EP0380920A2 - Thermal ink ribbon,method of its manufacture and its use - Google Patents

Thermal ink ribbon,method of its manufacture and its use Download PDF

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Publication number
EP0380920A2
EP0380920A2 EP90100263A EP90100263A EP0380920A2 EP 0380920 A2 EP0380920 A2 EP 0380920A2 EP 90100263 A EP90100263 A EP 90100263A EP 90100263 A EP90100263 A EP 90100263A EP 0380920 A2 EP0380920 A2 EP 0380920A2
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EP
European Patent Office
Prior art keywords
polymer beads
thermal
tape according
thermocarbon
melting
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
EP90100263A
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German (de)
French (fr)
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EP0380920A3 (en
EP0380920B1 (en
Inventor
Norbert Dr. Mecke
Heinrich Krauter
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.)
Pelikan Produktions AG
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Pelikan GmbH
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Publication date
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Priority to AT90100263T priority Critical patent/ATE97064T1/en
Publication of EP0380920A2 publication Critical patent/EP0380920A2/en
Publication of EP0380920A3 publication Critical patent/EP0380920A3/en
Application granted granted Critical
Publication of EP0380920B1 publication Critical patent/EP0380920B1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J31/00—Ink ribbons; Renovating or testing ink ribbons
    • 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.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • 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.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter

Definitions

  • the invention relates to a thermal ribbon, in particular thermocarbon ribbon, with a conventional carrier and with a layer of a wax- and / or plastic-bound melting ink formed on one side of the carrier for producing scratch-resistant, heat-stable markings by subsequent heat treatment, a particularly suitable method for producing this thermal ribbon and its special use for the production of scratch-resistant, heat-stable markings.
  • Thermal ribbons have been known for a long time. They have a melting color on a film-like carrier, which can consist of paper, a plastic or the like, in particular in the form of a plastic and / or wax-bound dye or pigment layer, in particular a plastic and / or wax-bound soot layer. In this transfer material, the melting ink is melted by means of a thermal print head and transferred to a recording paper or printing paper.
  • Thermal printers or thermal print heads that are used for this process are generally known. In particular, e.g. as follows: on the thermal print head of the printer, a letter consisting of heated dots and to be printed on a paper sheet is formed. The thermal print head presses the thermal ribbon onto the paper to be written on. The melting ink is melted in the heated areas and transferred to the paper sheet. The used part of the thermal ribbon is fed to a spool.
  • the thermal ink ribbon can have different melting colors next to each other. With the combination of the colors blue, yellow, red and black, color printed images can thus be produced.
  • Thermal printers can be operated at high speed (a DIN-A-4 sheet can be printed in about 10 seconds) and without annoying background noises.
  • thermal transfer printing systems are also generally known.
  • the prints obtained with the thermal ribbons described above, e.g. on paper have the disadvantage that they are not scratch-resistant.
  • scratch resistance is important in various technical areas, e.g. for labeled tool parts that are subject to strong mechanical influences.
  • thermocarbon tape in such a way that it enables the desirable scratch resistance of the symbols printed therewith in a wide variety of technical fields.
  • this object is achieved in that the melting ink in the thermal printing process contains non-melting, colorant-containing polymer beads which melt in a heat treatment downstream of the thermal printing process.
  • the minimum constituents which are contained in the melting color of the thermal ribbon according to the invention are consequently any binder which can be melted during the printing process.
  • This can be a wax or a wax-like material, as well as a plastic that melts at the printing temperature.
  • a wax or a wax-like material as well as a plastic that melts at the printing temperature.
  • the following are suitable: paraffins, natural waxes, such as carnauba wax, beeswax, ozokerite and paraffin wax, synthetic waxes, such as synthetic waxes, ester waxes, partially saponified ester waxes, poly ethylene waxes and polyglycols. This list is not exhaustive.
  • plastic binders which can be used instead of or in admixture with the waxes.
  • the waxes are mixed with these plastics. 1 part by weight of plastic preferably accounts for about 2 parts by weight of wax.
  • the polymer beads have a diameter of approximately 0.3 to 30 ⁇ m, in particular approximately 1 to 10 ⁇ m.
  • the type of colorant included is not essential, so it can be pigments and / or dyes according to the usual definitions.
  • the content of colorants in the polymer beads is preferably between about 10 and 30% by weight, in particular about 15 to 20% by weight, a pigment, in particular carbon black, being preferred as the colorant.
  • the polymeric plastic of the colorant-containing polymer beads can consist of polystyrene and styrene copolymers, polyvinyl acetate, polyamide, maleic acid resins, styrene hydrocarbon resins, (meth) acrylates, polyvinyl chloride, phenolic resins, polyvinyl ethers and / or epoxy resins.
  • An important requirement of the invention is that these materials differ in terms of melting point or softening point from the binders, which are a further component of the melting ink. This means that during the thermal printing process the polymer beads or toner particles should not melt, or should only melt insignificantly, while the part of the melting ink that creates the wax and / or plastic bond melts during the thermal printing process. This requirement is met for the plastic in the polymer beads when the melting point or softening point is between approximately 80 and 200 ° C., in particular approximately 100 to 150 ° C.
  • thermocarbon tape according to the invention can be compared with the fusible toner particles which are used in conventional copying machines.
  • the thickness of the layer of the melting color of the thermocarbon tape according to the invention is not essential for the objective according to the invention. In practical applications, the thickness of the melting ink layer will be approximately 3 to 20, in particular approximately 4 to 10 ⁇ m.
  • polyesters in particular polyethylene terephthalate, polycarbonates, polyamide, polyvinyl compounds, in particular polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol and polyvinyl propionate, polyethylene, polypropylene and polystyrene, are suitable for this purpose.
  • Condenser paper is also suitable, for example.
  • the carrier film will generally have a thickness of approximately 3 to 12 ⁇ m. Of course, this range can also be more or less far below or exceeded.
  • the type of colorant contained in the polymer beads mentioned is also not critical to achieving the object described above. It can be both inorganic and organic colorants, each in natural or synthetic form.
  • the inorganic colorants are pigments such as carbon black, iron oxide and magnetic pigments.
  • the organic pigments or dyes are those which are known in the toner technology mentioned, for example Nigrosine, phthalocyanine blue.
  • the production of the polymer beads contained in the thermocarbon tape according to the invention follows the technology that is also used in toner technology. This can be done, for example, by fusing and extruding the colorants and the plastic materials with subsequent granulation and painting.
  • the production of the thermal ink ribbon according to the invention is advantageously carried out as follows: dispersion in a commercially available aqueous dispersion of the binder, in particular in the form of a mixture of a wax and one during the thermal printing process melting plastic, the colorant-containing polymer particles.
  • the commercial dispersions used are about 30 to 50% by weight, in particular about 40% by weight.
  • the aqueous dispersion obtained is applied to the support by customary application techniques.
  • the application quantity (based on dry matter) is about 3 to 20 g / m2 of carrier area. For example, a doctor blade can be used for the application.
  • the job can be done at room temperature.
  • the coated carrier is then passed through a drying tunnel in which the aqueous phase of the applied aqueous dispersion is evaporated.
  • a system of meltable wax or meltable plastic / colorant-containing polymer particles in the form of a melt using customary technologies, such as, for example, using a screen printing method.
  • customary technologies such as, for example, using a screen printing method.
  • it is important here that the melting points of the polymer beads and the binder selected in each case are sufficiently far apart that the polymer beads themselves do not already melt in this application process.
  • a thermal tape 1 is shown.
  • the 8 mm thick melting ink 3 is located on the carrier 2 made of polyethylene terephthalate and has a thickness of about 6 ⁇ m. Copolymer is located. This means that the polymer beads 4 are embedded in the binder 5 mentioned.
  • the thermal printing process using a conventional thermal printer produces on the substrate 7, e.g. in the form of a paper, a printed symbol 6, which further contains the binder 5 and the polymer beads 4 in the structure shown in FIG. 1. Thus, the polymer beads 4 are still embedded in the binder 5.
  • An epoxy resin (trade name: EUMPOX (Schering)) with a melting point of about 120 ° C and carbon black were placed in a heat ratio of 90: 1 in a heatable extruder. The mixture was homogenized at temperatures above the melting point of the epoxy resin. The emerging strand was cut into pieces and ground in a pin mill to a grain size of about 2 to 8 microns.
  • Example 1 was modified such that instead of the epoxy resin with a melting point of about 120 ° C., a commercially available styrene copolymer (trade name: Radiant fusing copolymer / company: Diamond Shamrock) with a melting point of 90 ° C. was used.
  • the weight ratio of styrene copolymer to carbon black was approximately 80:20.
  • the thermal ribbons produced according to Examples 3 and 4 were used in a conventional thermal printer. Label paper has been written. Then this label paper with a Infrared heater mixed to about 200 ° C. The polymer beads melted together with the other particles contained in the melting ink to form a closed, uniform and scratch-resistant layer.

