EP0321388A1 - Dye ribbon for thermal dye transfer - Google Patents

Dye ribbon for thermal dye transfer Download PDF

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Publication number
EP0321388A1
EP0321388A1 EP19880730277 EP88730277A EP0321388A1 EP 0321388 A1 EP0321388 A1 EP 0321388A1 EP 19880730277 EP19880730277 EP 19880730277 EP 88730277 A EP88730277 A EP 88730277A EP 0321388 A1 EP0321388 A1 EP 0321388A1
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EP
European Patent Office
Prior art keywords
layer
cellulose nitrate
ink
ribbon
heat
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
EP19880730277
Other languages
German (de)
French (fr)
Other versions
EP0321388B1 (en
Inventor
Wolfgang Dipl.-Ing. Beyer
Monika Dr Rer. Nat. Kohla
Manuela Schneider
Eduard Dr. rer. nat. Schütz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
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Filing date
Publication date
Priority claimed from DE19873742924 external-priority patent/DE3742924A1/en
Priority claimed from DE19883817753 external-priority patent/DE3817753A1/en
Application filed by Siemens AG filed Critical Siemens AG
Priority to AT88730277T priority Critical patent/ATE71884T1/en
Publication of EP0321388A1 publication Critical patent/EP0321388A1/en
Application granted granted Critical
Publication of EP0321388B1 publication Critical patent/EP0321388B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • 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]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/3179—Next to cellulosic
    • 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]
    • Y10T428/31801—Of wax or waxy 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate

Definitions

  • the invention relates to an ink ribbon for dye transfer under the action of heat with a carrier layer, a color layer and an exothermic decomposable component which supports dye transfer when heat is supplied.
  • an ink layer applied to a carrier layer contains an aromatic azido compound which decomposes exothermically when a heat is applied by a thermal print head and has a reaction temperature in the range from 170 ° C. to 200 ° C. provides additional heat to soften the color layer.
  • a heat-sensitive ink ribbon with hydrazone derivatives is known as an exothermically decomposable component in the ink layer or as an intermediate layer between the carrier layer and the ink layer; the decomposition temperature is in the range between 150 ° C and 200 ° C; for the specific energy released in the process, the typical value is 200 J / g.
  • the invention has for its object the decomposition of an ink ribbon with an exothermic decomposable component to reduce the temperature even further and to increase the energy thereby released in order to be able to further reduce the drive energy for printing with this ink ribbon.
  • the component of the ribbon of the type specified at the outset consists of cellulose nitrate, the decomposition temperature of which is set in the range between 100 ° C. and 150 ° C. by catalytic additives.
  • the main advantage of the ink ribbon according to the invention is that the cellulose nitrate decomposes explosively when the ink ribbon is heated locally in the area of the printing zone, thereby supplying additional heat to soften the ink layer, as well as a firm bond due to the gases released explosively when the cellulose nitrate decomposes the color on the recording medium to be printed.
  • the energy released during the local exothermic decomposition of the cellulose nitrate is, depending on the respective degree of nitration of the cellulose nitrate, in the order of magnitude of conventional explosives such as TNT or nitroglycerin, so that the color is pressed deeply into the recording medium by the kinetic energy of the gases released during the decomposition and in particular fills up surface depressions of the record carrier.
  • the decomposition temperature i.e. the temperature threshold at which the decomposition of the cellulose nitrate starts, is on the one hand well above the normal ambient temperature and the operating temperature of a printer, while on the other hand the printing temperature required for printing and thus the control energy required for a thermal print head is relatively low .
  • the cellulose nitrate is contained as a component in the ink layer in a heat-meltable ink layer.
  • the latter in the case of a release layer formed between the ink layer on the carrier layer, the latter consists of the cellulose nitrate.
  • the high specific decomposition energy of the cellulose nitrate advantageously allows the release layer to be made very thin, the cellulose nitrate itself forming the release layer and not requiring any additional polymer as a binder. This results in a particularly sharp print image in thermal transfer printing because, due to the thinness of the release layer, its local decomposition area with respect to the heating area of the printing zone is defined with particularly sharp edges, for example by heating elements of a thermal print head or a heat radiation source.
  • the release layer decomposes completely in the area of its local heating, so that afterwards it is no longer possible for the color transferred to the recording medium to stick to the ink ribbon. It is therefore also not absolutely necessary to detach the ink ribbon immediately behind the printing zone from the recording medium, so that in connection with the ink ribbon according to the invention it is also possible to use thermal printheads which are only designed for use with ink ribbons without a release layer.
  • the release layer consisting of cellulose nitrate can be applied very easily from a solution on the carrier layer in the production of the ink ribbon according to the invention.
  • the cellulose nitrate preferably contains 1 to 20 percent by weight of amidosulfonic acid as a catalytic additive, as a result of which the decomposition temperature of the cellulose nitrate is significantly reduced from approximately 180 ° C. to 190 ° C. to approximately 130 ° C. to 140 ° C. A further reduction in the decomposition temperature to approximately 110 ° C. to 130 ° C. is advantageously achieved in that the cellulose nitrate as a catalytic additive has a weight of 1 to 20 percent toluene-4-sulfonic acid contains.
  • the ink ribbon 1 shown in Figure 1 has a carrier layer 2, which consists for example of polyethylene terephthalate or polycarbonate.
  • a color layer 3 is applied to the carrier layer 2, which contains dyes bound in waxes and / or thermoplastics and cellulose nitrate as an exothermic decomposable component.
  • the decomposition temperature of the cellulose nitrate is due to catalytic additives such.
  • amidosulfonic acid which is also known under the names amino-sulfuric acid or sulfamic acid, or toluene-4-sulfonic acid, also known as para-toluenesulfonic acid, are added to the cellulose nitrate as catalytic additives.
  • the decomposition temperature of the cellulose nitrate is reduced by these catalytic additives to about 130 ° to 140 ° C or 110 ° C to 130 °, the heat energy released as a function of temperature at catalyst concentrations below 10% very sharp and steep, at higher catalyst concentrations wider .
  • the specific amount of heat and gas released during the decomposition of the cellulose nitrate depends on the selected degree of nitration of the cellulose nitrate, which is 10.9% to 12.2%; the specific decomposition energy achieved ranges from 500 J / g to 2000 J / g and is thus far above the values for the hydrazone derivatives given in US Pat. No. 4,525,722.
  • the amount of gas released is up to 70% of the amount of cellulose nitrate.
  • the ink ribbon 1 on its side formed by the carrier layer 2 in a manner not shown here is locally heated to a temperature above the decomposition temperature of the cellulose nitrate with the catalytic additives by heating elements of a thermal print head or a heat radiation source (laser) warmed up.
  • the cellulose nitrate decomposes explosively, releasing additional heat and releasing gases (CO2, CO, N2, H2).
  • the additional heat causes the ink layer 3 to melt, while the released gases bind the melted ink particles with high kinetic energy to the recording medium in contact with the ink layer 3.
  • the ink ribbon 4 shown in Figure 2 has a carrier layer 5, which consists for example of polyethylene terephthalate or polycarbonate.
  • the carrier layer 5 carries a release layer (release layer) 6, which consists of cellulose nitrate and from an organic solution such as. B. butyl acetate, ethyl acetate or acetone is applied.
  • the decomposition temperature of the release layer is, as described above for the embodiment of Figure 1, by catalytic additives such as. B. acids or metal salts in adaptation to the heating capacity of different types of printer in which the ribbon 4 is used, adjustable, the amount of heat and gas released in the decomposition of the release layer 6 is dependent on the selected degree of nitration of the cellulose nitrate.
  • Adhesive layer 6 adheres to an ink layer 7, on which, during thermal transfer printing, a recording medium to be printed is guided past (not shown here) with the ink ribbon 4 interposed on a thermal printhead (also not shown) or a heat radiation source.
  • the color layer 7 contains dyes bound in waxes and / or thermoplastics.
  • the ink ribbon 4 is locally heated on its side formed by the carrier layer 5 in a manner not shown here by heating elements of the thermal print head or the heat radiation source to a temperature above the decomposition temperature of the release layer 6.
  • the release layer 6 decomposes explosively, releasing additional heat and releasing gases (CO2, CO, N2, H2).
  • the additional heat causes the ink layer 7 to melt, while the released gases bind the melted ink particles to the recording medium lying against the ink layer 7 with high kinetic energy. Since the release layer 6 decomposes almost completely in the area of its heating, the ink detached in this area can no longer stick to the ink ribbon 1 after the printing zone has cooled, so that perfect ink transfer to the recording medium is ensured.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Impression-Transfer Materials And Handling Thereof (AREA)
  • Decoration By Transfer Pictures (AREA)

