EP0278091A1 - Multiple-use thermal printing transfer ribbon - Google Patents

Multiple-use thermal printing transfer ribbon Download PDF

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Publication number
EP0278091A1
EP0278091A1 EP19870118528 EP87118528A EP0278091A1 EP 0278091 A1 EP0278091 A1 EP 0278091A1 EP 19870118528 EP19870118528 EP 19870118528 EP 87118528 A EP87118528 A EP 87118528A EP 0278091 A1 EP0278091 A1 EP 0278091A1
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EP
European Patent Office
Prior art keywords
thermal
ribbon
ink
melting ink
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
EP19870118528
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German (de)
French (fr)
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EP0278091B1 (en
Inventor
Norbert Dr. Mecke
Heinrich Krauter
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Pelikan Produktions AG
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Pelikan GmbH
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Priority to AT87118528T priority Critical patent/ATE57500T1/en
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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
    • 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
    • B41J31/05—Ink ribbons having coatings other than impression-material coatings
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the invention relates to a rewritable thermal ribbon, in particular a rewritable thermal carbon ribbon, with a conventional carrier and with a layer of a melting ink formed on one side of the carrier.
  • 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 and the like, in particular in the form of a plastic and / or wax-bound dye or 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 a printing paper.
  • Thermal printers or thermal print heads that are used for this process are e.g. B. from DE-ASen 2 062 494 and 2 406 613 and DE-OS 3 224 445 known. In particular, z. Example, proceed 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 heated letter of the thermal print head at a temperature of about 400 ° C leads to the melting ink being melted at the heated point and being transferred to the paper sheet.
  • the used part of the thermal ribbon is fed to a spool.
  • the thermal ribbon can have differently colored melting colors next to each other. With the combination of the three primary colors blue, yellow and red, colored print images can be produced. Compared to the usual color photography, there is no disadvantageous development and fixing. Thermal printers can be operated at high writing speeds (a DIN A4 sheet can be printed in about 10 seconds) and without annoying background noises.
  • 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. Experts refer to this as an "ETR” thermal ribbon ("Electro Thermal Ribbon”).
  • ETR Electro Thermal Ribbon
  • Thermal ribbons are already known which can be overwritten several times (key word: "Multiuse”). Such thermal ribbons are described, for example, in EP-A-0 063 000.
  • the melting ink of the thermal ink ribbon is a particulate material which is insoluble in the solvent of the coating liquid and does not melt below 100 ° C, and incorporates another particulate material with a melting point between 40 and 100 ° C.
  • the particulate material not melting below 100 ° C should preferably be a metal oxide, a metal, an organic resin or carbon black.
  • This special particulate material is intended to give the layer of the melting ink, which is a solid mixture, a heterogeneous structure; which consumes only a small amount of molten colored material to be transferred in each individual printing operation.
  • thermal ink ribbons of this type it has been shown that the printouts are in need of improvement, particularly with regard to the print sharpness.
  • the thermal ink ribbon known from DE-OS 35 20 308 with a sponge-like structure of the melting ink provides the greatest possible remedy. It is produced by a special process, according to which a coating liquid which dissolves a thermoplastic binder and contains a meltable wax or a wax-like substance in finely divided solid form is applied to the support of the thermal ink ribbon in a manner known per se, the coating liquid being Solvent is a mixture of a solvent for the thermoplastic binder at room temperature and a non-solvent therefor. The non-solvent / solvent mixture is evaporated, while reducing its solvency for the thermoplastic binder.
  • the melting ink cannot be fully used when overwritten several times. It is therefore desirable to develop the known thermal ribbons so that this objective is met.
  • the invention is therefore based on the object of proposing a rewritable thermal ink ribbon, in particular a rewritable thermal carbon ribbon, which, in addition to the desirable sharpness of the printout, makes it possible to use the melting ink as completely as possible.
  • the melting ink as a substance which melts and is transferable under the thermal printing conditions, is a copolymer of an alkene and a vinyl compound of the following formula: Where mean: R1 is a lower alkyl group with 1 to 4 carbon atoms or a hydrogen atom, R2 is a lower alkyl group having 1 to 3 carbon atoms n and m the number of monomeric units in the copolymer molecule, the ratio m / n is between 0.01 and 0.07.
  • the essence of the invention therefore consists in the choice of a special binder as a meltable substance in the melting ink.
  • This binder shows extensive parallels to the waxes that were conventionally used to form the melting ink.
  • the decisive difference can be seen in the fact that, in contrast to the melting ink according to the invention, multiple overprinting with the desirable print sharpness is not possible with the customary wax-based melting colors, since a complete color transfer regularly takes place during the printing process.
  • the binder chosen according to the invention therefore behaves quite differently.