Landscapes

  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Impression-Transfer Materials And Handling Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Artificial Filaments (AREA)

Abstract

A thermal ink ribbon, in particular a thermal carbon ribbon, having a conventional substrate and having a layer formed on one side of the substrate and consisting of wax- and/or plastics-bound fusion ink for producing scratch-resistant markings by subsequent heat treatment, which is characterised in that small non-melting, colorant-containing polymer spheres which melt in a heat treatment following the thermal printing process are present in the fusion ink during the thermal printing process. Such a thermal carbon ribbon can be produced in particular by a method in which an aqueous dispersion which contains the small polymer spheres and fine particles of the binder is applied to the substrate of the thermal carbon ribbon, and the aqueous part of the dispersion is removed in a customary manner. If, by means of the thermal carbon ribbon according to the invention, a symbol is applied to any substrate and this symbol is subjected to subsequent heat treatment which leads to melting of the small polymer spheres, the printed symbol has a different structure, with the result that the symbol is now scratch-resistant. The scratch resistance plays a role in various industrial areas, such as in labels and other recording media. <IMAGE>

Description

Die Erfindung betrifft ein Thermofarbband, insbesondere Thermo­carbonband, mit einem üblichen Träger und mit einer auf einer Seite des Trägers ausgebildeten Schicht einer wachs- und/oder kunststoffgebunde­nen Aufschmelzfarbe zur Erzeugung kratzfester, wärmestabiler Markie­rungen durch nachträgliche Wärmebehandlung, ein besonders geeignetes Verfahren zur Herstellung dieses Thermofarbbandes sowie dessen spezielle Verwendung zur Herstellung kratzfester, wärmestabiler Markierungen.The invention relates to a thermal ribbon, in particular thermocarbon ribbon, with a conventional carrier and with a layer of a wax- and / or plastic-bound melting ink formed on one side of the carrier for producing scratch-resistant, heat-stable markings by subsequent heat treatment, a particularly suitable method for producing this thermal ribbon and its special use for the production of scratch-resistant, heat-stable markings.