Abstract

A known ink ribbon consisting of a carrier layer and an ink layer also contains an exothermically decomposable component which, when heat is supplied, supports ink transfer. <??>In the new ink ribbon(1, 4) a particularly good release of the ink layer (3, 7) from the carrier layer (2, 5) and a firm attachment of the ink to a record carrier to be printed are attained by providing cellulose nitrate as a component in the ink layer (3) or in the form of a release layer (6) between the carrier layer (5) and the ink layer (7). The decomposition temperature of the cellulose nitrate is adjustable in the region between 100 DEG C and 150 DEG C by the addition of catalysts. <IMAGE>

Description

Die Erfindung betrifft ein Farbband zur Farbstoffübertragung unter Wärmeeinwirkung mit einer Trägerschicht, einer Farbschicht und einer die Farbstoffübertragung bei Wärme­zufuhr unterstützenden exotherm zersetzbaren Komponente.The invention relates to an ink ribbon for dye transfer under the action of heat with a carrier layer, a color layer and an exothermic decomposable component which supports dye transfer when heat is supplied.

Bei einem derartigen aus der EP-A-0 150 383 bekannten Farbband enthält eine auf einer Trägerschicht aufgebrachte Farbschicht eine aromatische Azido-Verbindung, die sich bei Wärmezufuhr durch einen Thermodruckkopf exotherm mit einer Reaktionstempe­ratur im Bereich von 170° C bis 200° C zersetzt und dabei zu­sätzliche Wärme zur Erweichung der Farbschicht liefert.In the case of such an ink ribbon known from EP-A-0 150 383, an ink layer applied to a carrier layer contains an aromatic azido compound which decomposes exothermically when a heat is applied by a thermal print head and has a reaction temperature in the range from 170 ° C. to 200 ° C. provides additional heat to soften the color layer.

Aus der US-A-4 525 722 ist ein wärmeempfindliches Farbband mit Hydrazonderivaten als exotherm zersetzbarer Komponente in der Farbschicht oder als Zwischenschicht zwischen der Trägerschicht und der Farbschicht bekannt; die Zersetzungstemperatur liegt im Bereich zwischen 150° C und 200° C; für die dabei freiwerden­de spezifische Energie ist als typischer Wert 200 J/g angegeben.From US-A-4 525 722 a heat-sensitive ink ribbon with hydrazone derivatives is known as an exothermically decomposable component in the ink layer or as an intermediate layer between the carrier layer and the ink layer; the decomposition temperature is in the range between 150 ° C and 200 ° C; for the specific energy released in the process, the typical value is 200 J / g.

Schließlich ist aus der JP-A-59 165690 (Patent Abstracts of Japan, Bd. 9, Nr. 18 (M-353)(1741), 25. Januar 1985) sowie aus "IBM Technical Disclosure Bulletin, Bd. 19, Nr. 2, Juli 1976, Seite 672 Cellulosenitrat (auch unter der Bezeichnung "Nitro­cellulose¨ bekannt) als Haftvermittler zwischen der Träger­schicht und der Farbe eines wärmeempfindlichen Farbbandes bekannt, jedoch dient dort das Cellulosenitrat lediglich der Haftvermittlung und ist nicht exotherm reaktiv.Finally, from JP-A-59 165690 (Patent Abstracts of Japan, Vol. 9, No. 18 (M-353) (1741), January 25, 1985) and from "IBM Technical Disclosure Bulletin, Vol. 19, No. 2 July 1976, page 672 Cellulose nitrate (also known under the name "nitrocellulose") is known as an adhesion promoter between the backing layer and the color of a heat-sensitive ink ribbon, but the cellulose nitrate is only used for adhesion promotion and is not exothermically reactive.

Der Erfindung liegt die Aufgabe zugrunde, bei einem Farbband mit einer exotherm zersetzbaren Komponente die Zersetzungs­ temperatur noch weiter zu verringern und die dabei freiwerdende Energie zu erhöhen, um die Ansteuerenergie zum Drucken mit diesem Farbband weiter verringern zu können.The invention has for its object the decomposition of an ink ribbon with an exothermic decomposable component to reduce the temperature even further and to increase the energy thereby released in order to be able to further reduce the drive energy for printing with this ink ribbon.