  • R1 is a hydrogen atom and R2 is a methyl group.
  • R2 is a methyl group.
  • the methyl, ethyl, propyl, isopropyl and butyl group should fall under the aforementioned term "lower alkyl group”.
  • the shown preferred structure of the copolymer contained in the melting ink of the thermal ribbon according to the invention is an ethylene / vinyl acetate copolymer, in which, as with all other further developments which fall within the scope of the invention, the ratio m / n between 0.01 and 0.07 is in particular between 0.025 and 0.035.
  • the binders selected according to the invention are preferably an ethylene wax which has been slightly modified by copolymerizing vinyl acetate.
  • the binder described above and contained in the melting ink of the thermal ink ribbon according to the invention is the main component.
  • a colorant preferably in an amount of about 10 to 40% by weight, is incorporated into this main component.
  • the type of colorant is not critical to the solution of the problem described above. It can be both inorganic and organic colorants, each in natural and synthetic form.
  • the inorganic colorants are pigments, such as carbon black, and may also have a filler character.
  • the dyes include colorants which are soluble in solvents and / or binders. Examples include:
  • Triphenylmethane dyes Viktoria Blue B (C.I. Basic Blue), Ink Blue (C.I. Acid Blue 93) and Water Blue T.B.A. (CI Acid Blue 22), azo dyes such as Sudan Deep Black BB (CI Solvent Black 2) and Sudan Brown 1 (CI Solvent Brown 1), metal complex dyes such as Neozapon Black RE (CI Solvent Black 27) and Neozapon Blue FLE (CI Solvent Blue 70) and spirit-soluble dyes such as Spirit Blue (CI Solvent Blue 3) and Spirit Soluble Fast Black (CI Solvent Blue 70).
  • azo dyes such as Sudan Deep Black BB (CI Solvent Black 2) and Sudan Brown 1 (CI Solvent Brown 1)
  • metal complex dyes such as Neozapon Black RE (CI Solvent Black 27) and Neozapon Blue FLE (CI Solvent Blue 70)
  • spirit-soluble dyes such as Spirit Blue (CI Solvent Blue 3) and Spirit Soluble Fast Black (CI Solvent Blue 70).
  • the minimum constituents which are contained in the melting ink of the thermal ink ribbon according to the invention are accordingly the special binder mentioned and the colorant.
  • the binder preferably makes up about 60 to 90% by weight of the melting ink.
  • the thickness of the layer of the melting ink is not essential for the objective according to the invention. However, the coarser the desired number of overrides, the greater it will be. In practical applications, the thickness of the melt ink layer will be approximately 5 to 20, in particular approximately 8 to 12, micrometers.
  • polyesters used in the prior art in particular polyethylene terephthalates, polycarbonates, polyamides, polyvinyl compounds, in particular polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol and polyvinyl propionate, polyethylene, polypropylene and polystyrene.
  • These films can also contain a plasticizer to improve flexibility.
  • the plastic carrier contains a conductive material in the finest dispersion, e.g. B. carbon black.
  • the carrier film is preferably about 10 to 15 micrometers thick, while this thickness is preferably about 3 to 6 micrometers when using a thermal print head.
  • these areas can also be exceeded or fallen below to a greater or lesser extent.
  • the production of the thermal ink ribbon according to the invention is advantageously carried out as follows: the binder of the melting ink used according to the invention is dissolved in a suitable aromatic solvent, such as toluene, in an approximately 15 to 25% by weight concentration. To this end, the colorant is preferably added in such an amount that it makes up about 10 to 40% by weight, based on dry matter.
  • the dispersion obtained is applied in a thickness of approximately 50 micrometers using customary application techniques. The order quantity would be about 50 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 solvent is evaporated.
  • Particularly suitable fatty acids are kyristic, palmitic, stearic and oleic acid.
  • Suitable derivatives thereof are, for example, fatty acid esters and fatty acid amides, in particular fatty acid esters of polyhydric alcohols, such as glycol and glycerin.
  • the amount of this dispersing aid in the applied solution or dispersion is preferably about 1 to 5% by weight, based on the dry matter.
  • the advantages that can be achieved with the invention can be outlined as follows:
  • the thermal ink ribbon according to the invention can be produced without difficulty. Its coloring capacity is fully used. Residual color does not remain with the last multiple overwriting. There is no framework substance that disturbs the sharpness of the font. Accordingly, when practicing the present invention, a variety of desirable advantages appear which have not been achieved in their entirety in the known thermal ribbons.
  • a modified polyethylene wax based on an ethylene / vinyl acetate copolymer with a vinyl acetate content of about 10% by weight was mixed with carbon black and toluene. 70 parts by weight of the polyethylene wax, 30 parts by weight of carbon black and 400 parts by weight of toluene were used. After briefly stirring, the modified polyethylene wax had gone into solution. It was applied in an amount of 50 g / m 2 to a polyester film with a thickness of about 6 micrometers by means of a doctor blade.
  • Coated supports were then passed through a conventional drying tunnel in order to evaporate the solvent in the form of the toluene at a temperature of approximately 80 °.
  • the ink ribbon obtained could easily be overwritten 20 times with a sharp printout.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Impression-Transfer Materials And Handling Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesive Tapes (AREA)
  • Organic Insulating Materials (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Fuses (AREA)

