EP0304672B1 - Process for manufacture of a thermally sensitive ribbon for use in thermal transfer printing and the printing ribbon obtained therefrom - Google Patents
Process for manufacture of a thermally sensitive ribbon for use in thermal transfer printing and the printing ribbon obtained therefrom Download PDFInfo
- Publication number
- EP0304672B1 EP0304672B1 EP88112415A EP88112415A EP0304672B1 EP 0304672 B1 EP0304672 B1 EP 0304672B1 EP 88112415 A EP88112415 A EP 88112415A EP 88112415 A EP88112415 A EP 88112415A EP 0304672 B1 EP0304672 B1 EP 0304672B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wax
- substance
- thermal
- ribbon
- aqueous
- 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.)
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Classifications
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- 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
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- 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
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- 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
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- 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 method for producing a thermal ink ribbon for thermal transfer printing with a layer of a melting ink on one side of a carrier film, the melting ink containing a wax and / or a wax-like substance, a colorant, a thermoplastic binder and optionally further additives, and one then available product.
- Thermal ribbons have been known for a long time. They have a layer of a melting ink on a film-like carrier, which can be made of paper or plastic, for example, in the form of a meltable wax-bound or plastic-bound colorant or carbon black layer. In these thermal ribbons, the melting ink is melted by means of a thermal print head and transferred to a recording paper or film. This is generally referred to as a thermal transfer ribbon or TCR ribbon ("Thermal Carbon Ribbon").
- Thermal printers which emboss a heat symbol during the printing process are known, for example, from DE-ASen 2062494 and 2406613 and DE-OS 3224445. The printing process is as follows:
- the print head of a thermal printer presses the thermal ink ribbon onto the recording substrate.
- the printhead develops temperatures that can reach a maximum of around 400 ° C.
- the uncoated back of the thermal ribbon or the film-like carrier is in direct contact with the printhead or the thermal symbol formed thereon during the printing process.
- the relative speed between the thermal ink ribbon and the printing paper or film is zero.
- the melting ink in the form of the symbol to be printed is transferred from the thermal ink ribbon to the recording substrate by a melting process.
- the thermal ink ribbon is detached from the recording substrate, the molten symbol adheres to it and solidifies.
- thermal ribbons with simple film-like carriers
- 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 represents the actual "functional layer” during the printing process, also contains the materials already described above. In professional circles this is called an electro-thermal transfer process ("Electro Thermal Ribbon").
- electro-thermal transfer process Such a thermal transfer printing system is described for example in US-PS 4309117.
- thermal ribbons that advertise several times (keyword: "multiuse”). Such thermal ribbons are described for example in EP-A-0063000.
- the melting ink of the thermal ink ribbon is then 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 allows only a small amount of the molten colored material to be transferred to be used in each individual printing operation.
- the invention was therefore based on the object of developing the method described at the outset in such a way that it precludes the need to use environmentally harmful solvents in its preparation.
- this object is achieved in that an aqueous coating dispersion which contains the thermoplastic binder, the wax or the wax-like substance and a fat-soluble dye in finely divided form is applied in a manner known per se to the support of the thermal ribbon, the aqueous portion of the Dispersion evaporated and a thermal treatment is carried out with melting of the wax or the wax-like substance.
- the essence of the invention is therefore that an aqueous coating dispersion containing the necessary fine-particle solids is applied to the carrier film and the aqueous portion of the dispersion evaporates below the melting point of the integrated wax particles or particles of the wax-like substance and these wax particles or particles of wax-like substance can be fused by thermal treatment.
- any plastic films are suitable, which are also used as supports in conventional carbon ribbons of typewriters, but which also withstand the high temperatures mentioned during the briefly running printing process and also release the melting ink at these temperatures.
- the plastic film consists in particular of thermoplastic plastics with a higher glass transition temperature.
- 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.
- polyethylene terephthalates and polycarbonates are preferred.
- the plastic film to be used according to the invention can also be a fabric laminated on one or both sides.
- similarly designed common composite films can be used within the scope of the invention.
- plasticizer in order to achieve improved flexibility.
- a substance that increases the thermal conductivity can also be incorporated.
- the thickness of the plastic film is determined according to the respective requirements. As a rule, however, it is relatively thin, e.g. about 3 to 6 micrometers to allow the necessary heat transfers to run optimally. This range can also be more or less far exceeded.
- wax used in connection with the invention is to be understood as far as possible.
- Such a material should generally have the following properties: not kneadable at 20 ° C, solid to brittle-hard, coarse to fine crystalline, translucent to opaque, but not glassy, meltable above 40 ° C without decomposition, but a little above the melting point relatively low-viscosity and non-stringy.
- wax-like substances should be understood to mean those materials which largely resemble the waxes with regard to the physical and chemical properties.
- the melting point of the wax or wax-like substance chosen in each case is preferably at least about 70 ° C.
- the upper limit is preferably about 90 ° C.
- the aqueous coating dispersion contains the mentioned solid particles, i.e. the thermoplastic, the wax or the wax-like substance and the fat-soluble dye and the pigment, preferably in a particle size of 0.5 to 100 micrometers and in particular of about 5 to 50 micrometers. Particularly good process products are obtained in this particle size range.
- the aqueous coating dispersion or suspension of these materials can be prepared in various ways. This can be done, for example, by suspending fine, solid particles of these materials or else by emulsifying in the melt and then cooling, preferably with stirring to maintain the finest dispersion.