Zur Lösung dieser Aufgabe besteht gemäß der Erfindung bei dem Farbband der eingangs angegebenen Art die Komponente aus Cellulosenitrat, dessen Zersetzungstemperatur durch katalyti­sche Zusätze im Bereich zwischen 100° C und 150° C eingestellt ist.To achieve this object, according to the invention, the component of the ribbon of the type specified at the outset consists of cellulose nitrate, the decomposition temperature of which is set in the range between 100 ° C. and 150 ° C. by catalytic additives.

Der wesentliche Vorteil des erfindungsgemäßen Farbbandes be­steht darin, daß sich das Cellulosenitrat bei lokaler Auf­heizung des Farbbandes im Bereich der Druckzone explosions­artig zersetzt und dabei sowohl zusätzliche Wärme zur Erweichung der Farbschicht liefert, als auch durch die bei der Zersetzung des Cellulosenitrats explosionsartig freiwerdenden Gase eine feste Anbindung der Farbe an dem zu bedruckenden Auf­zeichnungsträger bewirkt. Die bei der lokalen exothermen Zer­setzung des Cellulosenitrats freiwerdende Energie liegt in Abhängigkeit von dem jeweiligen Nitrierungsgrad des Cellulose­nitrats in der Größenordnung von üblichen Sprengstoffen wie TNT oder Nitroglycerin, so daß durch die kinetische Energie der bei der Zersetzung freiwerdenden Gase die Farbe tief in den Auf­zeichnungsträger eingedrückt wird und dabei insbesondere Ober­flächenvertiefungen des Aufzeichnungsträgers auffüllt. Aufgrund der katalytischen Zusätze liegt die Zersetzungstemperatur, also die Temperaturschwelle, bei der die Zersetzung des Cellulose­nitrats einsetzt, einerseits deutlich über der normalen Umgebungstemperatur und der Betriebstemperatur eines Druckers, während andererseits die zum Drucken erforderliche Drucktempe­ratur und damit die erforderliche Ansteuerenergie für einen Thermodruckkopf verhältnismäßig gering ist.The main advantage of the ink ribbon according to the invention is that the cellulose nitrate decomposes explosively when the ink ribbon is heated locally in the area of the printing zone, thereby supplying additional heat to soften the ink layer, as well as a firm bond due to the gases released explosively when the cellulose nitrate decomposes the color on the recording medium to be printed. The energy released during the local exothermic decomposition of the cellulose nitrate is, depending on the respective degree of nitration of the cellulose nitrate, in the order of magnitude of conventional explosives such as TNT or nitroglycerin, so that the color is pressed deeply into the recording medium by the kinetic energy of the gases released during the decomposition and in particular fills up surface depressions of the record carrier. Due to the catalytic additives, the decomposition temperature, i.e. the temperature threshold at which the decomposition of the cellulose nitrate starts, is on the one hand well above the normal ambient temperature and the operating temperature of a printer, while on the other hand the printing temperature required for printing and thus the control energy required for a thermal print head is relatively low .

Entsprechend einer ersten Ausbildung des erfindungsgemäßen Farbbandes ist bei einer wärmeschmelzbaren Farbschicht das Cellulosenitrat als Komponente in der Farbschicht enthalten.According to a first embodiment of the ink ribbon according to the invention, the cellulose nitrate is contained as a component in the ink layer in a heat-meltable ink layer.