Abstract

Die Erfindung bezieht sich auf ein mehrfach überschreibbares Thermofarbband mit einem üblichen Träger und mit einer auf einer Seite des Trägers ausgebildeten Schicht einer Aufschmelzfarbe. Die Aufschmelzfarbe enthält als unter den Thermodruckbedingungen schmelzende und übertragbare Substanz ein Copolymerisat aus einem Alken und einer Vinylverbindung der folgenden Formel: <IMAGE> Worin bedeuten: R1 eine niedrige Alkylgruppe mit 1 bis 4 Kohlenstoffatomen oder ein Wasserstoffatom, R2 eine niedrige Alkylgruppe mit 1 bis 3 Kohlenstoffatomen und n und m die Anzahl der monomeren Einheiten in dem Copolymerisatmolekül, wobei das Verhältnis m/n zwischen 0,01 und 0.07 liegt. Dieses Thermofarbband läßt sich ohne Schwierigkeiten herstellen. Seine färbende Kapazität wird voll genutzt, so daß keine Restfarbe beim letztmaligen Mehrfachüberschreiben zurückbleibt. Es liegt keine die Schriftstärke störende Gerüstsubstanz vor.The invention relates to a rewritable thermal ink ribbon with a conventional carrier and with a layer of a melting ink formed on one side of the carrier. The melting ink contains a copolymer of an alkene and a vinyl compound of the following formula as a meltable and transferable substance under the thermal printing conditions: <IMAGE> where: R1 denotes a lower alkyl group with 1 to 4 carbon atoms or a hydrogen atom, R2 denotes a lower alkyl group with 1 to 3 Carbon atoms and n and m the number of monomeric units in the copolymer molecule, the ratio m / n being between 0.01 and 0.07. This thermal ribbon can be produced without difficulty. Its coloring capacity is fully used, so that no residual color is left over when it is overwritten several times. There is no framework substance that disturbs the font thickness.

Description

Die Erfindung betrifft ein mehrfach überschreibbares Thermo­farbband, insbesondere ein mehrfach überschreibbares Thermo­carbonband, mit einem üblichen Träger und mit einer auf einer Seite des Trägers ausgebildeten Schicht einer Auf­schmelzfarbe.The invention relates to a rewritable thermal ribbon, in particular a rewritable thermal carbon ribbon, with a conventional carrier and with a layer of a melting ink formed on one side of the carrier.

Thermofarbbänder sind seit längerem bekannt. Sie weisen auf einem folienartigen Träger, der aus Papier, einem Kunststoff und dergleichen bestehen kann, eine Aufschmelzfarbe auf, insbesondere in Form einer kunststoff- und/oder wachsge­bundenen Farbstoff- oder Rußschicht auf. Die Aufschmelzfarbe wird bei diesem Übertragungsmaterial mittels eines Wärme­druckkopfes geschmolzen und auf ein Aufzeichnungspapier bzw. ein Druckpapier übertragen. Thermische Drucker bzw. Wärme­druckköpfe, die für diesen Vorgang verwendet werden, sind z. B. aus den DE-ASen 2 062 494 und 2 406 613 sowie der DE-OS 3 224 445 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. Der aufgeheizte Buchstabe des Wärme­druckkopfes einer Temperatur von etwa 400 °C führt dazu, daß die Aufschmelzfarbe an der beheizten Stelle aufgeschmolzen und auf das Papierblatt überträgen wird. 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 and the like, in particular in the form of a plastic and / or wax-bound dye or 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 a printing paper. Thermal printers or thermal print heads that are used for this process are e.g. B. from DE-ASen 2 062 494 and 2 406 613 and DE-OS 3 224 445 known. In particular, z. Example, proceed 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 heated letter of the thermal print head at a temperature of about 400 ° C leads to the melting ink being melted at the heated point and being transferred to the paper sheet. The used part of the thermal ribbon is fed to a spool.

Das Thermofarbband kann verschiedenfarbige Aufschmelzfarben nebeneinander aufweisen. Mit der Kombination der drei Grund­farben Blau, Gelb und Rot lassen sich somit farbige Druck­bilder herstellen. Gegenüber der üblichen Farbfotografie entfällt ein nachteiliges Entwickeln und Fixieren. Thermo­drucker lassen sich mit großer Schreibgeschwindigkeit (ein DIN-A4-Blatt läßt in etwa 10 Sekunden bedrucken) und ohne störende Nebengeräusche betreiben.The thermal ribbon can have differently colored melting colors next to each other. With the combination of the three primary colors blue, yellow and red, colored print images can be produced. Compared to the usual color photography, there is no disadvantageous development and fixing. Thermal printers can be operated at high writing speeds (a DIN A4 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. In der Fachwelt spricht man hier von einem "ETR"-Thermofarbband ("Electro Thermal Ribbon"). Ein derartiges Thermotransfer-Drucksystem wird beispiels­weise in US-PS 4 309 117 beschrieben.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. Experts refer to this as an "ETR" thermal ribbon ("Electro Thermal Ribbon"). Such a thermal transfer printing system is described, for example, in US Pat. No. 4,309,117.

