office
Prior art keywords
ink
ribbon according
ribbon
mobile
transferred
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
EP88909286A
Other languages
German (de)
French (fr)
Other versions
EP0387264B1 (en
Inventor
Ferdinand Quella
Wolfgang Pekruhn
Oskar Nuyken
Hartmut Grethen
Barbara Doerner
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.)
Siemens AG
Original Assignee
Siemens AG
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 Siemens AG filed Critical Siemens AG
Publication of EP0387264A1 publication Critical patent/EP0387264A1/en
Application granted granted Critical
Publication of EP0387264B1 publication Critical patent/EP0387264B1/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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
    • B41M5/395—Macromolecular additives, e.g. binders
    • 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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree

Definitions

  • the invention relates to an ink ribbon for a transfer printing process in which dye components are transferred from a carrier film to a material to be printed, in particular paper, by the targeted action of circuitry and / or heat.
  • Printer inks for known ribbons consist of a wax that contains the dye and a binder. This wax is applied to a carrier, which usually consists of a flexible plastic film, for example polybutylene terephthalate. For better heat conduction, an aluminum layer can still be present between the film and the wax layer.
  • the ribbons for the printers are produced from foils coated in this way.
  • a print head which can consist, for example, of a plurality of heatable elements arranged in the form of a matrix, transfers a certain amount of heat to the ink ribbon via these elements.
  • the wax is melted and transferred to the medium to be printed, in particular paper, by the pressure applied at the same time.
  • the wax layer containing the dye transferred onto the paper is relatively thick.
  • the multi-layer structure of the ink ribbon described is also disadvantageous.
  • the wax layer has to be melted during pressing and therefore, like all other layers, consumes a certain amount Heating output that limits the maximum achievable printing speed.
  • the mechanical stress on the ribbons also only allows a certain printing speed.
  • thermal efficiency in thermal printers with conventional printer ink compositions is only approximately 5%. This means that approx. 95% of the heating output is lost as waste heat and can no longer be used directly for ink transfer.
  • an ink ribbon of the type mentioned at the outset that at least one of the ink components to be transferred is provided on the carrier film in the form of a non-mobile connection which chemically decomposes by the action of radiation and / or heat and thereby the at least one ink component releases, this ink component is mobile and transferred to the material to be printed.
  • the at least one ink component is bound via an unstable group, upon its disintegration a gaseous compound is also released in addition to the ink component.
  • thermally labile chemical bonding of ink components in a non-mobile connection facilitates the release of these ink components. Release and mobilization mean the transfer of this ink component into a more mobile phase. This more mobile phase can be liquid or gaseous at the given temperature.
  • Releasable ink components can be: one or more Dyes or pigments, binder material for the dye, a "wax layer" which acts as an intermediate or cover layer or a compound which acts as a solvent for other ink components and is liquid in the released state at the given temperature.
  • the transfer of the ink components of the ink ribbon according to the invention requires less energy input than with conventional ink ribbons.
  • the covering wax layer on the ink ribbon can be made thinner or can even be omitted entirely.
  • a gas released during the printing process in one embodiment of the invention supports the transfer of the ink components onto the medium to be printed. Due to the pressure generated when the gas is released, the ink components receive enough kinetic energy to penetrate deeply into the material to be printed (for example paper). This results in increased dye adhesion on the paper.
  • This additional supportive effect can also be achieved by admixing another thermally unstable compound to the ink components.
  • a compound which acts as a "blowing agent” is, for example, azodicarbonamide.
  • This compound which can be added to the ink components up to about 10 percent by weight, is preferred since it does not release any toxic gases.
  • azo foamers can also be used, for example.
  • 2-t-butylazo-2'-cyanobutane the decomposition temperature can be set to approx. 80 ° C.
  • a blowing agent that thermally releases not only nitrogen but also carbon dioxide is 2,2'-diacetoxy-2,2'-azopropane.
  • the chemical disintegration reaction on the ink ribbon achieves a faster ink transfer than is possible with conventional ink ribbons, where the ink transfer is only achieved by melting a layer of wax and applying pressure.
  • the decay temperature of the labile compound is coordinated with the melting point of the one which may be present as a cover layer Additional benefits are achieved with wax.
  • the speed of the transfer of the ink components suddenly and steeply increases when the decay temperature in the color ribbons according to the invention is reached, and thus enables a sharper print image on, for example, paper.
  • the dye or its ink components can be bound to a carrier polymer.
  • this polymer simultaneously represents the carrier film for the ink ribbon.
  • a multi-layer structure of the ink ribbon can therefore be omitted in this case.
  • the ink ribbon can now be made significantly thinner, since the risk of mechanical damage to an ink ribbon with a single-layer structure is significantly lower during operation than with a multi-layer structure.
  • the amount of energy required for color transfer is also reduced in this embodiment.
  • only the heating power that is necessary to decompose the unstable groups has to be applied.
  • the decomposition areas i.e.
  • the areas in which a color transfer is to take place can be defined more sharply with the novel printer ink than is possible with the conventional wax layer technology. This results in a sharper print image, with the ink penetrating into the deepest paper cavities and pores, adhering accordingly and also providing good ink coverage.
  • printer ink allows the dye components to be transferred in solution.