Bei einer alternativen Ausbildung des erfindungsgemäßen Farb­bandes besteht bei einer zwischen der Farbschicht auf der Trägerschicht ausgebildeten Ablöseschicht diese aus dem Cellulosenitrat. Die hohe spezifische Zersetzungsenergie des Cellulosenitrats erlaubt dabei in vorteilhafter Weise eine sehr dünne Ausbildung der Ablöseschicht, wobei das Cellulose­nitrat selbst die Ablöseschicht bildet und kein zusätzliches Polymer als Binder erfordert. Hierdurch wird ein besonders scharfes Druckbild beim Thermotransferdruck erzielt, weil aufgrund der Dünne der Ablöseschicht deren lokaler Zer­setzungsbereich in bezug auf den Erwärmungsbereich der Druck­zone beispielsweise durch Heizelemente eines Thermodruckkopfes oder eine Wärmestrahlungsquelle besonders scharfrandig definiert wird. Ein weiterer Vorteil ist darin zu sehen, daß sich die Ablöseschicht im Bereich ihrer lokalen Erwärmung voll­ständig zersetzt, so daß danach ein Ankleben der auf den Auf­zeichnungsträger übertragenen Farbe an dem Farbband nicht mehr möglich ist. Es ist daher auch nicht zwingend erforderlich, das Farbband unmittelbar hinter der Druckzone von dem Aufzeichnungs­träger abzulösen, so daß in Verbindung mit dem erfindungsge­mäßen Farbband auch solche Thermodruckköpfe Verwendung finden können, die lediglich für eine Verwendung mit Farbbändern ohne Ablöseschicht ausgebildet sind. Schließlich läßt sich die aus Cellulosenitrat bestehende Ablöseschicht bei der Herstellung des erfindungsgemäßen Farbbandes sehr einfach aus einer Lösung auf der Trägerschicht aufbringen.In an alternative embodiment of the ink ribbon according to the invention, in the case of a release layer formed between the ink layer on the carrier layer, the latter consists of the cellulose nitrate. The high specific decomposition energy of the cellulose nitrate advantageously allows the release layer to be made very thin, the cellulose nitrate itself forming the release layer and not requiring any additional polymer as a binder. This results in a particularly sharp print image in thermal transfer printing because, due to the thinness of the release layer, its local decomposition area with respect to the heating area of the printing zone is defined with particularly sharp edges, for example by heating elements of a thermal print head or a heat radiation source. Another advantage can be seen in the fact that the release layer decomposes completely in the area of its local heating, so that afterwards it is no longer possible for the color transferred to the recording medium to stick to the ink ribbon. It is therefore also not absolutely necessary to detach the ink ribbon immediately behind the printing zone from the recording medium, so that in connection with the ink ribbon according to the invention it is also possible to use thermal printheads which are only designed for use with ink ribbons without a release layer. Finally, the release layer consisting of cellulose nitrate can be applied very easily from a solution on the carrier layer in the production of the ink ribbon according to the invention.

Als katalytische Zusätze kommen insbesondere Metallsalze und/oder organische Säuren in Betracht. Vorzugsweise enthält das Cellulosenitrat als katalytischen Zusatz 1 bis 20 Gewichts­prozente Amidosulfonsäure, wodurch die Zersetzungstemperatur des Cellulosenitrats von etwa 180° C bis 190° C signifikant auf etwa 130° C bis 140° C gesenkt wird. Eine noch weitere Absenkung der Zersetzungstemperatur auf etwa 110° C bis 130° C wird in vorteilhafter Weise dadurch erreicht, daß das Cellulosenitrat als katalytischen Zusatz 1 bis 20 Gewichts­ prozente Toluol-4-Sulfonsäure enthält.Metal salts and / or organic acids are particularly suitable as catalytic additives. The cellulose nitrate preferably contains 1 to 20 percent by weight of amidosulfonic acid as a catalytic additive, as a result of which the decomposition temperature of the cellulose nitrate is significantly reduced from approximately 180 ° C. to 190 ° C. to approximately 130 ° C. to 140 ° C. A further reduction in the decomposition temperature to approximately 110 ° C. to 130 ° C. is advantageously achieved in that the cellulose nitrate as a catalytic additive has a weight of 1 to 20 percent toluene-4-sulfonic acid contains.

Zur Erläuterung der Erfindung wird auf die Figuren der Zeichnung Bezug genommen, die zwei Ausführungsbeispiele des erfindungsgemäßen Farbbandes zeigen.To explain the invention, reference is made to the figures of the drawing, which show two exemplary embodiments of the ink ribbon according to the invention.