Es sind bereits Thermofarbbänder bekannt, die mehrfach über­schreibbar sind (Stickwort: "Multiuse"). Derartige Ther­mofarbbänder werden beispielsweise in der EP-A-0 063 000 beschrieben. Der Aufschmelzfarbe des Thermofarbbandes ist hierbei ein teilchenförmiges Material, das in dem Lösungs­mittel der Beschichtungsflüssigkeit unlöslich ist und nicht unter 100 °C schmilzt, und ein weiteres teilchenförmiges Material eines Schmelzpunktes zwischen 40 und 100 °C einver­leibt. Das nicht unter 100 °C schmelzende teilchenförmige Material soll vorzugsweise ein Metalloxid, ein Metall, ein organisches Harz oder Ruß sein. Durch dieses spezielle teil­chenförmige Material soll der Schicht der Aufschmelzfarbe, bei der es sich um ein festes Gemisch handelt, eine hetero­gene Struktur verliehen werden; die bei jedem einzelnen Druckvorgang lediglich eine kleine Menge zu übertra­genden geschmolzenen farbigen Materials verbrauchen läßt.Thermal ribbons are already known which can be overwritten several times (key word: "Multiuse"). Such thermal ribbons are described, for example, in EP-A-0 063 000. The melting ink of the thermal ink ribbon is a particulate material which is insoluble in the solvent of the coating liquid and does not melt below 100 ° C, and incorporates another particulate material with a melting point between 40 and 100 ° C. The particulate material not melting below 100 ° C should preferably be a metal oxide, a metal, an organic resin or carbon black. This special particulate material is intended to give the layer of the melting ink, which is a solid mixture, a heterogeneous structure; which consumes only a small amount of molten colored material to be transferred in each individual printing operation.

Bei Thermofarbbändern dieser Art hat es sich jedoch gezeigt, daß die Ausdrucke verbesserungsbedürftig sind, insbesondere im Hinblick auf die Druckschärfe. Hier schafft das aus der DE-OS 35 20 308 bekannte Thermofarbband mit schwammartiger Struktur der Aufschmelzfarbe weitestgehende Abhilfe. Es wird nach einem speziellen Verfahren hergestellt, wonach eine Beschichtungsflüssigkeit, die ein thermoplastisches Binde­mittel gelöst und ein schmelzbares Wachs bzw. eine wachsähn­liche Substanz in fein verteilter fester Form enthält, in an sich bekannter Weise auf den Träger des Thermofarbbandes aufgetragen wird, wobei die Beschichtungsflüssigkeit als Lösungsmittel eine Mischung eines Lösers für das thermopla­stische Bindemittel bei Raumtemperatur und eines Nichtlösers hierfür darstellt. Das Nichtlöser/Löser-Gemisch wird unter gleichzeitiger Herabsetzung seiner Lösefähigkeit für das thermoplastische Bindemittel abgedampft. Hier wie auch bei dem zuvor beschriebenen Thermofarbband ist die Aufschmelz­farbe beim mehrfachen überschreiben nicht vollständig nutz­bar. Es ist daher wünschenswert, die bekannten thermofarb­bänder so weiterzubilden, daß dieser Zielsetzung entsprochen wird.With thermal ribbons of this type, however, it has been shown that the printouts are in need of improvement, particularly with regard to the print sharpness. The thermal ink ribbon known from DE-OS 35 20 308 with a sponge-like structure of the melting ink provides the greatest possible remedy. It is produced by a special process, according to which a coating liquid which dissolves a thermoplastic binder and contains a meltable wax or a wax-like substance in finely divided solid form is applied to the support of the thermal ink ribbon in a manner known per se, the coating liquid being Solvent is a mixture of a solvent for the thermoplastic binder at room temperature and a non-solvent therefor. The non-solvent / solvent mixture is evaporated, while reducing its solvency for the thermoplastic binder. Here, as with the previously described thermal ink ribbon, the melting ink cannot be fully used when overwritten several times. It is therefore desirable to develop the known thermal ribbons so that this objective is met.

Der Erfindung liegt daher die Aufgabe zugrunde, ein mehrfach überschreibbares Thermofarbband, insbesondere ein mehrfach überschreibbares Thermocarbonband, vorzuschlagen, das neben der wünschenswerten Druckschärfe beim Ausdruck die möglichst vollständige Nutzung der Aufschmelzfarbe möglich macht.The invention is therefore based on the object of proposing a rewritable thermal ink ribbon, in particular a rewritable thermal carbon ribbon, which, in addition to the desirable sharpness of the printout, makes it possible to use the melting ink as completely as possible.

Erfindungsgemäß wird diese Aufgabe dadurch gelöst, daß die Aufschmelzfarbe als unter den Thermomodruckbedingungen schmelzende und übertragbare Substanz ein Copolymerisat aus einem Alken und einer Vinylverbindung der folgenden Formel:

Figure imgb0001
Worin bedeuten:
    R₁ eine niedrige Alkylgruppe mit 1 bis 4 Kohlenstoffatomen oder ein Wasserstoffatom,
    R₂ eine niedrige Alkylgruppe mit 1 bis 3 Kohlenstoffatomen
    n und m die Anzahl der monomeren Einheiten in dem Copoly­merisatmolekül,
wobei das Verhältnis m/n zwischen 0,01 und 0,07 liegt.According to the invention, this object is achieved in that the melting ink, as a substance which melts and is transferable under the thermal printing conditions, is a copolymer of an alkene and a vinyl compound of the following formula:
Figure imgb0001
 Where mean:
R₁ is a lower alkyl group with 1 to 4 carbon atoms or a hydrogen atom,
R₂ is a lower alkyl group having 1 to 3 carbon atoms
n and m the number of monomeric units in the copolymer molecule,
the ratio m / n is between 0.01 and 0.07.