Thermofarbbänder sind seit längerem bekannt. Sie weisen auf einem folienartigen Träger, der aus Papier, einem Kunststoff oder dergleichen bestehen kann, eine Aufschmelzfarbe auf, insbesondere in Form einer kunststoff- und/oder wachsgebundenen Farbstoff- oder Pigmentschicht, insbesondere eine Kunststoff und/oder wachsgebundene Rußschicht auf. Die Aufschmelzfarbe wird bei diesem Übertragungsmaterial mittels eines Wärmedruckkopfes geschmolzen und auf ein Aufzeichnungspapier bzw. Druckpapier übertragen. Thermische Drucker bzw. Wärmedruckköpfe, die für diesen Vorgang verwendet werden, sind allgemein bekannt. Im einzelnen kann dabei z.B. wie folgt vorgegangen werden: auf dem Wärme­druckkopf des Druckers wird ein aus beheizten Punkten bestehender und auf ein Papierblatt aufzudruckender Buchstabe ausgebildet. Der Wärme­druckkopf drückt das Thermofarbband auf das zu beschreibende Papier. Die Aufschmelzfarbe wird an den beheizten Stellen aufgeschmolzen und auf das Papierblatt übertragen. Der benutzte Teil des Thermofarbbandes wird einer Spule zugeführt.Thermal ribbons have been known for a long time. They have a melting color on a film-like carrier, which can consist of paper, a plastic or the like, in particular in the form of a plastic and / or wax-bound dye or pigment layer, in particular a plastic and / or wax-bound soot layer. In this transfer material, the melting ink is melted by means of a thermal print head and transferred to a recording paper or printing paper. Thermal printers or thermal print heads that are used for this process are generally known. In particular, e.g. as follows: on the thermal print head of the printer, a letter consisting of heated dots and to be printed on a paper sheet is formed. The thermal print head presses the thermal ribbon onto the paper to be written on. The melting ink is melted in the heated areas and transferred to the paper sheet. The used part of the thermal ribbon is fed to a spool.

Das Thermofarbband kann verschiedenartige Aufschmelzfarben neben­einander aufweisen. Mit der Kombination der Farben Blau, Gelb, Rot und Schwarz, lassen sich somit farbige Druckbilder herstellen. Thermo­drucker lassen sich mit großer Geschwindigkeit (ein DIN-A-₄-Blatt läßt sich in etwa 10 sec. bedrucken) und ohne störende Nebengeräusche betreiben.The thermal ink ribbon can have different melting colors next to each other. With the combination of the colors blue, yellow, red and black, color printed images can thus be produced. Thermal printers can be operated at high speed (a DIN-A-₄ sheet can be printed in about 10 seconds) and without annoying background noises.

Neben den oben geschilderten Thermofarbbändern gibt es auch solche, bei denen das Wärmesymbol nicht durch einen Wärmedruckkopf, sondern durch Widerstandsbeheizung eines speziell ausgestalteten folienartigen Trägers erfolgt. Die Aufschmelzfarbe, die die eigentliche "Funktions­schicht" beim Druckvorgang ist, enthält ebenfalls die bereits oben geschilderten Materialien. Hier spricht man von einem "ETR"-Thermofarb­band ("Electro Thermal Ribbon"). Auch derartige Thermotransfer-Druck­systeme sind allgemein bekannt.In addition to the thermal ribbons described above, there are also those in which the heat symbol is not generated by a thermal print head, but by resistance heating of a specially designed film-like carrier. The melting color, which is the actual "functional layer" during the printing process, also contains the materials already described above. Here one speaks of an "ETR" thermal ribbon ("Electro Thermal Ribbon"). Such thermal transfer printing systems are also generally known.

Die mit den oben beschriebenen Thermofarbbändern erzielten Aufdrucke, z.B. auf Papier, haben den Nachteil, daß sie nicht kratzfest sind. Die Kratzfestigkeit ist jedoch in verschiedenen technischen Bereichen von Bedeutung, so z.B. bei etikettierten Werkzeugteilen, die starken mechanischen Einwirkungen unterliegen.The prints obtained with the thermal ribbons described above, e.g. on paper have the disadvantage that they are not scratch-resistant. However, scratch resistance is important in various technical areas, e.g. for labeled tool parts that are subject to strong mechanical influences.

Der Erfindung lag daher die Aufgabe zugrunde, das eingangs bezeichnete Thermocarbonband so weiterzubilden, daß es die wünschenswerte Kratzfestigkeit der damit ausgedruckten Symbole in den verschiedensten technischen Bereichen ermöglicht.The invention was therefore based on the object of developing the above-mentioned thermocarbon tape in such a way that it enables the desirable scratch resistance of the symbols printed therewith in a wide variety of technical fields.

Erfindungsgemäß wird diese Aufgabe dadurch gelöst, daß in der Auf­schmelzfarbe beim Thermodruckvorgang nicht schmelzende, farbmittel­haltige Polymerkügelchen enthalten sind, die bei einer dem Thermodruck­vorgang nachgeschalteten Wärmebehandlung schmelzen.According to the invention, this object is achieved in that the melting ink in the thermal printing process contains non-melting, colorant-containing polymer beads which melt in a heat treatment downstream of the thermal printing process.

Die Mindestbestandteile, die in der Ausschmelzfarbe des erfindungsgemäßen Thermofarbbandes enthalten sind, sind demzufolge ein beliebiges beim Druckvorgang schmelzbares Bindemittel. Dabei kann es sich um ein Wachs oder auch um ein wachsähnliches Material, sowie um einen Kunststoff handeln, der bei Drucktemperatur schmilzt. So sind beispielsweise geeignet: Paraffine, Naturwachse, wie Carnaubawachs, Bienenwachs, Ozokerit und Paraffinwachs, Synthetikwachse, wie Synthesewachse, Esterwachse, teilverseifte Esterwachse, Poly­ ethylenwachse sowie Polyglykole. Diese Auflistung ist nicht erschöpfend. Als Kunststoffbindemittel, die anstelle der Wachse oder mit ihnen in Vermischung in Frage kommen, sind insbesondere Ethylen-/Vinylacetat-Co­polymerisat, Polyvinyläther, Polyethylen und Kohlenwasserstoffharz anzu­geben. Bei der praktischen Durchführung der Erfindung hat es sich von Vorteil erwiesen, wenn die Wachse mit diesen Kunststoffen in Ver­mischung eingesetzt werden. Dabei entfallen vorzugsweise auf 1 Gew.-Teil Kunststoff etwa 2 Gew.-Teile Wachs.The minimum constituents which are contained in the melting color of the thermal ribbon according to the invention are consequently any binder which can be melted during the printing process. This can be a wax or a wax-like material, as well as a plastic that melts at the printing temperature. For example, the following are suitable: paraffins, natural waxes, such as carnauba wax, beeswax, ozokerite and paraffin wax, synthetic waxes, such as synthetic waxes, ester waxes, partially saponified ester waxes, poly ethylene waxes and polyglycols. This list is not exhaustive. In particular, ethylene / vinyl acetate copolymer, polyvinyl ether, polyethylene and hydrocarbon resin are to be stated as plastic binders which can be used instead of or in admixture with the waxes. In the practical implementation of the invention, it has proven to be advantageous if the waxes are mixed with these plastics. 1 part by weight of plastic preferably accounts for about 2 parts by weight of wax.