  • other ink components can also be bound to the carrier polymer or as a non-mobile compound via labile groups or bonds, which form a liquid phase on disintegration and are able to dissolve the ink components.
  • a further embodiment of the inventive concept relates to a Ribbon in which at least one ink component is released from a depolymerizable polymer with a low decomposition temperature (ceiling temperature).
  • a depolymerizable polymer with a low decomposition temperature ceiling temperature
  • the ink component for example the dye
  • the ink component can be incorporated into such polymers by carrying out the polymerization in the presence of a dye. It is better to use dyes which carry a polymerizable functional group and can serve as monomers for copolymerization with the depolymerizable plastic.
  • the azo group and the carboxylate group which release the gases nitrogen and carbon dioxide on decay, are suitable as labile groups. Both groups are easy for the chemist and accessible in a variety of reactions.
  • the representation of the labile group can be used simultaneously with the linking reaction of the dye components with the carrier polymer. For example, polyamines bearing free amino groups can easily be coupled with suitable dyes to form azo groups.
  • Both the azo group and the carboxylate group decompose in the heat, the decomposition temperature being able to be set within certain limits by chemical modification, as is the case, for example, for blowing agents from an article by D. Braun in Monnatshefte für Chemie 110, pages 699 to 713, ( 1979) is known.
  • suitable modification it is therefore also possible to incorporate different dyes in a carrier polymer so that they are released at different temperatures.
  • An additional possibility for releasing the ink components of the ink ribbon according to the invention consists in the decomposition of the labile groups by radiation.
  • the azo group is unstable against UV light of 360 nm wavelength and disintegrates with the elimination of nitrogen.
  • the decomposition necessary energy is about 120 kJ / mol.
  • a similar amount of energy requires the decay of corresponding carboxylate groups, which in addition to heat can also be triggered by infrared radiation. This makes it possible to use the ink ribbon according to the invention in printers whose printheads do not transmit the ink from the ink ribbon to the paper with heat transfer, but with UV or IR radiation.
  • the monomer I is then polymerized in solution at about 60 ° by known methods.
  • this polymer for example with powdered polyethylene vinyl acetate, and subsequent coextrusion, films of, for example, 1 ⁇ m thick are produced therefrom and then bonded to a 2 ⁇ m thick polyethylene terephthalate film (carrier film).
  • carrier film A layer of paraffin up to approx. 2 ⁇ m thick can now be deposited from the solution on this layer. After drying, a ready-to-use printing film for an ink ribbon is created.
  • a solution containing about 0.5 to 10 percent by weight of polymer in a suitable solvent can also be used for coating.
  • R hexyl
  • a poly-p-aminostyrene can also be diazotized in a polymer-analogous reaction and reacted with the cyanoester.
  • the dye is released when heated to approx. 120o C and transferred to the paper. It is particularly advantageous that when the azo group decays, heat is released, which reduces the amount of energy necessary for the decay or to trigger the printing process.
  • a polymer that can be depolymerized for example poly methyl styrene (ceiling temperature approx. 60 ° C.), is dissolved in toluene and applied to the carrier film in a thickness of approx. 1 ⁇ m and provided with a dye-containing wax layer.
  • this is separated from a solution which, however, still contains a dye, for example carbon black, Duasyn black or others.
  • this wax layer can also be dispensed with if the dye is dissolved directly in the polymer or incorporated into it.
  • polystyrene In addition to poly- ⁇ -methylstyrene, there are numerous other polymerizable polymers with different decomposition temperatures that can be used as required.
  • polymers of isophthalic acid and 1,4-dibromotrahydronaphtaline which disintegrate under the influence of acid at approx. 120 ° C, while they are stable up to over 200 ° C without the influence of acid (see also JM 3. Fréchet, Emil Warburg Symposium, Elmau 1987, conference proceedings, page 73).
  • the dye is transferred by the thermally initiated disintegration of the intermediate layer or by the disintegration of the polymer, which is the layer containing the binder.

Landscapes

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

Abstract

Un ruban encreur pour imprimantes thermiques contient des éléments décomposables thermiquement ou sous l'effet de rayonnements, notamment des éléments qui libèrent un gaz en se décomposant. Les domaines de transfert d'encre (domaines de décomposition) de rubans encreurs ainsi fabriqués se laissent définir avec davantage de netteté, la puissance thermique requise pour l'impression peut être réduite et on obtient une meilleure adhérence de l'encre sur le papier.An ink ribbon for thermal printers contains elements which can be decomposed thermally or under the effect of radiation, in particular elements which release a gas by decomposing. The ink transfer areas (decomposition areas) of ink ribbons thus produced can be defined more clearly, the thermal power required for printing can be reduced and better adhesion of the ink to the paper is obtained.

Description

Farbband Ribbon
Die Erfindung betrifft ein Farbband für ein Transferdruckverfahren, bei dem durch gezieltes Einwirken von Schaltung und/oder Wärme Farbstoffkomponenten von einer Trägerfolie auf ein zu bedruckendes Material, insbesondere Papier, übertragen werden.The invention relates to an ink ribbon for a transfer printing process in which dye components are transferred from a carrier film to a material to be printed, in particular paper, by the targeted action of circuitry and / or heat.