Das in Figur 1 dargestellte Farbband 1 weist eine Trägerschicht 2 auf, die beispielsweise aus Polyethylenterephthalat oder Polycarbonat besteht. Auf der Trägerschicht 2 ist eine Farb­schicht 3 aufgebracht, die in Wachsen und/oder Thermoplasten gebundene Farbstoffe und als exotherm zersetzbare Komponente Cellulosenitrat enthält. Die Zersetzungstemperatur des Cellulosenitrats ist durch katalytische Zusätze wie z. B. organische Säuren und/oder Metallsalze in Anpassung an das Heizvermögen verschiedener Druckertypen, in denen das erfindungsgemäße Farbband 1 verwendet werden soll, angepaßt. Als katalytische Zusätze sind dem Cellulosenitrat 1 bis 20, vorzugsweise 5 bis 10 Gewichtsprozente Amidosulfonsäure, die auch unter den Bezeichnungen Aminoschwefelsäure oder Sulfamin­säure bekannt ist, oder Toluol-4-Sulfonsäure, auch als para-Toluolsulfonsäure bekannt, zugesetzt. Die Zersetzungs­temperatur des Cellulosenitrats wird durch diese katalytischen Zusätze auf etwa 130° bis 140° C bzw. 110° C bis 130° gesenkt, wobei die freiwerdende Wärmeenergie als Funktion der Temperatur bei Katalysatorkonzentrationen unter 10 % sehr scharf und steilflankig, bei höheren Katalysatorkonzentrationen breiter verläuft. Die bei der Zersetzung des Cellulosenitrats frei­werdende spezifische Wärme- und Gasmenge ist von dem gewählten Nitrierungsgrad des Cellulosenitrats abhängig, der 10,9 % bis 12,2 % beträgt; die erreichte spezifische Zersetzungsenergie reicht dabei von 500 J/g bis 2000 J/g und liegt damit weit über den in der US-A-4 525 722 angegebenen Werten für die Hydrazon­derivate. Die freiwerdende Gasmenge beträgt bis zu 70 % der Menge des Cellulosenitrats.The ink ribbon 1 shown in Figure 1 has a carrier layer 2, which consists for example of polyethylene terephthalate or polycarbonate. A color layer 3 is applied to the carrier layer 2, which contains dyes bound in waxes and / or thermoplastics and cellulose nitrate as an exothermic decomposable component. The decomposition temperature of the cellulose nitrate is due to catalytic additives such. B. organic acids and / or metal salts in adaptation to the heating capacity of different printer types in which the ribbon 1 according to the invention is to be used, adapted. 1 to 20, preferably 5 to 10 percent by weight of amidosulfonic acid, which is also known under the names amino-sulfuric acid or sulfamic acid, or toluene-4-sulfonic acid, also known as para-toluenesulfonic acid, are added to the cellulose nitrate as catalytic additives. The decomposition temperature of the cellulose nitrate is reduced by these catalytic additives to about 130 ° to 140 ° C or 110 ° C to 130 °, the heat energy released as a function of temperature at catalyst concentrations below 10% very sharp and steep, at higher catalyst concentrations wider . The specific amount of heat and gas released during the decomposition of the cellulose nitrate depends on the selected degree of nitration of the cellulose nitrate, which is 10.9% to 12.2%; the specific decomposition energy achieved ranges from 500 J / g to 2000 J / g and is thus far above the values for the hydrazone derivatives given in US Pat. No. 4,525,722. The amount of gas released is up to 70% of the amount of cellulose nitrate.

Zum Drucken eines Bildmusters auf einem hier nicht dargestell­ten Aufzeichnungsträger wird das Farbband 1 an seiner von der Trägerschicht 2 gebildeten Seite in hier nicht dargestell­ter Weise durch Heizelemente eines Thermodruckkopfes oder einer Wärmestrahlungsquelle (Laser) lokal auf eine Temperatur ober­halb der Zersetzungstemperatur des Cellulosenitrats mit den katalytischen Zusätzen erwärmt. An der Erwärmungsstelle zer­setzt sich das Cellulosenitrat explosionsartig unter Abgabe zusätzlicher Wärme und unter Freisetzung von Gasen (CO₂, CO, N₂, H₂). Die zusätzliche Wärme bewirkt ein Auf­schmelzen der Farbschicht 3, während die freiwerdenden Gase die aufgeschmolzenen Farbpartikel mit hoher kinetischer Energie an den an der Farbschicht 3 anliegenden Aufzeichnungsträger an­binden.To print an image pattern on a recording medium (not shown here), the ink ribbon 1 on its side formed by the carrier layer 2 in a manner not shown here is locally heated to a temperature above the decomposition temperature of the cellulose nitrate with the catalytic additives by heating elements of a thermal print head or a heat radiation source (laser) warmed up. At the heating point, the cellulose nitrate decomposes explosively, releasing additional heat and releasing gases (CO₂, CO, N₂, H₂). The additional heat causes the ink layer 3 to melt, while the released gases bind the melted ink particles with high kinetic energy to the recording medium in contact with the ink layer 3.