Besonders vorteilhafte Ergebnisse werden erzielt, wenn etwa 20 bis 70 Gew.-% Bindemittel der oben beschriebenen Art auf etwa 30 bis 80 Gew.-Teile Polymerkügelchen entfallen.Particularly advantageous results are achieved when about 20 to 70% by weight of binder of the type described above is accounted for by about 30 to 80 parts by weight of polymer beads.

Um besonders gute Ergebnisse bei der Verwirklichung der vorliegenden Erfindung zu erhalten, wird es bevorzugt, daß die Polymerkügelchen einen Durchmesser von etwa 0,3 bis 30 µm, insbesondere von etwa 1 bis 10 üm aufweisen. Die Art. der darin eingeschlossenen Farbittel ist nicht wesentlich, so kann es sich um Pigmente und/oder um Farbstoffe nach den üblichen Definitionen handeln. Vorzugsweise liegt der Gehalt an Farb­mitteln in den Polymerkügelchen zwischen etwa 10 und 30 Gew.-%, insbesondere etwa 15 bis 20 Gew.-%, wobei als Farbmittel ein Pigment, insbesondere Ruß, bevorzugt wird.In order to obtain particularly good results in the implementation of the present invention, it is preferred that the polymer beads have a diameter of approximately 0.3 to 30 μm, in particular approximately 1 to 10 μm. The type of colorant included is not essential, so it can be pigments and / or dyes according to the usual definitions. The content of colorants in the polymer beads is preferably between about 10 and 30% by weight, in particular about 15 to 20% by weight, a pigment, in particular carbon black, being preferred as the colorant.

Der polymere Kunststoff der farbmittelhaltigen Polymerkügelchen kann aus Polystyrol und Styrolcopolymeren, Polyvinylacetat, Polyamid, Malein­säureharzen, Styrolkohlenwasserstoffharzen, (Meth)acrylaten, Polyvinyl­chlorid, Phenolharzen, Polyvinyläther und/oder Epoxidharzen bestehen. Wichtiges Erfordernis der Erfindung ist, daß diese Materialien sich bezüglich des Schmelzpunktes bzw. Erweichungspunktes von den Binde­mitteln, die weiterer Bestandteil der Aufschmelzfarbe sind, unterschei­den. Das bedeutet, beim Thermodruckvorgang sollen die Polymerkügel­chen bzw. Tonerteilchen nicht oder nur unwesentlich schmelzen, während der Teil der Aufschmelzfarbe, der die Wachs- und/oder Kunststoffbindung schafft, beim Thermodruckvorgang schmilzt. Dieses Erfordernis wird für den Kunststoff in den Polymerkügelchen dann eingehalten, wenn der Schmelzpunkt oder der Erweichungspunkt zwischen etwa 80 und 200°C, insbesondere etwa 100 bis 150°C liegt.The polymeric plastic of the colorant-containing polymer beads can consist of polystyrene and styrene copolymers, polyvinyl acetate, polyamide, maleic acid resins, styrene hydrocarbon resins, (meth) acrylates, polyvinyl chloride, phenolic resins, polyvinyl ethers and / or epoxy resins. An important requirement of the invention is that these materials differ in terms of melting point or softening point from the binders, which are a further component of the melting ink. This means that during the thermal printing process the polymer beads or toner particles should not melt, or should only melt insignificantly, while the part of the melting ink that creates the wax and / or plastic bond melts during the thermal printing process. This requirement is met for the plastic in the polymer beads when the melting point or softening point is between approximately 80 and 200 ° C., in particular approximately 100 to 150 ° C.

Es zeigt sich somit, daß die in dem erfindungsgemäßen Thermo­carbonband in der Aufschmelzfarbe enthaltenen Polymerkügelchen mit den schmelzbaren Tonerteilchen verglichen werden können, die in üblichen Kopiergeräten eingesetzt werden.It is thus shown that the polymer beads contained in the melting ink in the thermocarbon tape according to the invention can be compared with the fusible toner particles which are used in conventional copying machines.

Die Stärke der Schicht der Aufschmelzfarbe des erfindungsgemäßen Thermocarbonbandes ist für die erfindungsgemäße Zielsetzung nicht wesentlich. In den praktischen Anwendungsfällen wird die Stärke der Aufschmelzfarbschicht etwa 3 bis 20, insbesondere etwa 4 bis 10 µm betragen.The thickness of the layer of the melting color of the thermocarbon tape according to the invention is not essential for the objective according to the invention. In practical applications, the thickness of the melting ink layer will be approximately 3 to 20, in particular approximately 4 to 10 μm.