Derartige Druckverfahren kommen zum Beispiel in Thermodruckern zur Anwendung. Druckertinten für bereits bekannte Farbbänder bestehen aus einem Wachs, das den Farbstoff und ein Bindemittel enthält. Dieses Wachs ist auf einem Träger aufgetragen, der üblicherweise aus einer flexiblen Kunststofffolie, zum Beispiel aus Polybutylenterephthalat besteht. Zur besseren Wärmeleitung kann zwischen Folie und Wachsschicht noch eine Aluminiumschicht vorhanden sein. Aus derart beschichteten Folien werαen die Farbbänder für die Drucker hergestellt.Such printing processes are used, for example, in thermal printers. Printer inks for known ribbons consist of a wax that contains the dye and a binder. This wax is applied to a carrier, which usually consists of a flexible plastic film, for example polybutylene terephthalate. For better heat conduction, an aluminum layer can still be present between the film and the wax layer. The ribbons for the printers are produced from foils coated in this way.
In dem auch Release-Technik genannten Druckverfahren überträgt ein Druckkopf, der zum Beispiel aus mehreren in Form einer Matrix angeordneten heizbaren Elementen bestehen kann, über diese Elemente eine bestimmte Wärmemenge auf das Farbband. Dadurch wird das Wachs zum Schmelzen gebracht und durch den gleichzeitig aufgewendeten Druck auf das zu bedruckende Medium, insbesondere Papier, übertragen. Die auf das Papier übertragene, den Farbstoff enthaltende Wachsschicht ist dabei relativ dick. Zwar wird dadurch eine gute Farbsattigung erzielt, die auch von der Oberfläche des Papiers unabhängig ist, jedoch ist die Farbstoffhaftung auf dem Papier und infolgedessen auch die Abriebfestigkeit bei dieser Technik noch sehr verbesserungsfähig.In the printing process, which is also called release technology, a print head, which can consist, for example, of a plurality of heatable elements arranged in the form of a matrix, transfers a certain amount of heat to the ink ribbon via these elements. As a result, the wax is melted and transferred to the medium to be printed, in particular paper, by the pressure applied at the same time. The wax layer containing the dye transferred onto the paper is relatively thick. Although this results in good color saturation, which is also independent of the surface of the paper, the dye adhesion on the paper and consequently the abrasion resistance can still be improved with this technique.
Bei zunehmender Druckgeschwindigkeit ist auch der mehrschichtige Aufbau des beschriebenen Farbbandes von Nachteil. Die Wachsschicht muß während des Drückens aufgeschmolzen werden und verbraucht daher ebenso wie alle anderen Schichten eine gewisse Heizleistung, die die maximal erreichbare Druckgeschwindigkeit begrenzt. Auch die mechanische Beanspruchung der Farbbänder erlaubt nur eine gewisse Druckgeschwindigkeit.As the printing speed increases, the multi-layer structure of the ink ribbon described is also disadvantageous. The wax layer has to be melted during pressing and therefore, like all other layers, consumes a certain amount Heating output that limits the maximum achievable printing speed. The mechanical stress on the ribbons also only allows a certain printing speed.
Außerdem beträgt der "thermische Wirkungsgrad" bei Thermodruckern mit herkömmlichen Druckertintenzusammensetzungen nach einer groben Schätzung nur ca. 5 % . Das heißt, ca. 95 % der aufgewendeten Heizleistung gehen als Abwärme verloren und können nicht mehr direkt für die Farbübertragung genutzt werden.In addition, according to a rough estimate, the "thermal efficiency" in thermal printers with conventional printer ink compositions is only approximately 5%. This means that approx. 95% of the heating output is lost as waste heat and can no longer be used directly for ink transfer.
Aufgabe der vorliegenden Erfindung ist es daher, ein Farbband für Transferdruckverfahren anzugeben, das eine gute Farbsättigung zum Beispiel auf Papier, verbesserte Druckqualität bei guter Farbhaftung und hohe Abriebfestigkeit des Farbbandes zeigt und das außerdem für die Farbübertragung weniger Heizleistung erfordert.It is therefore an object of the present invention to provide an ink ribbon for transfer printing processes which shows good color saturation, for example on paper, improved print quality with good ink adhesion and high abrasion resistance of the ink ribbon and which also requires less heating power for ink transfer.
Diese Aufgabe wird durch ein Farbband der eingangs genannten Art erfindungsgemäß dadurch gelöst, daß auf der Trägerfolie mindestens eine der zu übertragenden Tintenkomponenten in Form einer nicht mobilen Verbindung vorgesehen ist, welche durch Einwirken von Strahlung und/oder Wärme chemisch zerfällt und dadurch die mindestens eine Tintenkomponente freisetzt, wobei diese Tintenkomponente mobil und auf das zu bedruckende Material übertragen wird. Weiterhin liegt es im Rahmen der Erfindung, daß in der nicht mobilen Verbindung die zumindest eine Tintenkomponente über eine labile Gruppe gebunden ist, bei deren Zerfall neben der Tintenkomponente noch eine gasförmige Verbindung freigesetzt wird. Weitere Ausgestaltungen der Erfindung sind den Unteransprüchen zu entnehmen.This object is achieved according to the invention by means of an ink ribbon of the type mentioned at the outset, that at least one of the ink components to be transferred is provided on the carrier film in the form of a non-mobile connection which chemically decomposes by the action of radiation and / or heat and thereby the at least one ink component releases, this ink component is mobile and transferred to the material to be printed. Furthermore, it is within the scope of the invention that in the non-mobile connection the at least one ink component is bound via an unstable group, upon its disintegration a gaseous compound is also released in addition to the ink component. Further refinements of the invention can be found in the subclaims.