Das in Figur 2 dargestellte Farbband 4 weist eine Trägerschicht 5 auf, die beispielsweise aus Polyethylenterephthalat oder Polycarbonat besteht. Die Trägerschicht 5 trägt eine Ablöse­schicht (Release-Schicht) 6, die aus Cellulosenitrat besteht und aus einer organischen Lösung wie z. B. Butylacetat, Ethyl­acetat oder Aceton aufgetragen wird. Die Zersetzungstemperatur der Ablöseschicht ist ebenso, wie oben für das Ausführungsbei­spiel nach Figur 1 beschrieben, durch katalytische Zusätze wie z. B. Säuren oder Metallsalze in Anpassung an das Heizvermögen verschiedener Druckertypen, in denen das Farbband 4 verwendet wird, einstellbar, wobei die bei der Zersetzung der Ablöse­schicht 6 freiwerdenden Wärme- und Gasmenge von dem gewählten Nitrierungsgrad des Cellulosenitrats abhängig ist. An der Ab­löseschicht 6 haftet eine Farbschicht 7, an der beim Thermo­transferdruck ein zu bedruckender Aufzeichnungsträger anliegend (hier nicht dargestellt) unter Zwischenlage des Farbbandes 4 an einem ebenfalls nicht gezeigten Thermodruckkopf oder einer Wärme­strahlungsquelle vorbeigeführt wird. Die Farbschicht 7 enthält in Wachsen und/oder Thermoplasten gebundene Farbstoffe.The ink ribbon 4 shown in Figure 2 has a carrier layer 5, which consists for example of polyethylene terephthalate or polycarbonate. The carrier layer 5 carries a release layer (release layer) 6, which consists of cellulose nitrate and from an organic solution such as. B. butyl acetate, ethyl acetate or acetone is applied. The decomposition temperature of the release layer is, as described above for the embodiment of Figure 1, by catalytic additives such as. B. acids or metal salts in adaptation to the heating capacity of different types of printer in which the ribbon 4 is used, adjustable, the amount of heat and gas released in the decomposition of the release layer 6 is dependent on the selected degree of nitration of the cellulose nitrate. Adhesive layer 6 adheres to an ink layer 7, on which, during thermal transfer printing, a recording medium to be printed is guided past (not shown here) with the ink ribbon 4 interposed on a thermal printhead (also not shown) or a heat radiation source. The color layer 7 contains dyes bound in waxes and / or thermoplastics.

Zum Drucken eines Bildmusters wird das Farbband 4 an seiner von der Trägerschicht 5 gebildeten Seite in hier nicht dargestellter Weise durch Heizelemente des Thermodruckkopfes oder der Wärme­strahlungsquelle lokal auf eine Temperatur oberhalb der Zer­setzungstemperatur der Ablöseschicht 6 erwärmt. An dieser Stelle zersetzt sich die Ablöseschicht 6 explosionsartig unter Abgabe zusätzlicher Wärme und unter Freisetzung von Gasen (CO₂, CO, N₂, H₂). Die zusätzliche Wärme bewirkt ein Aufschmelzen der Farbschicht 7, während die freiwerdenden Gase die auf­geschmolzenen Farbpartikel mit hoher kinetischer Energie an den an der Farbschicht 7 anliegenden Aufzeichnungsträger anbinden. Da sich die Ablöseschicht 6 im Bereich ihrer Erwärmung nahezu vollständig zersetzt, kann die in diesem Bereich abgelöste Farbe nach dem Abkühlen der Druckzone nicht mehr an dem Farb­band 1 kleben, so daß eine einwandfreie Farbübertragung auf den Aufzeichnungsträger gewährleistet ist.To print an image pattern, the ink ribbon 4 is locally heated on its side formed by the carrier layer 5 in a manner not shown here by heating elements of the thermal print head or the heat radiation source to a temperature above the decomposition temperature of the release layer 6. At this point, the release layer 6 decomposes explosively, releasing additional heat and releasing gases (CO₂, CO, N₂, H₂). The additional heat causes the ink layer 7 to melt, while the released gases bind the melted ink particles to the recording medium lying against the ink layer 7 with high kinetic energy. Since the release layer 6 decomposes almost completely in the area of its heating, the ink detached in this area can no longer stick to the ink ribbon 1 after the printing zone has cooled, so that perfect ink transfer to the recording medium is ensured.