- thermoplastics are hard or even brittle plastics, which soften reversibly when heat is applied and become mechanically easily deformable, in order to finally change to a viscous liquid state at high temperatures.
- thermoplastics which do not melt during the final thermal treatment, or which at most soften at most.
- thermoplastic binders include in particular polystyrene, polyvinyl acetate, polyvinyl acetal, polyvinyl chloride, polyethylene, copolymers of vinyl acetate and vinyl chlorides, polyvinyl ether, polyvinyl propionates, polyacrylates, ethylene / vinyl acetate copolymers.
- thermoplastic binders serve as a framework substance in the layer of the melting ink designed according to the invention.
- suitable known plasticizers can also be incorporated into the thermoplastic binder, e.g.
- Phthalic acid esters such as di-2-ethylhexyl phthalate, di-isononyl phthalate and di-isodecyl phthalate, aliphatic dicarboxylic acid esters, such as that of adipic acid, in particular di-2-ethylhexyl adipate and diisodecyl adipate, phosphates, such as tricresyl phosphate and triphenyl phosphate, such as fatty acid glycol, fatty acid esters -ethylbutyrate) and the like. In individual cases it can also be advantageous to incorporate stabilizers into the thermoplastic binder.
- the ratio of wax or wax-like substance to the thermoplastic binder in the aqueous coating dispersion can vary widely and is not critical for the purposes of the invention.
- the weight ratio can easily be between about 10: 1 to 1: 5.
- a weight ratio of approximately 5: 1 to 1: 1 is preferred.
- the solids content of the coating dispersion or starting dispersion originally used can likewise vary within wide limits, for example between about 20 and 80% by weight, preferably between about 30 and 60% by weight.
- fat-soluble dyes or "fat dyes” meet this requirement.
- This class includes, for example, simple azo and anthraquinone dyes, e.g. the products sold by Bayer AG under the name "Ceres dyes”.
- This also includes, in particular, the dyes Solvent Yellow 16, Solvent Yellow 29, Solvent Yellow 14, Solvent Red 1, Solvent Red 18, Solvent Red 25, Solvent Red 24, Solvent Red 19, Smoke Dye and Solvent Yellow 16 Solvent Blue 63, Solvent Blue 68, Solvent Green, Solvent Brown 1, Solvent Red 3, Solvent Green 3 and Solvent Black 3. This list is not intended to be limiting.
- pigments can also be used, such as carbon blacks, organic and / or inorganic color pigments, but also so-called fillers such as chalk, china clay, kaolin, clay, etc.
- the aqueous coating dispersion can be applied to the support in any manner, for example with a doctor knife.
- the application technology is therefore not critical. It can also be evaporated or concentrated in any way, for example by passing warm air over it.
- the temperature during evaporation or concentration of the aqueous portion of the applied aqueous coating dispersion should only be chosen so high that the wax particles or the particles of the wax-like substance are preferably not melted during the thermal treatment.
- work can also be carried out at room temperature, whereby the thermal treatment or the transfer of air would require a longer time.
- the thermal treatment of the product obtained, which is at or above the melting temperature of the wax or the wax-like substance.
- the wax or the wax-like material is fused by this thermal treatment.
- This thermal treatment can be carried out using customary measures, for example by treatment with heated rollers, exposure to warm air and thermal radiation. Through this heat treatment, the fat-soluble dye is transferred into the phase of the fused wax or the fused wax-like substance. A particularly high color yield is therefore achieved when using the thermal ink ribbon in conventional writing systems.
- the layer thickness of the melting ink should generally be between about 5 and 30 micrometers and preferably 10 to 20 micrometers (dry layer). If appropriate, an adhesion-promoting layer with a thickness of approximately 0.1 to 5 micrometers, preferably approximately 0.5 to 2 micrometers, can be arranged between the color layer and the carrier film. This preferably consists of polymeric materials of a known type.
- An aqueous dispersion was prepared using the following recipe:
- the dispersion which made up a total of 41 parts by weight, was applied by means of a doctor blade in a layer thickness of approximately 20 micrometers (based on the product which was subsequently dried) to a polyester support.
- a doctor blade By passing warm air at a temperature of 80 ° C, the aqueous portion of the applied dispersion was evaporated within a few minutes.
- a thermal treatment was then carried out with air at a temperature of about 100 ° C., the wax particles fusing together.
- the product obtained could be used directly as a thermal ribbon. It allowed an 8x multiuse.
- a thermal ribbon was produced using the following recipe:
- the 49 parts by weight of the dispersion obtained were applied to the support of a thermal ink ribbon in the manner described in Example 1 and dried. This is followed by a thermal treatment with hot air at a temperature of 100 ° C. to fuse the wax particles.
- the process product obtained also enabled an 8-fold multiuse.
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines Thermofarbbandes für den Thermotransferdruck mit einer Schicht einer Aufschmelzfarbe auf einer Seite einer Trägerfolie, wobei die Aufschmelzfarbe eine Wachs- und/oder eine wachsähnliche Substanz, ein Farbmittel, ein thermoplastisches Bindemittel sowie gegebenenfalls weitere Additive enthält, sowie ein danach erhältliches Erzeugnis.The invention relates to a method for producing a thermal ink ribbon for thermal transfer printing with a layer of a melting ink on one side of a carrier film, the melting ink containing a wax and / or a wax-like substance, a colorant, a thermoplastic binder and optionally further additives, and one then available product.