Durch die thermisch labile chemische Anbindung von Tintenkomponenten in einer nicht mobilen Verbindung wird die Freisetzung dieser Tintenkomponenten erleichtert. Unter Freisetzen und Mobilmachen ist dabei die Überführung dieser Tintenkomponente in eine mobilere Phase zu verstehen. Diese mobilere Phase kann flüssig, oder bei der gegebenen Temperatur auch gasförmig sein.The thermally labile chemical bonding of ink components in a non-mobile connection facilitates the release of these ink components. Release and mobilization mean the transfer of this ink component into a more mobile phase. This more mobile phase can be liquid or gaseous at the given temperature.
Freisetzbare Tintenkomponenten können sein: ein oder mehrere Farbstoffe oder Pigmente, Bindermaterial für den Farbstoff, eine als Zwischen- oder Abdeckschicht fungierende "Wachsschicht" oder eine als Lösungsmittel für andere Tintenkomponenten wirkende, im freigesetzten Zustand bei der gegebenen Temperatur flüssige Verbindung.Releasable ink components can be: one or more Dyes or pigments, binder material for the dye, a "wax layer" which acts as an intermediate or cover layer or a compound which acts as a solvent for other ink components and is liquid in the released state at the given temperature.
Der Transfer der Tintenkomponenten des erfindungsgemäßen Farbbandes erfordert eine geringere Energiezufuhr als bei herkömmlichen Farbbändern. Durch die erfindungsgemäße chemische Anbindung von Tintenkomponenten kann die abdeckende Wachsschicht auf dem Farbband dünner ausgeführt werden oder auch ganz entfallen.The transfer of the ink components of the ink ribbon according to the invention requires less energy input than with conventional ink ribbons. As a result of the chemical bonding of ink components according to the invention, the covering wax layer on the ink ribbon can be made thinner or can even be omitted entirely.
Ein in einer Ausführungsform der Erfindung beim Druckvorgang freigesetztes Gas unterstützt die Übertragung der Tintenkomponenten auf das zu bedruckende Medium. Durch den bei der Freisetzung des Gases entstehenden Druck erhalten die Tintenkomponenten genügend kinetische Energie, um tief in das zu bedruckende Material (zum Beispiel Papier) einzudringen. Dadurch wird eine erhöhte Farbstoffhaftung auf dem Papier erreicht.A gas released during the printing process in one embodiment of the invention supports the transfer of the ink components onto the medium to be printed. Due to the pressure generated when the gas is released, the ink components receive enough kinetic energy to penetrate deeply into the material to be printed (for example paper). This results in increased dye adhesion on the paper.
Dieser unterstützende zusätzliche Effekt kann auch durch Beimischen einer weiteren thermisch labilen Verbindung zu den Tintenkomponenten erzielt werden. Eine solche als "Treibmittel" wirkende Verbindung stellt zum Beispiel Azodicarbonamid dar. Diese bis ca. 10 Gewichtsprozent zu den Tintenkomponenten zusetzbare Verbindung ist bevorzugt, da es keine toxischen Gase freisetzt. Doch können zum Beispiel auch Azoschäumer verwendet werden. Mit 2-t-Butylazo-2'-cyanobutan läßt sich die Zerfallstemperatur auf ca. 80°C einstellen. Ein Treibmittel, das thermisch neben Stickstoff auch Kohlendioxid abspaltet, ist das 2,2'-Diacetoxy-2,2'-azopropan.This additional supportive effect can also be achieved by admixing another thermally unstable compound to the ink components. Such a compound which acts as a "blowing agent" is, for example, azodicarbonamide. This compound, which can be added to the ink components up to about 10 percent by weight, is preferred since it does not release any toxic gases. However, azo foamers can also be used, for example. With 2-t-butylazo-2'-cyanobutane, the decomposition temperature can be set to approx. 80 ° C. A blowing agent that thermally releases not only nitrogen but also carbon dioxide is 2,2'-diacetoxy-2,2'-azopropane.
Durch die chemische Zerfallsreaktion auf dem Farbband wird (auch ohne dabei freigesetztes Gas) ein schnellerer Farbtransfer erzielt, als dies bei herkömmlichen Farbbändern möglich ist, wo der Farbtransfer einzig durch Aufschmelzen einer Wachsschicht und den ausgeübten Druck erzielt wird. Insbesondere bei einer Abstimmung der Zerfallstemperatur der labilen Verbindung mit dem Schmelzpunkt des gegebenenfalls als Deckschicht vorhandenen Wachses werden weitere Vorteile erreicht. Die Geschwindigkeit des Transfers der Tintenkomponenten steigt beim Erreichen der Zerfallstemperatur in den erfindungsgemäßen Farbbändern plötzlich und steil an und ermöglicht so ein schärferes Druckbild auf zum Beispiel Papier.The chemical disintegration reaction on the ink ribbon (even without any gas released) achieves a faster ink transfer than is possible with conventional ink ribbons, where the ink transfer is only achieved by melting a layer of wax and applying pressure. In particular, if the decay temperature of the labile compound is coordinated with the melting point of the one which may be present as a cover layer Additional benefits are achieved with wax. The speed of the transfer of the ink components suddenly and steeply increases when the decay temperature in the color ribbons according to the invention is reached, and thus enables a sharper print image on, for example, paper.