Claims (5)

1. Farbband (1;4) zur Farbstoffübertragung unter Wärmeeinwirkung mit einer Trägerschicht (2;5), einer Farbschicht (3;7) und einer die Farbstoffübertragung bei Wärmezufuhr unterstützenden, zersetzbaren Komponente,
dadurch gekennzeichnet, daß die Komponente aus Cellulosenitrat esteht, dessen Zersetzungs­temperatur durch katalytische Zusätze im Bereich zwischen 100° C und 150° C eingestellt ist.1. Ribbon (1; 4) for dye transfer under the action of heat with a carrier layer (2; 5), a color layer (3; 7) and a decomposable component that supports dye transfer when heat is applied,
characterized in that the component consists of cellulose nitrate, the decomposition temperature of which is set by catalytic additives in the range between 100 ° C and 150 ° C. 2. Farbband nach Anspruch 1,
dadurch gekennzeichnet, daß bei einer wärmeschmelzbaren Farbschicht das Cellulosenitrat als Komponente in der Farbschicht (3) enthalten ist.2. Ribbon according to claim 1,
characterized in that in the case of a heat-meltable color layer, the cellulose nitrate is contained as a component in the color layer (3). 3. Farbband nach Anspruch 1,
dadurch gekennzeichnet, daß bei einer zwischen der Farbschicht (7) und der Trägerschicht (5) ausgebildeten Ablöseschicht (6) diese aus dem Cellulosenitrat besteht.3. Ribbon according to claim 1,
characterized in that, in the case of a release layer (6) formed between the color layer (7) and the carrier layer (5), the latter consists of the cellulose nitrate. 4. Farbband nach einem der vorangehenden Ansprüche,
dadurch gekennzeichnet, daß das Cellulosenitrat als katalytischen Zusatz 1 bis 20 Gewichts­prozente Amidosulfonsäure enthält.4. Ribbon according to one of the preceding claims,
characterized in that the cellulose nitrate contains 1 to 20 percent by weight of amidosulfonic acid as a catalytic additive. 5. Farbband nach einem der Ansprüche 1 bis 3,
dadurch gekennzeichnet, daß das Cellulosenitrat als katalytischen Zusatz 1 bis 20 Gewichts­prozente Toluol-4-Sulfonsäure enthält.5. Ribbon according to one of claims 1 to 3,
characterized in that the cellulose nitrate contains 1 to 20 percent by weight of toluene-4-sulfonic acid as a catalytic additive.
EP19880730277 1987-12-15 1988-12-08 Dye ribbon for thermal dye transfer Expired - Lifetime EP0321388B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88730277T ATE71884T1 (en) 1987-12-15 1988-12-08 RIBBON FOR HEAT DYE TRANSFER.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3742924 1987-12-15
DE19873742924 DE3742924A1 (en) 1987-12-15 1987-12-15 Colour ribbon for dye transfer under the action of heat
DE19883817753 DE3817753A1 (en) 1988-05-20 1988-05-20 Colour ribbon for dye transfer under the action of heat
DE3817753 1988-05-20

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EP0321388A1 true EP0321388A1 (en) 1989-06-21
EP0321388B1 EP0321388B1 (en) 1992-01-22

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EP (1) EP0321388B1 (en)
JP (1) JPH01196381A (en)
AT (1) ATE71884T1 (en)
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WO1991008908A1 (en) * 1989-12-15 1991-06-27 Siemens Aktiengesellschaft Thermo-transfer ribbon

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US5945249A (en) * 1995-04-20 1999-08-31 Imation Corp. Laser absorbable photobleachable compositions
GB9617416D0 (en) * 1996-08-20 1996-10-02 Minnesota Mining & Mfg Thermal bleaching of infrared dyes
US7423286B2 (en) * 2003-09-05 2008-09-09 Si2 Technologies, Inc. Laser transfer article and method of making

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EP0432506A2 (en) * 1989-12-14 1991-06-19 M.A.N.-ROLAND Druckmaschinen Aktiengesellschaft Thermal transfer foil for forming images directly onto a printing cylinder
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WO1991008908A1 (en) * 1989-12-15 1991-06-27 Siemens Aktiengesellschaft Thermo-transfer ribbon

Also Published As

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US4897310A (en) 1990-01-30
EP0321388B1 (en) 1992-01-22
ATE71884T1 (en) 1992-02-15
DE3868033D1 (en) 1992-03-05
JPH01196381A (en) 1989-08-08

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