Der Kern der Erfindung besteht demzufolge in der Wahl eines speziellen Bindemittels als schmelzbare Substanz in der Auf­schmelzfarbe. Dieses Bindemittel zeigt weitgehende Parallelen zu den Wachsen, die herkömmlicherweise zur Aus­bildung der Aufschmelzfarbe eingesetzt wurden. Der entschei­dende Unterschied ist darin zu sehen, daß bei den üblichen wachsgebundenen Aufschmelzfarben, anders als bei der Auf­schmelzfarbe gemäß der Erfindung, ein mehrfaches Überdrucken mit der wünschenswerten Druckschärfe nicht möglich ist, da regelmäßig ein vollständiger Farbübertrag beim Druckvorgang stattfindet. Ganz anders verhält sich demzufolge das Binde­mittel, das gemäß der Erfindung gewählt wird.The essence of the invention therefore consists in the choice of a special binder as a meltable substance in the melting ink. This binder shows extensive parallels to the waxes that were conventionally used to form the melting ink. The decisive difference can be seen in the fact that, in contrast to the melting ink according to the invention, multiple overprinting with the desirable print sharpness is not possible with the customary wax-based melting colors, since a complete color transfer regularly takes place during the printing process. The binder chosen according to the invention therefore behaves quite differently.

Es hat sich gezeigt, daß unter den unter vorgenannte Formel fallenden Verbindungen insbesondere solche von Vor­teil sind, bei denen R₁ ein Wasserstoffatom und R₂ eine Methylgruppe ist. Wie ersichtlich, sollen unter dem vorge­nannten Begriff "niedere Alkylgruppe" die Methyl-, Ethyl-, Propyl-, Isopropyl- und Butylgruppe fallen.It has been shown that those compounds which come under the abovementioned formula are particularly advantageous in which R₁ is a hydrogen atom and R₂ is a methyl group. As can be seen, the methyl, ethyl, propyl, isopropyl and butyl group should fall under the aforementioned term "lower alkyl group".

Bei der aufgezeigten bevorzugten Struktur des in der Auf­schmelzfarbe des erfindungsgemäßen Thermofarbband enthal­tenen Copolymerisates handelt es sich um ein Äthylen/Vinyl­acetat-Copolymerisat, bei dem, wie auch bei allen anderen weiteren Ausgestaltungen, die in den Rahmen der Erfindung fallen, das Verhältnis m/n zwischen 0,01 und 0,07 insbe­sondere zwischen 0,025 bis 0,035 liegt.The shown preferred structure of the copolymer contained in the melting ink of the thermal ribbon according to the invention is an ethylene / vinyl acetate copolymer, in which, as with all other further developments which fall within the scope of the invention, the ratio m / n between 0.01 and 0.07 is in particular between 0.025 and 0.035.

Dies bedeutet im Ergebnis, daß die erfindungsgemäß gewählten Bindemittel vorzugsweise ein Äthylenwachs darstellen, das geringfügig durch Einpolymerisieren von Vinylacetat modifi­ziert worden ist.As a result, this means that the binders selected according to the invention are preferably an ethylene wax which has been slightly modified by copolymerizing vinyl acetate.

Bei der Erprobung der vorliegenden Erfindung hat es sich des weiteren gezeigt, daß ein im Handel erhältliches Bindemittel dere Bezeichnung EVA 1-Wachs (hergestellt von der Firma BASF) besonders häufig überschreibbar ist, so bis zu 20mal. Auch die hiermit erzielten Ausdrucke stellen bezüglich der Druck­schärfe sehr zufrieden. Es läßt sich wie folgt durch physi­kalische Parameter kennzeichnen: Schmelzpunkt (Monoskrupt): 87 bis 92 °C; Erstarrungspunkt (nach der Einheitsmethode der "Deutschen Gesellschaft für Fettwissenschaft e. V." (DGF), Münster/Westfalen: M-III 4 a): 83-87 °C; Höppler-Härte bei 23 °C (DGF-M-III 9 a) 100-140 bar; Schmelzviskosität bei 120 °C (DGF-M-III 8): bis 1850 nm²/s; mittlere molare Masse (viskosimetrisch): 6500-7000; Vinylacetat-Gehalt: 8,5 bis 9,5 %.When the present invention was tested, it was further shown that a commercially available binder of the name EVA 1 wax (manufactured by BASF) can be overwritten particularly frequently, up to 20 times. The printouts achieved here are also very satisfactory in terms of print sharpness. It can be characterized by physical parameters as follows: Melting point (monoscrupt): 87 to 92 ° C; Freezing point (according to the standard method of the "German Society for Fat Science" (DGF), Münster / Westphalia: M-III 4 a): 83-87 ° C; Höppler hardness at 23 ° C (DGF-M-III 9 a) 100-140 bar; Melt viscosity at 120 ° C (DGF-M-III 8): up to 1850 nm² / s; average molar mass (viscometric): 6500-7000; Vinyl acetate content: 8.5 to 9.5%.