Thermofarbbänder sind seit langem bekannt. Sie weisen auf einem folienartigen Träger, der z.B. aus Papier oder Kunststoff bestehen kann, eine Schicht einer Aufschmelzfarbe auf, so in Form einer schmelzbaren wachsgebundenen oder kunststoffgebundenen Farbmittel- oder Rußschicht. Die Aufschmelzfarbe wird bei diesen Thermofarbbändern mittels eines Wärmedruckkopfes geschmolzen und auf ein Aufzeichnungspapier bzw. eine Aufzeichnungsfolie übertragen. Hier wird allgemein von einem Thermotransferband oder TCR-Band gesprochen ("Thermal Carbon Ribbon"). Thermische Drucker, die beim Druckvorgang ein Wärmesymbol aufprägen, sind z.B. aus den DE-ASen 2062494 und 2406613 sowie der DE-OS 3224445 bekannt. Beim Druckvorgang wird im einzelnen wie folgt vorgegangen:Thermal ribbons have been known for a long time. They have a layer of a melting ink on a film-like carrier, which can be made of paper or plastic, for example, in the form of a meltable wax-bound or plastic-bound colorant or carbon black layer. In these thermal ribbons, the melting ink is melted by means of a thermal print head and transferred to a recording paper or film. This is generally referred to as a thermal transfer ribbon or TCR ribbon ("Thermal Carbon Ribbon"). Thermal printers which emboss a heat symbol during the printing process are known, for example, from DE-ASen 2062494 and 2406613 and DE-OS 3224445. The printing process is as follows:
Der Druckkopf eines thermischen Druckers drückt das Thermofarbband auf das Aufzeichnungssubstrat. Der Druckkopf entwickelt dabei Temperaturen, die maximal bei etwa 400°C liegen können. Die unbeschichtete Rückseite des Thermofarbbandes bzw. der folienartige Träger steht während des Druckvorganges in direktem Kontakt mit dem Druckkopf bzw. dem darauf ausgebildeten Wärmesymbol. Im Zeitpunkt des eigentlichen Druckvorganges beträgt die relative Geschwindigkeit zwischen dem Thermofarbband und dem Druckpapier bzw. der Druckfolie Null. Durch die Einwirkung des Drucksymbols wird die Aufschmelzfarbe in Form des aufzudruckenden Symbols durch einen Schmelzvorgang von dem Thermofarbband auf das Aufzeichnungssubstrat übertragen. Beim Ablösen des Thermofarbbandes von dem Aufzeichnungssubstrat bleibt das geschmolzene Symbol hierauf haften und erstarrt.The print head of a thermal printer presses the thermal ink ribbon onto the recording substrate. The printhead develops temperatures that can reach a maximum of around 400 ° C. The uncoated back of the thermal ribbon or the film-like carrier is in direct contact with the printhead or the thermal symbol formed thereon during the printing process. At the time of the actual printing process, the relative speed between the thermal ink ribbon and the printing paper or film is zero. Through the action of the print symbol, the melting ink in the form of the symbol to be printed is transferred from the thermal ink ribbon to the recording substrate by a melting process. When the thermal ink ribbon is detached from the recording substrate, the molten symbol adheres to it and solidifies.
Neben den oben geschilderten Thermofarbbändern mit einfachen folienartigen Trägern gibt es auch noch solche Thermofarbbänder, 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 darstellt, enthält ebenfalls die bereits oben geschilderten Materialien. In der Fachwelt spricht man hier von einem elektro-thermischen Transferprozeß ("Electro Thermal Ribbon"). Ein derartiges Thermotransfer-Drucksystem wird beispielsweise in der US-PS 4309117 beschrieben.In addition to the above-described thermal ribbons with simple film-like carriers, there are also those thermal ribbons 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 represents the actual "functional layer" during the printing process, also contains the materials already described above. In professional circles this is called an electro-thermal transfer process ("Electro Thermal Ribbon"). Such a thermal transfer printing system is described for example in US-PS 4309117.
Es sind bereits Thermofarbbänder bekannt, die mehrfach ausschreiben (Stichwort: "multiuse"). Derartige Thermofarbbänder werden beispielsweise in der EP-A-0063000 beschrieben. Der Aufschmelzfarbe des Thermofarbbandes ist danach 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.There are already known thermal ribbons that advertise several times (keyword: "multiuse"). Such thermal ribbons are described for example in EP-A-0063000. The melting ink of the thermal ink ribbon is then 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.
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 des zu übertragenden geschmolzenen farbigen Materials verbrauchen läßt.This special particulate material is intended to give the layer of the melting ink, which is a solid mixture, a heterogeneous structure which allows only a small amount of the molten colored material to be transferred to be used in each individual printing operation.
Die bekannten Verfahren zur Herstellung obiger Thermofarbbänder zeigen u.a. den wesentlichen Nachteil, daß sie auf den Einsatz von umweltschädlichen Lösungsmitteln angewiesen sind. Die DE-OS 3623467 beschreibt zwar ein Verfahren zur Thermoübertragungsaufzeichnung, bei dem das Thermofarbband ebenfalls auf den Einsatz umweltschädlicher Lösungsmittel verzichtet. Es ist allerdings nur für den Einfachausdruck und nicht für den sogenannten "Multiuse" geeignet.The known methods for producing the above thermal ribbons show, among other things. the main disadvantage that they rely on the use of environmentally harmful solvents. DE-OS 3623467 describes a method for thermal transfer recording, in which the thermal ink ribbon also dispenses with the use of environmentally harmful solvents. However, it is only suitable for simple printing and not for the so-called "multiuse".