Auch die Art des Trägers ist für die mit der Erfindung angestrebten Effekte nicht kritisch. Hierzu kommen beispielsweise Polyester, insbesondere Polyethylenterephthalat, Polycarbonate, Polyamid, Polyvinyl­verbindungen, insbesondere Polyvinylchlorid, Polyvinylacetat, Polyvinyl­alkohol und Polyvinylpropionat, Polyethylen, Polypropylen und Polystyrol in Frage. Auch ist beispielsweise Kondensatorpapier geeignet. Die Träger­folie wird dabei in der Regel etwa eine Stärke von etwa 3 bis 12 µm auf­weisen. Selbstverständlich kann dieser Bereich auch mehr oder weniger weit unter- oder überschritten werden. Auch die Art des in den erwähnten Polymerkügelchen enthaltenen Farbmittels ist für die Lösung der vorstehend bezeichneten Aufgabe nicht entscheidend. Es kann sich dabei sowohl um anorganische als auch um organische Farbmittel handeln, jeweils in natürlicher oder synthetischer Form. Die anorganischen Farbmittel sind Pigmente, wie Ruß, Eisenoxid und Magnet­pigmente. Die organischen Pigmente bzw. Farbstoffe sind solche, die in der angesprochenen Tonertechnologie bekannt sind, so z.B. Nigrosin, Phthalocyanin-Blau. Die Herstellung der in dem erfindungsgemäßen Thermocarbonband enthaltenen Polymerkügelchen folgt entsprechend der Technologie, die auch in der Tonertechnologie angewandt wird. So kann das beispielsweise durch Verschmelzen und Extrudieren der Farbmittel und der Kunststoffmaterialien mit anschließendem Granulieren und Malen erfolgen.The type of carrier is also not critical for the effects sought with the invention. For example, polyesters, in particular polyethylene terephthalate, polycarbonates, polyamide, polyvinyl compounds, in particular polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol and polyvinyl propionate, polyethylene, polypropylene and polystyrene, are suitable for this purpose. Condenser paper is also suitable, for example. The carrier film will generally have a thickness of approximately 3 to 12 μm. Of course, this range can also be more or less far below or exceeded. The type of colorant contained in the polymer beads mentioned is also not critical to achieving the object described above. It can be both inorganic and organic colorants, each in natural or synthetic form. The inorganic colorants are pigments such as carbon black, iron oxide and magnetic pigments. The organic pigments or dyes are those which are known in the toner technology mentioned, for example Nigrosine, phthalocyanine blue. The production of the polymer beads contained in the thermocarbon tape according to the invention follows the technology that is also used in toner technology. This can be done, for example, by fusing and extruding the colorants and the plastic materials with subsequent granulation and painting.

Bei der Herstellung des erfindungsgemäßen Thermofarbbandes geht man vorteilhafterweise wie folgt vor: man dispergiert in einer handelsüblichen wässrigen Dispersion des Bindemittels, insbesondere in Form eines Gemisches aus einem Wachs und einem beim Thermodruckvorgang schmelzenden Kunststoff, die farbmittelhaltigen Polymerteilchen. Die eingesetzten handelsüblichen Dispersionen sind etwa 30 bis 50 gew.- %ig, insbesondere etwa 40 gew.-%ig. Die erhaltene wässrige Dispersion wird nach üblichen Auftragstechniken auf den Träger aufgetragen. Die Auftragsmenge (bezogen auf Trockensubstanz) beträgt hier etwa 3 bis 20 g/m² Trägerfläche. Zum Auftrag kann beispielsweise eine Rakel herange­zogen werden. Der Auftrag kann bei Zimmertemperatur erfolgen. Anschließend wird der beschichtete Träger durch einen Trockentunnel geführt, in dem die wässrige Phase der aufgetragenen wässrigen Dispersion abgedampft wird. Neben diesem Auftragsverfahren besteht darüber hinaus noch die Möglichkeit, ein System schmelzbares Wachs bzw. schmelzbarer Kunststoff / farbmittelhaltige Polymerteilchen in Form einer Schmelze nach üblichen Technologien, wie beispielsweise mit einem Rasterdruckverfahren aufzutragen. Hierbei ist es jedoch wichtig, daß die Schmelzpunkte der Polymerkügelchen und des jeweils gewählten Bindemittels ausreichend weit auseinanderliegen, daß bei diesem Auftrags­verfahren nicht bereits die Polymerkügelchen selbst schmelzen.The production of the thermal ink ribbon according to the invention is advantageously carried out as follows: dispersion in a commercially available aqueous dispersion of the binder, in particular in the form of a mixture of a wax and one during the thermal printing process melting plastic, the colorant-containing polymer particles. The commercial dispersions used are about 30 to 50% by weight, in particular about 40% by weight. The aqueous dispersion obtained is applied to the support by customary application techniques. The application quantity (based on dry matter) is about 3 to 20 g / m² of carrier area. For example, a doctor blade can be used for the application. The job can be done at room temperature. The coated carrier is then passed through a drying tunnel in which the aqueous phase of the applied aqueous dispersion is evaporated. In addition to this application method, there is also the possibility of applying a system of meltable wax or meltable plastic / colorant-containing polymer particles in the form of a melt using customary technologies, such as, for example, using a screen printing method. However, it is important here that the melting points of the polymer beads and the binder selected in each case are sufficiently far apart that the polymer beads themselves do not already melt in this application process.

Wird nun mit dem in der obigen Weise beschriebenen Thermofarbband auf beliebige Substrate ein Symbol aufgedruckt, dann hat dieses zunächst nicht die wünschenswerte Kratzfestigkeit. Die Kratzfestigkeit läßt sich jedoch dadurch erzielen, indem diesem Symbol weitere Wärme mit dem Ergebnis zugeführt wird, daß es in sich schmilzt und eine geschlossene Phase bildet, wobei die Wachse bzw. der beim Thermodruckvorgang schmelzbare Kunststoffe nunmehr teilweise oder vollständig von den Polymerkügelchen aufgenommen werden. Auf diese Weise stellt sich eine neue Struktur des aufgedruckten Symbols ein. Diese strukturellen Unterschiede lassen sich anhand der nachfolgend beschriebenen Figuren verdeutlichen. In diesen Figuren bedeuten:

  • Fig. 1 einen Querschnitt durch das erfindungsgemäße Farbband,
  • Fig. 2 einen Querschnitt durch ein Drucksystem aus Farbband und Sub­strat nach dem Druckvorgang,
  • Fig. 3 das Substrat mit aufgedrucktem Symbol nach Fig. 2 unter Be­strahlung und
  • Fig. 4 das Substrat mit verschmolzenem Symbol.
If a symbol is now printed on any substrate using the thermal ink ribbon described above, then this does not initially have the desirable scratch resistance. However, the scratch resistance can be achieved by adding further heat to this symbol, with the result that it melts in itself and forms a closed phase, the waxes or the plastics which can be melted during the thermal printing process being now partially or completely absorbed by the polymer beads. This creates a new structure for the printed symbol. These structural differences can be illustrated using the figures described below. In these figures:
  • 1 shows a cross section through the ribbon according to the invention,
  • 2 shows a cross section through a printing system consisting of ink ribbon and substrate after the printing process,
  • Fig. 3 shows the substrate with the printed symbol of FIG. 2 under irradiation and
  • Fig. 4 shows the substrate with the fused symbol.