Das oben beschriebene und in der Aufschmelzfarbe des erfin­dungsgemäßen Thermofarbbandes enthaltende Bindemittel ist der Hauptbestandteil. Diesem Hauptbestandteil ist ein Farb­mittel, vorzugsweise in einer Menge von etwa 10 bis 40 Gew.%, einverleibt. Die Art des Farbmittels ist für die Lösung der vorstehend bezeichneten Aufgabe nicht entschei­dend. Es kann sich dabei sowohl um anorganische als auch um organische Farbmittel, jeweils in natürlicher und synthe­tischer Form, handeln. Die anorganischen Farbmittel sind Pigmente, wie Ruß, und haben gegebenenfalls auch Füllstoff­charakter. Zu den Farbstoffen zählen in Lösungsmitteln und/oder Bindemitteln lösliche Farbmittel. Als Beispiele seien genannt:The binder described above and contained in the melting ink of the thermal ink ribbon according to the invention is the main component. A colorant, preferably in an amount of about 10 to 40% by weight, is incorporated into this main component. The type of colorant is not critical to the solution of the problem described above. It can be both inorganic and organic colorants, each in natural and synthetic form. The inorganic colorants are pigments, such as carbon black, and may also have a filler character. The dyes include colorants which are soluble in solvents and / or binders. Examples include:

Triphenylmethan-Farbstoffe, Viktoria Blue B (C.I. Basic Blue), Ink Blue (C.I. Acid Blue 93) und Water Blue T.B.A. (C.I. Acid Blue 22), Azo-Farbstoffe, wie Sudan Deep Black BB (C.I. Solvent Black 2) und Sudan Brown 1 (C.I. Solvent Brown 1), Metall-Komplex-Farbstoffe, wie Neozapon Black RE (C.I. Solvent Black 27) und Neozapon Blue FLE (C.I. Solvent Blue 70) und spiritlösliche Farbstoffe, wie Spirit Blue (C.I. Solvent Blue 3) und Spirit Soluble Fast Black (C.I. Solvent Blue 70).Triphenylmethane dyes, Viktoria Blue B (C.I. Basic Blue), Ink Blue (C.I. Acid Blue 93) and Water Blue T.B.A. (CI Acid Blue 22), azo dyes such as Sudan Deep Black BB (CI Solvent Black 2) and Sudan Brown 1 (CI Solvent Brown 1), metal complex dyes such as Neozapon Black RE (CI Solvent Black 27) and Neozapon Blue FLE (CI Solvent Blue 70) and spirit-soluble dyes such as Spirit Blue (CI Solvent Blue 3) and Spirit Soluble Fast Black (CI Solvent Blue 70).

Die Mindestbestandteile, die in der Aufschmelzfarbe des erfindungsgemäßen Thermofarbbandes enthalten sind, sind dem­zufolge das erwähnte spezielle Bindemittel sowie das Farb­mittel. Das Bindemittel macht vorzugsweise etwa 60 bis 90 Gew.% der Aufschmelzfarbe aus.The minimum constituents which are contained in the melting ink of the thermal ink ribbon according to the invention are accordingly the special binder mentioned and the colorant. The binder preferably makes up about 60 to 90% by weight of the melting ink.

Die Stärke der Schicht der Aufschmelzfarbe ist für die erfindungsgemäße Zielsetzung nicht wesentlich. Sie wird jedoch um so größer sein, je gröber die angestrebte Zahl der Überschreibungen ist. In den praktischen Anwendungsfällen wird die Stärkie der Aufschmelzfarbschicht etwa 5 bis 20, insbesondere etwa 8 bis 12 Mikrometer betragen.The thickness of the layer of the melting ink is not essential for the objective according to the invention. However, the coarser the desired number of overrides, the greater it will be. In practical applications, the thickness of the melt ink layer will be approximately 5 to 20, in particular approximately 8 to 12, micrometers.

Auch die Art des Trägers ist für die mit der Erfindung ange­strebten Effekte nicht kritisch. Vielmehr kann der Fachmann, je nach den Bedürfnissen des Einzelfalls, unter den vorste­hend bei der Schilderung des Standes der Technik erwähnten Folien im Rahmen rein handwerklicher Bemühungen die beson­ders geeigneten ermitteln. Es hat sich jedoch gezeigt, daß die Kunststoffolien im Hinblick auf thermische und mecha­nische Stabilität bevorzugt sind. Dabei stehen folgende Materialien im Vordergrund: Im Stand der Technik herange­zogene Polyester, insbesondere Polyethylenterephthalate, Polycarbonate, Polyamide, Polyvinylverbindungen, insbeson­dere Polyvinylchlorid, Polyvinylacetat, Polyvinylalkohol und Polyvinylpropionat, Polyethylen, Polypropylen und Polystyrol. Diese Folien können auch zur Verbesserung der Flexibilität einen Weichmacher enthalten.The type of carrier is also not critical for the effects sought with the invention. Rather, depending on the needs of the individual case, the person skilled in the art can determine the particularly suitable films from the films mentioned above in the description of the prior art as part of purely manual efforts. However, it has been shown that the plastic films are preferred in terms of thermal and mechanical stability. The focus here is on the following materials: polyesters used in the prior art, in particular polyethylene terephthalates, polycarbonates, polyamides, polyvinyl compounds, in particular polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol and polyvinyl propionate, polyethylene, polypropylene and polystyrene. These films can also contain a plasticizer to improve flexibility.