Der Erfindung lag daher die Aufgabe zugrunde, das eingangs beschriebene Verfahren so weiterzubilden, daß es die Notwendigkeit des Einsatzes umweltschädlicher Lösungsmittel bei seiner Herstellung ausschließt.The invention was therefore based on the object of developing the method described at the outset in such a way that it precludes the need to use environmentally harmful solvents in its preparation.
Erfindungsgemäß wird diese Aufgabe dadurch gelöst, daß eine wäßrige Beschichtungsdispersion, die das thermoplastische Bindemittel, das Wachs bzw. die wachsähnliche Substanz sowie einen fettlöslichen Farbstoff in fein verteilter Form enthält, in an sich bekannter Weise auf den Träger des Thermofarbbandes aufgetragen, der wäßrige Anteil der Dispersion abgedampft und unter Schmelzen des Wachses bzw. der wachsähnlichen Substanz eine thermische Behandlung durchgeführt wird.According to the invention, this object is achieved in that an aqueous coating dispersion which contains the thermoplastic binder, the wax or the wax-like substance and a fat-soluble dye in finely divided form is applied in a manner known per se to the support of the thermal ribbon, the aqueous portion of the Dispersion evaporated and a thermal treatment is carried out with melting of the wax or the wax-like substance.
Das Wesen der Erfindung besteht demzufolge darin, daß eine wäßrige Beschichtungsdispersion mit dem Gehalt an den nötigen feinteiligen Feststoffen auf die Trägerfolie aufgetragen und der wäßrige Anteil der Dispersion unterhalb des Schmelzpunktes der integrierten Wachsteilchen bzw. Teilchen der wachsartigen Substanz abgedampft und diese Wachsteilchen bzw. Teilchen der wachsähnlichen Substanz durch thermische Behandlung verschmolzen werden. Eine technologische Erläuterung folgt später.The essence of the invention is therefore that an aqueous coating dispersion containing the necessary fine-particle solids is applied to the carrier film and the aqueous portion of the dispersion evaporates below the melting point of the integrated wax particles or particles of the wax-like substance and these wax particles or particles of wax-like substance can be fused by thermal treatment. A technological explanation follows later.
Für die Zwecke der Erfindung kommen beliebige Kunststoffolien in Frage, die auch als Träger bei herkömmlichen Carbonbändern von Schreibmaschinen herangezogen werden, die aber auch den erwähnten hohen Temperaturen bei dem kurzzeitig ablaufenden Druckvorgang standhalten und ferner bei diesen Temperaturen die Aufschmelzfarbe freigeben. Die Kunstoffolie besteht insbesondere aus thermoplastischen Kunststoffen höherer Glasübergangstemperatur. 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. Als bevorzugt gelten unter diesen Materialien Polyethylenterephthalate und Polycarbonate.For the purposes of the invention, any plastic films are suitable, which are also used as supports in conventional carbon ribbons of typewriters, but which also withstand the high temperatures mentioned during the briefly running printing process and also release the melting ink at these temperatures. The plastic film consists in particular of thermoplastic plastics with a higher glass transition temperature. 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. Among these materials, polyethylene terephthalates and polycarbonates are preferred.
Bei der erfindungsgemäß heranzuziehenden Kunststoffolie kann es sich auch um ein ein- oder beidseitig kunststoffkaschiertes Gewebe handeln. Selbstverständlich lassen sich im Rahmen der Erfindung ähnlich konzipierte geläufige Verbundfolien einsetzen.The plastic film to be used according to the invention can also be a fabric laminated on one or both sides. Of course, similarly designed common composite films can be used within the scope of the invention.
In Einzelfällen ist es vorteilhaft, dem jeweils gewählten Kunststoffträger einen Weichmacher einzuverleiben, um eine verbesserte Flexibilität zu erzielen. Des weiteren kann auch eine die Wärmeleitfähigkeit erhöhende Substanz eingearbeitet werden. Die Stärke der Kunststoffolie wird nach den jeweiligen Erfordernissen bestimmt. In der Regel ist sie jedoch relativ dünn, z.B. etwa 3 bis 6 Mikrometer, um die erforderlichen Wärmeübergänge optimal ablaufen zu lassen. Dieser Bereich kann auch mehr oder weniger weit unter- oder überschritten werden.In individual cases, it is advantageous to incorporate a plasticizer into the plastic carrier chosen in order to achieve improved flexibility. Furthermore, a substance that increases the thermal conductivity can also be incorporated. The thickness of the plastic film is determined according to the respective requirements. As a rule, however, it is relatively thin, e.g. about 3 to 6 micrometers to allow the necessary heat transfers to run optimally. This range can also be more or less far exceeded.
Der im Zusammenhang mit der Erfindung verwendete Begriff "Wachs" ist weitestgehend zu verstehen. Ein solches Material soll in der Regel folgende Eigenschaften haben: Bei 20°C nicht knetbar, fest bis brüchig-hart, grob bis feinkristallin, durchscheinend bis opak, jedoch nicht glasartig, über 40°C ohne Zersetzung schmelzbar, allerdings schon wenig oberhalb des Schmelzpunktes verhältnismäßig niedrig-viskos und nicht fadenziehend.The term "wax" used in connection with the invention is to be understood as far as possible. Such a material should generally have the following properties: not kneadable at 20 ° C, solid to brittle-hard, coarse to fine crystalline, translucent to opaque, but not glassy, meltable above 40 ° C without decomposition, but a little above the melting point relatively low-viscosity and non-stringy.