In der Fig. 1 wird ein Thermoband 1 dargestellt. Dabei befindet sich auf dem Träger 2 aus Polyethylenterephthalat einer Stärke von etwa 6 µm die etwa 8 µm starke Aufschmelzfarbe 3. In der Aufschmelzfarbe 3 sind farbmittelhaltige Polymerkügelchen 4 enthalten, zwischen denen sich ein Bindemittel 5 in Form eines Gemisches aus Paraffinwachs und Ethylen/Vinylacetat-Copolymerisat befindet. Das bedeutet, daß die Polymerkügelchen 4 in dem angesprochenen Bindemittel 5 eingebettet sind.1, a thermal tape 1 is shown. The 8 mm thick melting ink 3 is located on the carrier 2 made of polyethylene terephthalate and has a thickness of about 6 µm. Copolymer is located. This means that the polymer beads 4 are embedded in the binder 5 mentioned.

Durch den Thermodruckvorgang mittels eines üblichen Thermodruckers entsteht auf dem Substrat 7, z.B. in Form eines Papiers, ein aufge­drucktes Symbol 6, das das Bindemittel 5 und die Polymerkügelchen 4 weiterhin in der in der Fig. 1 gezeigten Struktur enthalten. Somit sind weiterhin die Polymerkügelchen 4 in dem Bindemittel 5 eingebettet.The thermal printing process using a conventional thermal printer produces on the substrate 7, e.g. in the form of a paper, a printed symbol 6, which further contains the binder 5 and the polymer beads 4 in the structure shown in FIG. 1. Thus, the polymer beads 4 are still embedded in the binder 5.

Wird das auf das Papier aufgedruckte Symbol 6, wie es in der Fig. 2 dargestellt ist, nach Fig. 3 mit z.B. einer Infrarotheizung 8 unter aus­reichender Wärmeentwicklung aufgeheizt, so auf etwa 200°C, dann führt dies dazu, daß die Polymerkügelchen schmelzen und aufgrund dieses Schmelzvorganges das Bindemittel 5 mehr oder weniger weit aufnehmen. Es bildet sich eine geschlossene Phase 7, wie in Fig. 4 dargestellt.Is the symbol 6 printed on the paper, as shown in Fig. 2, according to Fig. 3 with e.g. an infrared heater 8 heated with sufficient heat, so to about 200 ° C, then this leads to the fact that the polymer beads melt and absorb the binder 5 more or less due to this melting process. A closed phase 7 is formed, as shown in FIG. 4.

Der mit der Erfindung erzielbare Vorteil ist demzufolge darin zu sehen, daß dort, wo kratzfeste Aufdrucke erforderlich sind, wie Etiketten und andere Aufzeichnungsträger, diese dadurch erhalten werden können, indem das aufgedruckte Symbol einer nachfolgenden Wärmebehandlung unterzogen wird, wodurch sich eine geeignete Struktur des Aufdrucks ergibt. Somit wurde hier der Vorteil vom Thermodruck in bisher dafür noch nicht in Betracht gezogenen technischen Bereichen genutzt.The advantage which can be achieved with the invention is therefore to be seen in the fact that where scratch-resistant imprints such as labels and other recording media are required, these can be obtained by subjecting the imprinted symbol to a subsequent heat treatment, which results in a suitable structure of the imprint results. Thus, the advantage of thermal printing was used in technical areas not previously considered.

Die Erfindung soll nachfolgend anhand einiger Beispiele noch näher erläutert werden.The invention will be explained in more detail below with the aid of a few examples.

Beispiel 1example 1 (Herstellung des Toners)(Production of the toner)

Ein Epoxidharz (Handelsname: EUMPOX (Schering)) eines Schmelzpunktes von etwa 120°C und Ruß wurden in einem Gewichtsverhältnis von 90:1 in einen heizbaren Extruder gegeben. Bei Temperaturen oberhalb des Schmelzpunktes des Epoxidharzes wurde das Gemisch homogenisiert. Der austretende Strang wurde in Stücke geschnitten und in einer Stiftmühle auf eine Korngröße von etwa 2 bis 8 µm vermahlen.An epoxy resin (trade name: EUMPOX (Schering)) with a melting point of about 120 ° C and carbon black were placed in a heat ratio of 90: 1 in a heatable extruder. The mixture was homogenized at temperatures above the melting point of the epoxy resin. The emerging strand was cut into pieces and ground in a pin mill to a grain size of about 2 to 8 microns.

Beispiel 2Example 2 (Herstellung der Polymerkügelchen)(Production of the polymer beads)

Das Beispiel 1 wurde dahingehend abgeändert, daß statt des Epoxidharzes eines Schmelzpunktes von etwa 120°C ein handelsübliches Styrol­copolymerisat (Handelsname: Radiant fusing Copolymer / Firma: Diamond Shamrock) eines Schmelzpunktes von 90°C verwendet wurde. Das Gewichtsverhältnis von Styrolcopolymerisat zu Ruß betrug etwa 80:20.Example 1 was modified such that instead of the epoxy resin with a melting point of about 120 ° C., a commercially available styrene copolymer (trade name: Radiant fusing copolymer / company: Diamond Shamrock) with a melting point of 90 ° C. was used. The weight ratio of styrene copolymer to carbon black was approximately 80:20.