Das weiteren kann auch eine die Wärmeleitfähigkeit erhöhende Substanz eingearbeitet werden. Im Falle der Verwendung des erfindungsgemäßen Thermofarbbandes und der Widerstands­beheizung (ETR-System) enthält der Kunststoffträger in feinster Dispersion ein leitfähiges Material, z. B. Ruß. Hierbei ist die Trägerfolie vorzugsweise etwa 10 bis 15 Mikrometer stark, während diese Stärke bei der Verwendung eines Wärmedruckkopfes vorzugsweise etwa 3 bis 6 Mikrometer ist. Selbstverständlich können diese Bereiche auch mehr oder weniger weit unter- oder überschritten werden.Furthermore, a substance that increases the thermal conductivity can also be incorporated. In the case of the use of the thermal ribbon and resistance heating (ETR system), the plastic carrier contains a conductive material in the finest dispersion, e.g. B. carbon black. Here, the carrier film is preferably about 10 to 15 micrometers thick, while this thickness is preferably about 3 to 6 micrometers when using a thermal print head. Of course, these areas can also be exceeded or fallen below to a greater or lesser extent.

Bei der Herstellung des erfindungsgemäßen Thermofarbbandes geht man vorteilhafterweise wie folgt vor: Man löst das erfindungsgemäß herangezogene Bindemittel der Aufschmelz­farbe in einem geeigneten aromatischen Lösungsmittel, wie beispielsweise Toluol, in einer etwa 15 bis 25 gew.%igen Konzentration. Hierzu fügt man vorzugsweise das Farbmittel in einer solchen Menge hinzu, daß es, auf Trockensubstanz bezogen, etwa 10 bis 40 Gew.% ausmacht. Die erhaltene Dispersion wird in einer Stärke von etwa 50 Mikrometern nach üblichen Auftragstechniken aufgetragen. Die Auftragsmenge würde hier etwa 50 g/m² Trägerfläche betragen. 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 das Lösungsmittel abgedampft wird. Bei dem Auftrag aus einer Lösung bzw. Dispersion hat es sich gezeigt, daß die Qualität der ausgebildeten Aufschmelzfarbe deutlich ver­bessert wird, wenn der aufgetragenen Flüssigkeit ein Disper­gierhilfsmittel in Form von vorzugsweise Fettsäuren und/oder speziellen Derivaten hiervon einverleibt ist.The production of the thermal ink ribbon according to the invention is advantageously carried out as follows: the binder of the melting ink used according to the invention is dissolved in a suitable aromatic solvent, such as toluene, in an approximately 15 to 25% by weight concentration. To this end, the colorant is preferably added in such an amount that it makes up about 10 to 40% by weight, based on dry matter. The dispersion obtained is applied in a thickness of approximately 50 micrometers using customary application techniques. The order quantity would be about 50 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 solvent is evaporated. When applying from a solution or dispersion, it has been shown that the quality of the melting ink formed is significantly improved if a dispersing aid in the form of preferably fatty acids and / or special derivatives thereof is incorporated into the applied liquid.

Als Fettsäuren kommt insbesondere Kyristin-, Palmitin-, Stearin- und Ölsäure in Frage. Geeignete Derivate hiervon sind beispielsweise Fettsäureester und Fettsäureamide, ins­besondere Fettsäureester mehrwertiger Alkohole, wie Glykol und Glyzerin. Die Menge dieses Dispergierhilfsmittels in der aufgetragenen Lösung bzw. Dispersion liegt vorzugsweise bei etwa 1 bis 5 Gew.%, bezogen auf Trockensubstanz.Particularly suitable fatty acids are kyristic, palmitic, stearic and oleic acid. Suitable derivatives thereof are, for example, fatty acid esters and fatty acid amides, in particular fatty acid esters of polyhydric alcohols, such as glycol and glycerin. The amount of this dispersing aid in the applied solution or dispersion is preferably about 1 to 5% by weight, based on the dry matter.

Die mit der Erfindung erzielbaren Vorteile sind wie folgt zu umreißen: Das erfindungsgemäße Thermofarbband läßt sich ohne Schwierigkeiten herstellen. Seine färbende Kapazität wird voll genutzt. Restfarbe bleibt beim letztmaligen Mehrfach­überschreiben nicht zurück. Es liegt keine die Schrift­schärfe störende Gerüstsubstanz vor. Bei der Praktizierung der vorliegenden Erfindung treten demzufolge eine Vielzahl wünschenswerter Vorteile in Erscheinung, die bei den bekannten Thermofarbbändern in ihrer Gesamtheit bisher nicht erreicht wurden.The advantages that can be achieved with the invention can be outlined as follows: The thermal ink ribbon according to the invention can be produced without difficulty. Its coloring capacity is fully used. Residual color does not remain with the last multiple overwriting. There is no framework substance that disturbs the sharpness of the font. Accordingly, when practicing the present invention, a variety of desirable advantages appear which have not been achieved in their entirety in the known thermal ribbons.

Die Erfindung soll nachfolgend anhand eines Beispiels noch näher erläutert werden.The invention will be explained in more detail below using an example.