Unter "wachsähnlichen Substanzen" sollen im Rahmen der Erfindung solche Materialien verstanden werden, die den Wachsen im Hinblick auf die physikalischen und chemischen Eigenschaften weitgehend ähneln. Bei der Durchführung des erfindungsgemäßen Verfahrens hat es sich gezeigt, daß der Schmelzpunkt des jeweils gewählten Wachses bzw. der wachsähnlichen Substanz vorzugsweise mindestens etwa 70°C beträgt. Die obere Begrenzung beträgt vorzugsweise etwa 90°C.In the context of the invention, “wax-like substances” should be understood to mean those materials which largely resemble the waxes with regard to the physical and chemical properties. When carrying out the process according to the invention, it has been shown that the melting point of the wax or wax-like substance chosen in each case is preferably at least about 70 ° C. The upper limit is preferably about 90 ° C.
Die wäßrige Beschichtungsdispersion enthält die angesprochenen Feststoffteilchen, d.h. den thermoplastischen Kunststoff, das Wachs bzw. die wachsähnliche Substanz sowie den fettlöslichen Farbstoff und das Pigment, vorzugsweise in einer Teilchengröße von 0,5 bis 100 Mikrometer und insbesondere von etwa 5 bis 50 Mikrometer. In diesem Teilchengrößenbereich werden besonders gute Verfahrensprodukte erhalten. Die wäßrige Beschichtungsdispersion bzw. -suspension dieser Materialien läßt sich auf verschiedenen Wegen herstellen. Dies kann beispielsweise durch Suspendierung feiner fester Teilchen dieser Materialien oder auch durch Emulgieren in der Schmelze und nachfolgendes Abkühlen, vorzugsweise unter Rühren zur Beibehaltung der Feinstdispergierung, erfolgen.The aqueous coating dispersion contains the mentioned solid particles, i.e. the thermoplastic, the wax or the wax-like substance and the fat-soluble dye and the pigment, preferably in a particle size of 0.5 to 100 micrometers and in particular of about 5 to 50 micrometers. Particularly good process products are obtained in this particle size range. The aqueous coating dispersion or suspension of these materials can be prepared in various ways. This can be done, for example, by suspending fine, solid particles of these materials or else by emulsifying in the melt and then cooling, preferably with stirring to maintain the finest dispersion.
Wesentlicher Bestandteil der erfindungsgemäß auszubildenden Schicht der Aufschmelzfarbe ist ein Thermoplast. Thermoplaste sind bei gewöhnlicher Temperatur hart oder sogar spröde Kunststoffe, die bei Wärmezufuhr reversibel erweichen und mechanisch leicht verformbar werden, um schließlich bei hohen Temperaturen in den Zustand einer viskosen Flüssigkeit überzugehen.An essential component of the layer of the melting ink to be formed according to the invention is a thermoplastic. At normal temperature, thermoplastics are hard or even brittle plastics, which soften reversibly when heat is applied and become mechanically easily deformable, in order to finally change to a viscous liquid state at high temperatures.
Sie durchlaufen eine Erweichungs- oder Schmelzbereich. Im Rahmen der Erfindung sind vorzugsweise solche thermoplastischen Kunststoffe einzusetzen, die bei der abschließend thermischen Behandlung nicht schmelzen bzw. allenfalls maximal erweichen.They go through a softening or melting range. Within the scope of the invention, preference is given to using thermoplastics which do not melt during the final thermal treatment, or which at most soften at most.
Unter Berücksichtigung dieses Erfordernisses ist es dem Fachmann leicht möglich, geeignete thermoplastische Bindemittel auszuwählen. Hierzu zählen insbesondere Polystyrol, Polyvinylacetat, Polyvinylacetal, Polyvinylchlorid, Polyethylen, Copolymerisate aus Vinylacetat und Vinylchloride, Polyvinylether, Polyvinylpropionate, Polyacrylate, Ethylen/Vinylacet-Copolymere.Taking this requirement into account, it is easily possible for the person skilled in the art to select suitable thermoplastic binders. These include in particular polystyrene, polyvinyl acetate, polyvinyl acetal, polyvinyl chloride, polyethylene, copolymers of vinyl acetate and vinyl chlorides, polyvinyl ether, polyvinyl propionates, polyacrylates, ethylene / vinyl acetate copolymers.
Die thermoplastischen Bindemittel dienen in der erfindungsgemäß ausgebildeten Schicht der Aufschmelzfarbe als Gerüstsubstanz. Zur Steuerung der Härte dieser Gerüstsubstanz in der fertigen Aufschmelzfarbe können dem thermoplastischen Bindemittel auch geeignete bekannte Weichmacher einverleibt werden, so z.B. Phthalsäureester, wie Di-2-ethylhexylphthalat, Di-isononylphthalat und Di-isodecylphthalat, aliphatische Dicarbonsäureester, wie die von Adipinsäure, insbesondere Di-2-ethylhexyladipat und Diisodecyladipat, Phosphate, wie Trikresylphospat und Triphenylphosphat, Fettsäureester, wie Triethylenglykol-2-(2-ethylbutyrat) und dergleichen. In Einzelfällen kann es auch vorteilhaft sein, dem thermoplastischen Bindemittel Stabilisatoren einzuverleiben.The thermoplastic binders serve as a framework substance in the layer of the melting ink designed according to the invention. In order to control the hardness of this framework substance in the finished melting ink, suitable known plasticizers can also be incorporated into the thermoplastic binder, e.g. Phthalic acid esters, such as di-2-ethylhexyl phthalate, di-isononyl phthalate and di-isodecyl phthalate, aliphatic dicarboxylic acid esters, such as that of adipic acid, in particular di-2-ethylhexyl adipate and diisodecyl adipate, phosphates, such as tricresyl phosphate and triphenyl phosphate, such as fatty acid glycol, fatty acid esters -ethylbutyrate) and the like. In individual cases it can also be advantageous to incorporate stabilizers into the thermoplastic binder.