Beispiel 3Example 3 (Herstellung der Aufschmelzfarbe)(Production of the melting ink)

30 Gew.-Teile des nach Beispiel 1 hergestellten Toners wurden mit 20 Gew.-Teilen Ethylenvinylacetat (Handelsname: EVA (JCJ)) und 50 Gew.-Teilen Paraff in bei 90°C zusammengeschmolzen und vermischt. Die so erhaltene Aufschmelzfarbe wird bei 90°C mitels eines Flexodruck­werkes auf eine 6 µm starke Polyesterfolie in einer Dicke von etwa 8 µm aufgetragen.30 parts by weight of the toner prepared according to Example 1 were melted together with 20 parts by weight of ethylene vinyl acetate (trade name: EVA (JCJ)) and 50 parts by weight of paraffin at 90 ° C. and mixed. The melting ink thus obtained is applied at 90 ° C. using a flexographic printing unit to a 6 μm thick polyester film in a thickness of approximately 8 μm.

Beispiel 4Example 4 (Herstellung der Aufschmelzfarbe)(Production of the melting ink)

30 Gew Teile des nach Beispiel 2 hergestellten Toners wurden mit 35 Gew.-Teilen einer 35 gew.-%igen wässrigen Polyvinylacetat-Dispersion (Handelsname: Mowilith DC / Firma Hoechst) und 50 Gew.-Teilen einer gew.-%igen wässrigen Paraffin-Dispersion (Handelsname: Vikonyl GL / Firma: Süddeutsche Emulsions-Chemie) miteinander vermischt. Die so erhaltene Farbe wurde mittels einer Rakel auf eine etwa 8 µm starke Polyesterfolie aufgetragen. Das Wasser wurde durch Überleiten von etwa 80°C warmer Luft abgedampft. Die getrocknete Farbschicht hatte eine Stärke von etwa 10 µm.30 parts by weight of the toner prepared according to Example 2 were mixed with 35 parts by weight of a 35% by weight aqueous polyvinyl acetate dispersion (trade name: Mowilith DC / Hoechst) and 50 parts by weight of a% by weight aqueous paraffin -Dispersion (trade name: Vikonyl GL / company: Süddeutsche Emulsions-Chemie) mixed together. The ink thus obtained was applied to an approximately 8 μm thick polyester film using a doctor knife. The water was evaporated by passing about 80 ° C warm air. The dried color layer had a thickness of about 10 microns.

Die nach den Beispielen 3 und 4 hergestellten Thermofarbbänder wurden in einen üblichen Thermodrucker eingesetzt. Es wurde Etikettenpapier beschrieben. Anschließend wurde dieses Etikettenpapier mit einem Infrarot-Strahler auf etwa 200°C vermischt. Dabei verschmolzen die Polymerkügelchen mit den weiteren in der Aufschmelzfarbe enthaltenen Teilchen zu einer geschlossenen einheitlichen und kratzfesten Schicht.The thermal ribbons produced according to Examples 3 and 4 were used in a conventional thermal printer. Label paper has been written. Then this label paper with a Infrared heater mixed to about 200 ° C. The polymer beads melted together with the other particles contained in the melting ink to form a closed, uniform and scratch-resistant layer.

Claims (14)