Weiterhin können der Farbstoff-, bzw. dessen Tintenkomponenten an ein Trägerpolymer gebunden sein. Dieses Polymer stellt in einer bevorzugten Ausführungsform gleichzeitig die Trägerfolie für das Farbband dar. Ein mehrschichtiger Aufbau des Farbbands kann daher in diesem Fall entfallen. Bei gleichbleibender Druckgeschwindigkeit kann das Farbband nun deutlich dünner ausgeführt werden, da die Gefahr einer mechanischen Beschädigung eines Farbbandes mit Einschichtaufbau beim Betrieb bedeutend geringer ist, als beim Mehrschichtaufbau. Auch die Energiemenge, die zur Farbübertragung nötig ist, reduziert sich in dieser Ausführungsform. Neben einem geringen Beitrag zum Aufheizen der Folie muß nur noch die Heizleistung aufgebracht werden, die nötig ist, die labilen Gruppen zu zersetzen. Die Zersetzungsbereiche, das heißt die Bereiche, in denen eine Farbübertragung stattfinden soll, können mit der neuartigen Druckertinte schärfer definiert werden, als dies mit der herkömmlichen Wachsschichttechnik möglich ist. Somit wird ein schärferes Druckbild erzielt, wobei die Druckfarbe bis in tiefste Papierhohlräume und Poren eindringt, dementsprechend gut haftet und auch eine gute Farbdeckung ergibt.Furthermore, the dye or its ink components can be bound to a carrier polymer. In a preferred embodiment, this polymer simultaneously represents the carrier film for the ink ribbon. A multi-layer structure of the ink ribbon can therefore be omitted in this case. With the printing speed remaining the same, the ink ribbon can now be made significantly thinner, since the risk of mechanical damage to an ink ribbon with a single-layer structure is significantly lower during operation than with a multi-layer structure. The amount of energy required for color transfer is also reduced in this embodiment. In addition to a small contribution to heating the film, only the heating power that is necessary to decompose the unstable groups has to be applied. The decomposition areas, i.e. the areas in which a color transfer is to take place, can be defined more sharply with the novel printer ink than is possible with the conventional wax layer technology. This results in a sharper print image, with the ink penetrating into the deepest paper cavities and pores, adhering accordingly and also providing good ink coverage.
Eine weitere Ausführungsform der Druckertinte erlaubt es, die Übertragung der Farbstoffkomponenten in Lösung vorzunehmen. Dazu können neben den zum Beispiel Farbstoff enthaltenden Komponenten auch andere Tintenkomponenten über labile Gruppen oder Bindungen an das Trägerpolymer oder als nicht mobile Verbindung gebunden sein, die beim Zerfall eine flüssige Phase bilden und die Tintenkomponenten zu lösen vermögen. Durch die Übertragung der Tintenkomponenten in Lösung oder flüssiger Phase wird ein noch besseres Eindringen der Farbe in Poren und Hohlräume von Papier erreicht.Another embodiment of the printer ink allows the dye components to be transferred in solution. For this purpose, in addition to the components containing, for example, dye, other ink components can also be bound to the carrier polymer or as a non-mobile compound via labile groups or bonds, which form a liquid phase on disintegration and are able to dissolve the ink components. By transferring the ink components in solution or liquid phase, an even better penetration of the color into the pores and voids of paper is achieved.
Eine weitere Ausgestaltung des Erfindungsgedankens betrifft ein Farbband, bei den mindestens eine Tintenkomponente aus einem depolymerisierbaren Polymer mit niedriger Zerfallstemperatur (Ceiling-Temperatur) freigesetzt wird. Ein Beispiel dafür bildet oas Poly-α-methylstyrol, das eine Ceiling-Temperatur von ca. 61ºC besitzt. Die Einbindung der Tintenkomponente, zum Beispiel des Farbstoffs in derartige Polymere kann im einfachsten Fall dadurch erfolgen, daß die Polymerisation in Anwesenheit eines Farbstoffes ausgeführt wird. Besser werden Farbstoffe eingesetzt, die eine polymerisationsfähige funktioneile Gruppe tragen und als Monomere für eine Copolymerisation mit dem depolymerisierbaren Kunststoff dienen können.A further embodiment of the inventive concept relates to a Ribbon in which at least one ink component is released from a depolymerizable polymer with a low decomposition temperature (ceiling temperature). An example of this is oas poly-α-methylstyrene, which has a ceiling temperature of approx. 61ºC. In the simplest case, the ink component, for example the dye, can be incorporated into such polymers by carrying out the polymerization in the presence of a dye. It is better to use dyes which carry a polymerizable functional group and can serve as monomers for copolymerization with the depolymerizable plastic.