Das Verhältnis von Wachs bzw. wachsähnlicher Substanz zu dem thermoplastischen Bindemittel in der wäßrigen Beschichtungsdispersion kann weitesten Schwankungen unterliegen und ist für die Zwecke der Erfindung nicht kritisch. Das Gewichtsverhältnis kann ohne weiteres zwischen etwa 10: 1 bis 1: 5 liegen. Bevorzugt wird ein Gewichtsverhältnis von etwa 5: 1 bis 1: 1.The ratio of wax or wax-like substance to the thermoplastic binder in the aqueous coating dispersion can vary widely and is not critical for the purposes of the invention. The weight ratio can easily be between about 10: 1 to 1: 5. A weight ratio of approximately 5: 1 to 1: 1 is preferred.
Der Feststoffgehalt der ursprünglich eingesetzten Beschichtungsdispersion bzw. Ausgangsdispersion kann ebenfalls in weiten Grenzen schwanken, so z.B. zwischen etwa 20 und 80 Gew.-%, vorzugsweise zwischen etwa 30 und 60 Gew.-%.The solids content of the coating dispersion or starting dispersion originally used can likewise vary within wide limits, for example between about 20 and 80% by weight, preferably between about 30 and 60% by weight.
Wichtig für die erfolgreiche Ausübung der Erfindung ist es, daß ein spezieller Farbstoff eingesetzt wird, der in dem Wachs oder der wachsähnlichen Substanz löslich ist. Dieses Erfordernis erfüllen die sogenannten fettlöslichen Farbstoffe bzw. "Fettfarbstoffe". Zu dieser Klasse gehören beispielsweise einfach aufgebaute Azo- und Anthrachinon-Farbstoffe, so z.B. die von der Firma Bayer AG unter der Bezeichnung "Ceres-Farbstoffe" vertriebenen Erzeugnisse. Hierunter fallen des weiteren insbesondere die nach dem Color-Index Teil I angegebenen Farbstoffe Solvent Yellow 16, Solvent Yellow 29, Solvent Yellow 14, Solvent Red 1, Solvent Red 18, Solvent Red 25, Solvent Red 24, Solvent Red 19, Smoke Dye und Solvent Blue 63, Solvent Blue 68, Solvent Green, Solvent Brown 1, Solvent Red 3, Solvent Green 3 und Solvent Black 3. Diese Auflistung soll nicht beschränkend sein. Der Fachliteratur lassen sich weitere geeignete fettlösliche Farbstoffe entnehmen. Neben den Farbstoffen können auch Pigmente herangezogen werden, so Ruße, organische und/oder anorganische Farbpigmente, aber auch sogenannte Füllstoffe, wie Kreide, China-Clay, Kaolin, Tonerde etc.It is important for the successful practice of the invention that a special dye is used which is soluble in the wax or the wax-like substance. The so-called fat-soluble dyes or "fat dyes" meet this requirement. This class includes, for example, simple azo and anthraquinone dyes, e.g. the products sold by Bayer AG under the name "Ceres dyes". This also includes, in particular, the dyes Solvent Yellow 16, Solvent Yellow 29, Solvent Yellow 14, Solvent Red 1, Solvent Red 18, Solvent Red 25, Solvent Red 24, Solvent Red 19, Smoke Dye and Solvent Yellow 16 Solvent Blue 63, Solvent Blue 68, Solvent Green, Solvent Brown 1, Solvent Red 3, Solvent Green 3 and Solvent Black 3. This list is not intended to be limiting. Other suitable fat-soluble dyes can be found in the specialist literature. In addition to the dyes, pigments can also be used, such as carbon blacks, organic and / or inorganic color pigments, but also so-called fillers such as chalk, china clay, kaolin, clay, etc.
Die mit der Erfindung angestrebten Vorteile werden insbesondere dann erreicht, wenn als Dispersionsmittel in der aufzutragenden wäßrigen Beschichtungsdispersion allein Wasser enthalten ist. Demzulfoge sollten weitere polare und/oder unpolare organische Lösungsmittel möglichst darin nicht enthalten sein. In Einzelfällen kann es jedoch auch unschädlich sein, wenn beispielsweise im wäßrigen Medium kleinere Anteile dieser Lösungsmittel enthalten sind, so beispielsweise geringe Mengen an Ethanol.The advantages sought by the invention are achieved in particular when water is the only dispersing agent in the aqueous coating dispersion to be applied. Demzulfoge should not contain other polar and / or non-polar organic solvents if possible. In individual cases, however, it can also be harmless if, for example, small amounts of these solvents are present in the aqueous medium, for example small amounts of ethanol.
Die wäßrige Beschichtungsdispersion kann in beliebiger Weise auf den Träger aufgetragen werden, so beispielsweise mit einer Rakel. Die Auftragstechnologie ist demzufolge nicht kritisch. Sie kann auch in beliebiger Weise abgedampft bzw. eingeengt werden, z.B. durch Überleiten warmer Luft.The aqueous coating dispersion can be applied to the support in any manner, for example with a doctor knife. The application technology is therefore not critical. It can also be evaporated or concentrated in any way, for example by passing warm air over it.