1. Thermofarbband, insbesondere Thermocarbonband, mit einem üblichen Träger und mit einer auf einer Seite des Trägers ausgebildeten Schicht einer wachs- und/oder kunststoffgebundenen Aufschmelzfarbe zur Erzeugung kratzfester, wärmestabiler Markierungen durch nachträgliche Wärmebehandlung, dadurch gekennzeichnet, daß in der Aufschmelzfarbe (3) beim Thermodruckvorgang nicht schmelzende, farbmittelhaltige Poly­merkügelchen (4) enthalten sind, die bei einer dem Thermodruckvorgang nachgeschalteten Wärmebehandlung schmelzen. 1. A thermal dye ribbon, especially thermal carbon ribbon, with a usual carrier and a layer formed on one side of the carrier layer of a wax and / or plastics-bonded fusible dye for producing scratch-resistant, heat stable markings through subsequent heat treatment, characterized in that in the hot-melt dye (3) when Thermal printing process contains non-melting, colorant-containing polymer beads (4), which melt during a heat treatment downstream of the thermal printing process. 2. Thermofarbband nach Anspruch 1, dadurch gekennzeichnet, daß die Polymerkügelchen (4) schmelzbare Tonerteilchen sind. 2. Thermal ribbon according to claim 1, characterized in that the polymer beads (4) are fusible toner particles. 3. Thermofarbband nach Anspruch 2, dadurch gekennzeichnet, daß der polymere Kunststoff der Tonermaterialien Polystyrol, Styrolcopolymere, Polyvinylacetat, Polyamide, Maleinsäureharz, Styrolkohlenwasserstoff­harz, (Meth-)acrylate, Polyvinylchlorid, Phenolharze, Polyvinyläther und/oder Epoxidharze sind. 3. Thermal ribbon according to claim 2, characterized in that the polymeric plastic of the toner materials are polystyrene, styrene copolymers, polyvinyl acetate, polyamides, maleic acid resin, styrene hydrocarbon resin, (meth) acrylates, polyvinyl chloride, phenolic resins, polyvinyl ether and / or epoxy resins. 4. Thermocarbonband nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Bindemittel (5) der Aufschmelzfarbe (3) aus einer Mischung eines Kohlenwasserstoff wachses und/oder Ester­wachses mit einem Ethylen/Vinylacetat-Copolymerisat und/oder Kohlen­wasserstoffharz besteht. 4. Thermocarbon tape according to at least one of claims 1 to 3, characterized in that the binder (5) of the melting ink (3) consists of a mixture of a hydrocarbon wax and / or ester wax with an ethylene / vinyl acetate copolymer and / or hydrocarbon resin. 5. Thermocarbonband nach mindestens einem der Ansprüche 1 bis 4, da­durch gekennzeichnet, daß auf etwa 30 bis 80 Gew.-Teile Polymerkügel­chen (4) etwa 20 bis 70 Gew.-Teile Bindemittel entfallen. 5. Thermocarbon tape according to at least one of claims 1 to 4, characterized in that about 20 to 70 parts by weight of binder are used for about 30 to 80 parts by weight of polymer beads (4). 6. Thermocarbonband nach mindestens einem der Ansprüche 1 bis 5, da­ durch gekennzeichnet, daß die Polymerkülgelchen (4) einen Durchmesser von etwa 0,3 bis 30 µm aufweisen. 6. Thermocarbon tape according to at least one of claims 1 to 5, there characterized in that the polymer beads (4) have a diameter of about 0.3 to 30 µm. 7. Thermocarbonband nach Anspruch 6, dadurch gekennzeichnet, daß die Polymerkügelchen (4) einen Durchmesser von etwa 1 bis 10 µm auf­weisen. 7. Thermocarbon tape according to claim 6, characterized in that the polymer beads (4) have a diameter of about 1 to 10 microns. 8. Thermocarbonband nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Polymerkügelchen (4) etwa 10 bis 30 Gew.-% Farbmittel enthalten. 8. Thermocarbon tape according to at least one of claims 1 to 7, characterized in that the polymer beads (4) contain about 10 to 30 wt .-% colorant. 9. Thermocarbonband nach Anspruch 8, dadurch gekennzeichnet, daß die Polymerkügelchen (4) etwa 15 bis 20 Gew.-% Farbmittel enthalten. 9. Thermocarbon tape according to claim 8, characterized in that the polymer beads (4) contain about 15 to 20 wt .-% colorant. 10. Thermocarbonband nach mindestens einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Polymerkügelchen (4) als Farbmittel ein Pigment enthalten. 10. Thermocarbon tape according to at least one of claims 1 to 9, characterized in that the polymer beads (4) contain a pigment as a colorant. 11. Thermocarbonband nach Anspruch 10, dadurch gekennzeichnet, daß das Pigment Ruß ist. 11. Thermocarbon tape according to claim 10, characterized in that the pigment is carbon black. 12. Thermocarbonband nach mindestens einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß der Kunststoff in den Polymerkügelchen (4) einen Schmelzpunkt von etwa 80 bis 200, insbesondere etwa 100 bis 150°C aufweist. 12. Thermocarbon tape according to at least one of claims 1 to 11, characterized in that the plastic in the polymer beads (4) has a melting point of about 80 to 200, in particular about 100 to 150 ° C. 13. Verfahren zur Herstellung des Thermocarbonbandes nach den vorausgehenden Ansprüchen, dadurch gekennzeichnet, daß auf den Träger (2) des Thermocarbonbandes eine wässrige Dispersion aufgebracht wird, die die Polymerkügelchen (4) und feine Teilchen des Bindemittels enthält, und der wässrige Anteil der Dispersion in üblicher Weise entfernt wird. 13. A method for producing the thermocarbon tape according to the preceding claims, characterized in that an aqueous dispersion is applied to the carrier (2) of the thermocarbon tape, which contains the polymer beads (4) and fine particles of the binder, and the aqueous portion of the dispersion in is removed in the usual way. 14. Verwendung des Thermocarbonbandes nach mindestens einem der Ansprüche 1 bis 12, wobei die damit durch den Thermodruck erzeugten Symbole anschließend durch erhöhte Wärmezufuhr zum Aufschmelzen der Polymerkügelchen (4) und zur Ausbildung einer einheitlichen kratzfesten Phase (9) verschmolzen werden. 14. Use of the thermocarbon tape according to at least one of claims 1 to 12, wherein the symbols thus generated by the thermal printing are then fused by increased heat supply to melt the polymer beads (4) and to form a uniform scratch-resistant phase (9).
EP90100263A 1989-02-03 1990-01-08 Thermal ink ribbon,method of its manufacture and its use Expired - Lifetime EP0380920B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90100263T ATE97064T1 (en) 1989-02-03 1990-01-08 THERMAL RIBBON, PROCESS FOR ITS MANUFACTURE AND ITS USE.

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DE3903259A DE3903259C1 (en) 1989-02-03 1989-02-03
DE3903259 1989-02-03

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WO2021194465A1 (en) * 2020-03-23 2021-09-30 Hewlett-Packard Development Company, L.P. Dye sublimation printing

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EP0206036A2 (en) * 1985-06-26 1986-12-30 Pelikan Aktiengesellschaft Thermal ink ribbon and process for making the same
JPS62218171A (en) * 1986-03-19 1987-09-25 Hitachi Maxell Ltd Thermal transfer material
EP0266526A1 (en) * 1986-10-15 1988-05-11 Pelikan Aktiengesellschaft Thermal carbon ribbon containing a resin-bonded fusible dye, and a process for the production of this ribbon

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DE3108367A1 (en) * 1980-03-06 1982-01-28 Canon K.K., Tokyo PRINTER
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EP0106663A2 (en) * 1982-10-20 1984-04-25 Xerox Corporation Thermal marking printer system
EP0206036A2 (en) * 1985-06-26 1986-12-30 Pelikan Aktiengesellschaft Thermal ink ribbon and process for making the same
JPS62218171A (en) * 1986-03-19 1987-09-25 Hitachi Maxell Ltd Thermal transfer material
EP0266526A1 (en) * 1986-10-15 1988-05-11 Pelikan Aktiengesellschaft Thermal carbon ribbon containing a resin-bonded fusible dye, and a process for the production of this ribbon

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US5158813A (en) 1992-10-27
DE59003381D1 (en) 1993-12-16
JPH02235678A (en) 1990-09-18
JPH0739199B2 (en) 1995-05-01
EP0380920A3 (en) 1991-02-06
EP0380920B1 (en) 1993-11-10
DE3903259C1 (en) 1990-05-23

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