Die Auswahl geeigneter Farbstoffe ist groß, wenn die geforderten Bedingungen erfüllt werden. Für die Ausführungsformen der Erfindung, die an die Farbstoffkomponenten gebundene labile Gruppen vorsehen, bieten sich als labile Gruppen die Azogruppe und die Carboxylatgruppe an, die beim Zerfall die Gase Stickstoff bzw. Kohlendioxid freisetzen. Beide Gruppen sind dem Chemiker leicht und in einer Vielzahl von Reaktionen zugänglich. Zum Teil läßt sich die Darstellung der labilen Gruppe gleichzeitig mit der Verknüpfungsreaktion der Farbstoffkomponenten mit dem Trägerpolymer verwenden. So können etwa freie Aminogruppen tragende Polyamine leicht unter Ausbildung von Azogruppen mit geeigneten Farbstoffen gekuppelt werden.There is a large selection of suitable dyes if the required conditions are met. For the embodiments of the invention which provide labile groups bonded to the dye components, the azo group and the carboxylate group, which release the gases nitrogen and carbon dioxide on decay, are suitable as labile groups. Both groups are easy for the chemist and accessible in a variety of reactions. In part, the representation of the labile group can be used simultaneously with the linking reaction of the dye components with the carrier polymer. For example, polyamines bearing free amino groups can easily be coupled with suitable dyes to form azo groups.
Sowohl die Azogruppe als auch die Carboxylatgruppe zerfallen in der Wärme, wobei sich die Zerfallstemperatur durch chemische Modifikation in gewissen Grenzen einstellen läßt, wie es zum Beispiel für Treibmittel aus einem Artikel von D. Braun in Monnatshefte für Chemie 110, Seiten 699 bis 713, (1979) bekannt ist. Durch geeignete Modifikation ist es daher auch möglich, verschiedene Farbstoffe in ein Trägerpolymer so einzubauen, daß sie bei unterschiedlichen Temperaturen freigesetzt werden.Both the azo group and the carboxylate group decompose in the heat, the decomposition temperature being able to be set within certain limits by chemical modification, as is the case, for example, for blowing agents from an article by D. Braun in Monnatshefte für Chemie 110, pages 699 to 713, ( 1979) is known. By suitable modification it is therefore also possible to incorporate different dyes in a carrier polymer so that they are released at different temperatures.
Eine zusätzliche Möglichkeit, die Tintenkomponenten des erfindungsgemäßen Farbbandes freizusetzen, besteht in der Zersetzung der labilen Gruppen durch Strahlung. So ist zum Beispiel die Azogruppe gegen UV-Licht von 360 nm Wellenlänge instabil und zerfällt unter Abspaltung von Stickstoff. Die zur Zersetzung nötige Energie beträgt etwa 120 kJ/mol. Eine ähnliche Energiemenge erfordert der Zerfall entsprechender Carboxylatgruppen, der neben Wärme auch durch Infrarotstrahlung ausgelöst werden kann. Dadurch ist es möglich, das erfindungsgemäße Farbband auch in solchen Druckern einzusetzen, deren Druckköpfe nicht mit Wärmeübertragung, sondern mit UV- bzw. IR-Strahlung die Farbübertragung vom Farbband auf das Papier bewirken.An additional possibility for releasing the ink components of the ink ribbon according to the invention consists in the decomposition of the labile groups by radiation. For example, the azo group is unstable against UV light of 360 nm wavelength and disintegrates with the elimination of nitrogen. The decomposition necessary energy is about 120 kJ / mol. A similar amount of energy requires the decay of corresponding carboxylate groups, which in addition to heat can also be triggered by infrared radiation. This makes it possible to use the ink ribbon according to the invention in printers whose printheads do not transmit the ink from the ink ribbon to the paper with heat transfer, but with UV or IR radiation.
Im folgenden wird die Erfindung anhand von zwei Ausführungsbeispielen noch näher erläutert.The invention is explained in more detail below with the aid of two exemplary embodiments.
1. Ausführunosbeispiel1. Execution example
Ein polymerisierbares olefinisches Monomer, welches ein aromatisches Amin trägt, zum Beispiel p-Amino-methacrylsäurebenzylester wird diazotiert und mit einem einen Farbstoff X tragenden Alkylcyanessigester nach Formel 1 umgesetzt.A polymerizable olefinic monomer which carries an aromatic amine, for example benzyl p-aminomethacrylic acid, is diazotized and reacted with an alkylcyanoacetic acid ester of formula 1 bearing a dye X.
Das Monomer I wird anschließend nach bekannten Methoden in Lösung bei ca. 60° polymerisiert. Durch Mischen dieses Polymeren, zum Beispiel mit pulverförmigem Polyethylenvinylacetat, und anschließender Coextrusion werden daraus Folien von zum Beispiel 1 μm Stärke erzeugt und dann mit einer 2 μm dicken Polyethylenterephthalatfolie (Trägerfolie) verbunden. Auf dieser Schicht kann nun noch eine bis ca. 2 μm dicke Parafinschicht aus der Lösung abgeschieden werden. Nach dem Trocknen ist eine gebrauchsfertige Druckfolie für ein Farbband entstanden.The monomer I is then polymerized in solution at about 60 ° by known methods. By mixing this polymer, for example with powdered polyethylene vinyl acetate, and subsequent coextrusion, films of, for example, 1 μm thick are produced therefrom and then bonded to a 2 μm thick polyethylene terephthalate film (carrier film). A layer of paraffin up to approx. 2 μm thick can now be deposited from the solution on this layer. After drying, a ready-to-use printing film for an ink ribbon is created.