Vorzugsweise sollte jedoch die Temperatur beim Abdampfen bzw. Einengen des wäßrigen Anteils der aufgetragenen wäßrigen Beschichtungsdispersion nur so hoch gewählt werden, daß die Wachsteilchen bzw. die Teilchen der wachsähnlichen Substanz bei der thermischen Behandlung möglichst nicht geschmolzen werden. Generell kann auch bei Raumtemperatur gearbeitet werden, wobei die thermische Behandlung bzw. das Überleiten der Luft längere Zeit erfordern würde.Preferably, however, the temperature during evaporation or concentration of the aqueous portion of the applied aqueous coating dispersion should only be chosen so high that the wax particles or the particles of the wax-like substance are preferably not melted during the thermal treatment. In general, work can also be carried out at room temperature, whereby the thermal treatment or the transfer of air would require a longer time.
Nachdem der wäßrige Anteil der aufgetragenen Beschichtungsdispersion abgedampft ist, schließt sich eine thermische Behandlung des erhaltenen Erzeugnisses an, die bei oder über der Schmelztemperatur des Wachses bzw. der wachsähnlichen Substanz liegt. Im Ergebnis wird durch diese thermische Behandlung das Wachs bzw. das wachsähnliche Material verschmolzen. Diese thermische Behandlung kann anhand üblicher Maßnahmen erfolgen, so beispielsweise durch Behandlung mit beheizten Walzen, Einwirkung warmer Luft und Wärmestrahlung. Durch diese Wärmebehandlung wird der fettlösliche Farbstoff in die Phase des verschmolzenen Wachses bzw. der verschmolzenen wachsähnlichen Substanz überführt. Bei der Verwendung des Thermofarbbandes in üblichen Schreibsystemen wird daher eine besonders hohe Farbergiebigkeit erzielt.After the aqueous portion of the applied coating dispersion has evaporated, there follows a thermal treatment of the product obtained, which is at or above the melting temperature of the wax or the wax-like substance. As a result, the wax or the wax-like material is fused by this thermal treatment. This thermal treatment can be carried out using customary measures, for example by treatment with heated rollers, exposure to warm air and thermal radiation. Through this heat treatment, the fat-soluble dye is transferred into the phase of the fused wax or the fused wax-like substance. A particularly high color yield is therefore achieved when using the thermal ink ribbon in conventional writing systems.
Die Schichtstärke der Aufschmelzfarbe sollte in der Regel zwischen etwa 5 und 30 Mikrometer liegen und vorzugsweise 10 bis 20 Mikrometer betragen (trockene Schicht). Gegebenenfalls kann zwischen der Farbschicht und Trägerfolie eine haftvermittelnde Schicht einer Stärke von etwa 0,1 bis 5 Mikrometer, vorzugsweise etwa 0,5 bis 2 Mikrometer, angeordnet sein. Diese besteht vorzugsweise aus polymeren Materialien bekannter Art.The layer thickness of the melting ink should generally be between about 5 and 30 micrometers and preferably 10 to 20 micrometers (dry layer). If appropriate, an adhesion-promoting layer with a thickness of approximately 0.1 to 5 micrometers, preferably approximately 0.5 to 2 micrometers, can be arranged between the color layer and the carrier film. This preferably consists of polymeric materials of a known type.
Die Erfindung soll nachfolgend anhand von Beispielen noch näher erläutert werden.The invention will be explained in more detail below using examples.
Anhand folgender Rezeptur wurde eine wäßrige Dispersion hergestellt:
Die insgesamt 41 Gewichtsteile ausmachende Dispersion wurde mittels einer Rakel in einer Schichtstärke von etwa 20 Mikrometern (bezogen auf das später getrocknete Erzeugnis) auf einen Polyester-Träger aufgebracht. Durch Überleiten warmer Luft einer Temperatur von 80°C wurde der wäßrige Anteil der aufgetragenen Dispersion innerhalb weniger Minuten abgedampft. Anschließend wurde mit Luft einer Temperatur von etwa 100°C eine thermische Behandlung vorgenommen, wobei die Wachsteilchen miteinander verschmolzen. Das erhaltene Erzeugnis konnte unmittelbar als Thermofarbband verwendet werden. Es gestattete einen 8fachen Multiuse.The dispersion, which made up a total of 41 parts by weight, was applied by means of a doctor blade in a layer thickness of approximately 20 micrometers (based on the product which was subsequently dried) to a polyester support. By passing warm air at a temperature of 80 ° C, the aqueous portion of the applied dispersion was evaporated within a few minutes. A thermal treatment was then carried out with air at a temperature of about 100 ° C., the wax particles fusing together. The product obtained could be used directly as a thermal ribbon. It allowed an 8x multiuse.