Beispielexample

Ein modifiziertes Polyethylenwachs auf der Basis eines Ethylen/Vinylacetat-Copolymers eines Vinylacetatgehaltes von etwa 10 Gew.% wurde mit Ruß und Toluol gemischt. Dabei wurden 70 Gewichsteile des Polyethylenwachses, 30 Gewichts­teile Ruß 400 Gewichsteile Toluol herangezogen. Nach kurzzeitigem Rühren war das modifizierte Polyethylenwachs in Lösung gegangen. Es wurde in einer Menge von 50 g/m² auf eine Polyesterfolie einer Stärke von etwa 6 Mikrometern mittels einer Rakel aufgetragen.A modified polyethylene wax based on an ethylene / vinyl acetate copolymer with a vinyl acetate content of about 10% by weight was mixed with carbon black and toluene. 70 parts by weight of the polyethylene wax, 30 parts by weight of carbon black and 400 parts by weight of toluene were used. After briefly stirring, the modified polyethylene wax had gone into solution. It was applied in an amount of 50 g / m 2 to a polyester film with a thickness of about 6 micrometers by means of a doctor blade.

Anschließend wurde beschichtete Träger durch einen üblichen Trocknungstunnel geführt, um das Lösungsmittel in Form des Toluols bei einer Temperatur von etwa 80° abzu­dampfen. Das erhaltene Farbband ließ sich ohne weiteres mit scharfem Ausdruck 20mal überschreiben.Coated supports were then passed through a conventional drying tunnel in order to evaporate the solvent in the form of the toluene at a temperature of approximately 80 °. The ink ribbon obtained could easily be overwritten 20 times with a sharp printout.

Claims (7)

1. Mehrfach überschreibbares Thermofarbband, insbesondere Thermocarbonband, mit einem üblichen Träger und mit einer auf einer Seite des Trägers ausgebildeten Schicht einer Auf- schmelzfarbe, dadurch gekennzeichnet, daß die Aufschmelzfarbe als unter den Thermodruck­bedingungen schmelzende und übertragbare Substanz ein Copolymerisat aus einem Alken und einer Vinylverbindung der folgenden Formel besteht:
Figure imgb0002
 Worin bedeuten:
R₁ eine niedrige Alkylgruppe mit 1 bis 4 Kohlenstoff­atomen oder ein Wasserstoffatom,
R₂ eine niedrige Alkylgruppe mit 1 bis 3 Kohlenstoff­atomen,
n und m die Anzahl der monomeren Einheiten in dem Copoly­merisatmolekül, wobei das Verhältnis m/n zwischen 0,01 und 0,07 liegt.1. Multiple rewritable thermal ink ribbon, in particular thermocarbon ribbon, with a conventional carrier and with a layer of a melting ink formed on one side of the carrier, characterized in that the melting ink is a copolymer of an alkene and a vinyl compound as a meltable and transferable substance under the thermal printing conditions of the following formula:
Figure imgb0002
 Where mean:
R₁ is a lower alkyl group with 1 to 4 carbon atoms or a hydrogen atom,
R₂ is a lower alkyl group with 1 to 3 carbon atoms,
n and m the number of monomeric units in the copolymer molecule, the ratio m / n being between 0.01 and 0.07. 2. Thermofarbband nach Anspruch 1, dadurch gekennzeichnet, daß es als Bindemittel ein Ethylen/Vinylacetat-Copoly­merisat enthält.2. Thermal ribbon according to claim 1, characterized in that it contains an ethylene / vinyl acetate copolymer as a binder. 3. Thermofarbband nach Anspruch 2, dadurch gekennzeichnet, daß es 10 bis 40 Gew.% Farbmittel enthält.3. Thermal ribbon according to claim 2, characterized in that it contains 10 to 40% by weight of colorant. 4. Thermofarbband nach Anspruch 3, dadurch gekennzeichnet, daß es Ruß als Farbmittel enthält.4. Thermal ribbon according to claim 3, characterized in that it contains carbon black as a colorant. 5. Thermofarbband nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es ein Dispergierhilfsmittel für das Farbmittel enthält.5. Thermal ribbon according to one of claims 1 to 4, characterized in that it contains a dispersing agent for the colorant. 6. Thermofarbband nach Anspruch 5, dadurch gekennzeichnet, daß es ein Dispergierhilfsmittel in Form von Fettsäuren und/oder Derivaten hiervon enthält.6. Thermal ribbon according to claim 5, characterized in that it contains a dispersing aid in the form of fatty acids and / or derivatives thereof. 7. Thermofarbband nach Anspruch 6, dadurch gekennzeichnet, daß das Dispergierhilfsmittel in einer Menge von 1 bis 5 Gew.% in der Aufschmelzfarbe vorliegt.7. Thermal ribbon according to claim 6, characterized in that the dispersing agent is present in the melting ink in an amount of 1 to 5% by weight.
EP19870118528 1987-02-07 1987-12-15 Multiple-use thermal printing transfer ribbon Expired - Lifetime EP0278091B1 (en)

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DE19873703813 DE3703813A1 (en) 1987-02-07 1987-02-07 MULTIPLE OVERWRITABLE THERMAL RIBBON

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