Zur Beschichtung kann auch eine etwa 0,5 bis 10 Gewichtsprozent Polymer enthaltende Lösung in einem geeigneten Lösungsmittel eingesetzt werden. Als Lösungsvermittler kann in diesem Fall (bei Abscheidung der Schicht aus Lösung) ein längerkettiger Alkylrest R (zum Beispiel R = Hexyl) dienen. Anstelle des Mono- meren kann alternativ auch ein Poly-p-aminostyrol in einer polymer-analogen Umsetzung diazotiert und mit dem Cyanester umgesetzt werden.A solution containing about 0.5 to 10 percent by weight of polymer in a suitable solvent can also be used for coating. In this case, a longer-chain alkyl radical R (for example R = hexyl) can serve as a solubilizer (when the layer is separated from solution). Instead of the mono Alternatively, a poly-p-aminostyrene can also be diazotized in a polymer-analogous reaction and reacted with the cyanoester.
Im fertigen Farbband wird beim Erwärmen auf ca. 120º C der Farbstoff freigesetzt und auf das Papier übertragen. Dabei ist von besonderem Vorteil, daß beim Zerfall der Azogruppe Wärme frei wird, welche die zum Zerfall bzw. zum Auslösen des Druckvorgangs notwendige Energiemenge reduziert.In the finished ribbon, the dye is released when heated to approx. 120º C and transferred to the paper. It is particularly advantageous that when the azo group decays, heat is released, which reduces the amount of energy necessary for the decay or to trigger the printing process.
2. Ausführungsbeispiel2nd embodiment
Ein depolymerisierbares Polymer, zum Beispiel Poly- ck Methylstyrol (Ceiling-Temperatur ca. 60°C) wird in Toluol gelöst und in ca. 1 μm Dicke auf die Trägerfolie aufgebracht und mit einer farbstoffhaltigen Wachsschicht versehen. Diese wird wie im ersten Beispiel aus einer Lösung abgeschieden, welche allerdings noch einen Farbstoff, zum Beispiel Ruß, Duasyn-Schwarz oder andere enthält. In einer Variante kann auch auf diese Wachsechicht verzichtet werden, wenn der Farbstoff direkt im Polymer gelöst oder in dieses eingearbeitet wird.A polymer that can be depolymerized, for example poly methyl styrene (ceiling temperature approx. 60 ° C.), is dissolved in toluene and applied to the carrier film in a thickness of approx. 1 μm and provided with a dye-containing wax layer. As in the first example, this is separated from a solution which, however, still contains a dye, for example carbon black, Duasyn black or others. In a variant, this wax layer can also be dispensed with if the dye is dissolved directly in the polymer or incorporated into it.
Neben dem Poly-α-methylstyrol gibt es noch zahlreiche andere depolymiersierbare Polymere mit unterschiedlichen Zerfallstemperaturen, die je nach Bedarf eingesetzt werden können. So sind zum Beispiel Polymere aus Isophthalsäure und 1,4-Dibromtetrahydronaphtalin bekannt, die unter Säureeinfluß bei ca. 120°C zerfallen, während sie ohne Säureeinfluß bis über 200°C stabil sind (siehe dazu J. M. 3. Fréchet, Emil Warburg Symposium, Elmau 1987, Tagungsband, Seite 73).In addition to poly-α-methylstyrene, there are numerous other polymerizable polymers with different decomposition temperatures that can be used as required. For example, polymers of isophthalic acid and 1,4-dibromotrahydronaphtaline are known which disintegrate under the influence of acid at approx. 120 ° C, while they are stable up to over 200 ° C without the influence of acid (see also JM 3. Fréchet, Emil Warburg Symposium, Elmau 1987, conference proceedings, page 73).
Die Farbstoffübertragung geschieht in diesem Ausführungsbeispiel durch den thermisch initiierten Zerfall der Zwischenschicht bzw. durch den Zerfall des Polymeren, welches den Binder den Farbstoff enthaltenden Schicht darstellt. In this exemplary embodiment, the dye is transferred by the thermally initiated disintegration of the intermediate layer or by the disintegration of the polymer, which is the layer containing the binder.

Claims

Patentansprüche. Claims.
1. Farbband für ein Transferdruckverfahren, bei dem durch gezieltes Einwirken mit Strahlung und/oder Wärme Tintenkomponenten von einer Trägerfolie auf ein zu bedruckendes Material, insbesondere Papier, übertragen werden, d a d u r c h g e k e n n z e i c h n e t , daß auf der Trägerfolie mindestens eine der zu übertragenden Tintenkomponenten in Form einer nicht mobilen Verbindung vorgesehen ist, welche durch Einwirken von Strahlung und/oder Wärme chemisch zerfällt und dadurch die mindestens eine Tintenkomponente freisetzt, wobei diese Tintenkomponente mobil und auf das zu bedruckende Material übertragen wird.1. Ribbon for a transfer printing process in which, by targeted exposure to radiation and / or heat, ink components are transferred from a carrier film to a material to be printed, in particular paper, characterized in that on the carrier film at least one of the ink components to be transferred in the form of a non Mobile connection is provided, which decomposes chemically through the action of radiation and / or heat and thereby releases the at least one ink component, this ink component being transferred mobile and onto the material to be printed.