Es wurde ein Thermofarbband anhand der folgenden Rezeptur hergestellt:
Die erhaltenen 49 Gewichtsteile der Dispersion wurden in der im Beispiel 1 beschriebenen Weise auf den Träger eines Thermofarbbandes aufgetragen und getrocknet. Es schließt sich eine thermische Behandlung mit heißer Luft einer Temperatur von 100°C zum Verschmelzen der Wachsteilchen an. Das erhaltene Verfahrenserzeugnis ermöglichte ebenfalls einen 8fachen Multiuse.The 49 parts by weight of the dispersion obtained were applied to the support of a thermal ink ribbon in the manner described in Example 1 and dried. This is followed by a thermal treatment with hot air at a temperature of 100 ° C. to fuse the wax particles. The process product obtained also enabled an 8-fold multiuse.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88112415T ATE67448T1 (en) | 1987-08-22 | 1988-07-30 | PROCESS FOR MAKING A THERMAL TRANSFER RIBBON AND THE THERMAL RIBBON AVAILABLE AFTERWARDS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3728076 | 1987-08-22 | ||
| DE19873728076 DE3728076A1 (en) | 1987-08-22 | 1987-08-22 | METHOD FOR PRODUCING A THERMOFIBB BAND FOR THE THERMOTRANSFER PRINT AND THEREFORE THERMOFARB BAND THEREOF |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0304672A1 EP0304672A1 (en) | 1989-03-01 |
| EP0304672B1 true EP0304672B1 (en) | 1991-09-18 |
Family
ID=6334290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88112415A Expired - Lifetime EP0304672B1 (en) | 1987-08-22 | 1988-07-30 | Process for manufacture of a thermally sensitive ribbon for use in thermal transfer printing and the printing ribbon obtained therefrom |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4950501A (en) |
| EP (1) | EP0304672B1 (en) |
| JP (1) | JPS6469388A (en) |
| AT (1) | ATE67448T1 (en) |
| DE (2) | DE3728076A1 (en) |
| ES (1) | ES2024599B3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3825438A1 (en) * | 1988-07-27 | 1990-02-15 | Pelikan Ag | THERMAL RIBBON AND A METHOD FOR THE PRODUCTION THEREOF |
| DE3935347A1 (en) * | 1989-10-24 | 1991-04-25 | Ancker Joergensen As | DEVICE FOR PRINTING A RECORD CARRIER |
| DE3935348A1 (en) * | 1989-10-24 | 1991-05-02 | Ancker Joergensen As | Transfer printer using fusible ink - has adjustable mounting for counter-pressure roller at rear of printed web |
| AU2004204345B2 (en) * | 2003-01-08 | 2010-02-25 | Johnson & Johnson Gmbh | Products comprising a sheet and a wax dispersion |
| CN106274090A (en) * | 2016-08-10 | 2017-01-04 | 河南卓立膜材料股份有限公司 | A kind of aqueous environment protection concora crush resin base carbon ribbon and preparation method thereof |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5468253A (en) * | 1977-11-09 | 1979-06-01 | Gen Corp | Heat sensitive transfer medium |
| US4238549A (en) * | 1978-11-27 | 1980-12-09 | Columbia Ribbon And Carbon Mfg. Co., Inc. | Transfer elements |
| JPS57160691A (en) * | 1981-03-31 | 1982-10-04 | Fujitsu Ltd | Ink composition for heat transfer recording and heat transfer recording ink sheet employing said composition |
| JPS5849296A (en) * | 1981-09-18 | 1983-03-23 | Ricoh Co Ltd | Recording material for thermal transfer |
| JPS5957791A (en) * | 1982-09-28 | 1984-04-03 | Fujitsu Ltd | Production of heat transfer ink sheet |
| JPS59145191A (en) * | 1983-02-09 | 1984-08-20 | Fujitsu Ltd | Production of ink sheet |
| JPS59165696A (en) * | 1983-03-11 | 1984-09-18 | Brother Ind Ltd | Thermal multiple-time transfer sheet and production thereof |
| JPS6049993A (en) * | 1983-08-31 | 1985-03-19 | Toyo Ink Mfg Co Ltd | Thermal transfer material |
| US4651177A (en) * | 1984-05-31 | 1987-03-17 | Mitsubishi Paper Mills, Ltd. | Thermal transfer recording material |
| DE3520308A1 (en) * | 1985-06-07 | 1986-12-11 | Pelikan Ag, 3000 Hannover | METHOD FOR PRODUCING A THERMAL RIBBON TAPE FOR THERMAL TRANSFER PRINTING AND THE THERMAL RIBBON TAPE AVAILABLE AFTER THIS |
| US4783360A (en) * | 1985-07-22 | 1988-11-08 | Canon Kabushiki Kaisha | Thermal transfer material |
| GB2178553B (en) * | 1985-07-29 | 1990-01-04 | Canon Kk | Thermal transfer material |
| JPS63134289A (en) * | 1986-11-26 | 1988-06-06 | Canon Inc | Method for thermal transfer recording and thermal transfer recording medium |
-
1987
- 1987-08-22 DE DE19873728076 patent/DE3728076A1/en active Granted
-
1988
- 1988-07-30 EP EP88112415A patent/EP0304672B1/en not_active Expired - Lifetime
- 1988-07-30 DE DE8888112415T patent/DE3864953D1/en not_active Expired - Lifetime
- 1988-07-30 ES ES88112415T patent/ES2024599B3/en not_active Expired - Lifetime
- 1988-07-30 AT AT88112415T patent/ATE67448T1/en not_active IP Right Cessation
- 1988-08-19 JP JP63204879A patent/JPS6469388A/en active Pending
- 1988-08-19 US US07/234,969 patent/US4950501A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ATE67448T1 (en) | 1991-10-15 |
| DE3728076A1 (en) | 1989-03-02 |
| DE3864953D1 (en) | 1991-10-24 |
| DE3728076C2 (en) | 1989-11-09 |
| EP0304672A1 (en) | 1989-03-01 |
| US4950501A (en) | 1990-08-21 |
| ES2024599B3 (en) | 1992-03-01 |
| JPS6469388A (en) | 1989-03-15 |
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