2. Farbband nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t , daß in der nicht mobilen Verbindung die zumindest eine Tintenkomponente über eine labile Gruppe gebunden ist, bei deren Zerfall neben der Tintenkomponente noch eine gasförmige Verbindung freigesetzt wird.2. Ribbon according to claim 1, d a d u r c h g e k e n n z e i c h n e t that in the non-mobile connection, the at least one ink component is bound via an unstable group, in the decay of which a gaseous compound is released in addition to the ink component.
3. Farbband nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t , daß die zumindest eine Tintenkomponente an ein Trägerpolymer gebunden ist.3. Ribbon according to claim 1 or 2, so that the at least one ink component is bound to a carrier polymer.
4. Farbband nach Anspruch 3, d a d u r c h g e k e n n z e i c h n e t , daß das Trägerpolymer gleichzeitig die Trägerfolie des Farbbands darstellt.4. Ribbon according to claim 3, d a d u r c h g e k e n n z e i c h n e t that the carrier polymer is also the carrier film of the ribbon.
5. Farbband nach mindestens einem der Ansprüche 1 bis 4, d a d u r c h g e k e n n z e i c h n e t , daß eine der durch chemischen Zerfall freisetzbaren Tintenkomponenten in flüssiger Phase freigesetzt wird und ein Lösungsmittel für die zu übertragenden Tintenkomponenten darstellt.5. Ribbon according to at least one of claims 1 to 4, d a d u r c h g e k e n n z e i c h n e t that one of the ink components releasable by chemical decay is released in the liquid phase and is a solvent for the ink components to be transferred.
6. Farbband nach mindestens einem der Ansprüche 1 bis 5, d a d u r c h g e k e n n z e i c h n e t , daß die nicht mobile Verbindung ein Polymer mit niedriger Ceilingtemperatur ist, welches durch Copolymerisation von Monomeren eines Kunststoffes mit Tintenkomponenten erhalten wird. 6. Ribbon according to at least one of claims 1 to 5, characterized in that the non-mobile compound is a polymer with a low ceiling temperature, which is obtained by copolymerizing monomers of a plastic with ink components.
7. Farbband nach mindestens einem der Ansprüche 1 bis 6, d a d u r c h g e k e n n z e i c h n e t , daß die nicht mobile Verbindung eine labile Gruppe enthält, welche eine Azo- oder eine Carboxylatgruppe ist.7. Ribbon according to at least one of claims 1 to 6, that the non-mobile compound contains an unstable group which is an azo or a carboxylate group.
8. Farbband nach mindestens einem der Ansprüche 1 bis 7, d a d u r c h g e k e n n z e i c h n e t , daß zwei bei unterschiedlicher Temperatur aus der nicht mobilen Verbindung freisetzbare Tintenkomponenten vorgesehen sind.8. Ribbon according to at least one of claims 1 to 7, d a d u r c h g e k e n n z e i c h n e t that two ink components releasable from the non-mobile connection are provided at different temperatures.
9. Farbband nach mindestens einem der Ansprüche 1 bis 8, d a d u r c h g e k e n n z e i c h n e t , daß auf der Trägerfolie eine weitere thermisch labile Verbindung vorgesehen ist, die beim Zerfall mindestens ein Gas freisetzt.9. Ribbon according to at least one of claims 1 to 8, d a d u r c h g e k e n n z e i c h n e t that a further thermally labile connection is provided on the carrier film, which releases at least one gas during decay.
10. Farbband nach Anspruch 9, d a d u r c h g e k e n n z e i c h n e t , daß die weitere thermisch labile Verbindung Azodicarbonamid ist. 10. Ribbon according to claim 9, d a d u r c h g e k e n n z e i c h n e t that the further thermally labile compound is azodicarbonamide.
EP88909286A 1987-10-29 1988-10-28 Inking ribbon Expired - Lifetime EP0387264B1 (en)

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DE3941517A1 (en) * 1989-12-15 1991-06-27 Siemens Ag THERMAL TRANSFER RIBBON
CA2782774A1 (en) * 2012-07-06 2014-01-06 Pharmascience Inc. Protein kinase inhibitors
CN102936438B (en) * 2012-11-29 2014-05-28 天津市赢事达办公用品厂 Water-based ink type food date label

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GB1344991A (en) * 1970-03-31 1974-01-23 Kodak Ltd Dyeing or treating films and fibres
GB1480748A (en) * 1975-03-13 1977-07-20 Kodak Ltd Materials for transfer printing
NO774518L (en) * 1977-06-02 1978-12-05 Polychrome Corp NEW IMAGINATING SYSTEMS AND PRODUCTS FOR USE IN THESE
JPS5964390A (en) * 1982-10-05 1984-04-12 Nec Corp Heat transfer recording method
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