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EP0481200B1 - Dye-acceptor element for thermal sublimation printing process - Google Patents

Dye-acceptor element for thermal sublimation printing process Download PDF

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Publication number
EP0481200B1
EP0481200B1 EP19910114420 EP91114420A EP0481200B1 EP 0481200 B1 EP0481200 B1 EP 0481200B1 EP 19910114420 EP19910114420 EP 19910114420 EP 91114420 A EP91114420 A EP 91114420A EP 0481200 B1 EP0481200 B1 EP 0481200B1
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EP
European Patent Office
Prior art keywords
acid
dye
polyester
acceptor element
layer
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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Application number
EP19910114420
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German (de)
French (fr)
Other versions
EP0481200A1 (en
Inventor
Rolf Dr. Wehrmann
Hermann Dr. Uytterhoeven
Richard Dr. Weider
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Agfa Gevaert AG
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Agfa Gevaert AG
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Priority to US07/773,036 priority Critical patent/US5250494A/en
Priority to JP3296629A priority patent/JPH04263991A/en
Publication of EP0481200A1 publication Critical patent/EP0481200A1/en
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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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5272—Polyesters; Polycarbonates

Definitions

  • the present invention relates to a color acceptor element for the thermal sublimation printing process.
  • thermo sublimation printing process There are a number of methods for printing out video or computer-stored images, of which the thermal sublimation printing process has proven to be superior in certain requirements due to its advantages over other processes.
  • a sheet-like or ribbon-shaped donor material which contains a dye capable of sublimation is brought into contact with a dye (dye) acceptor layer and heated imagewise to transfer the dye.
  • the thermal head is controlled and the dye is transferred from the donor material to the acceptor element in accordance with the stored template.
  • a detailed description of the process can be found, for example, in "High Quality Image Recording by Sublimation Transfer Recording Material", Electronic Photography Association Documents 27 (2), 1988, and the literature cited therein.
  • a particular advantage of this printing process is the ability to fine-tune color intensities.
  • Color acceptor elements for thermal sublimation printing usually include a backing, e.g. Paper or transparent films that are coated with the actual color acceptor layer.
  • An adhesive layer can be applied between the base and the acceptor layer.
  • (Co) polyester is a commonly used binder. They are obtained by the reaction of one or more dicarboxylic acids with one or more diols. At least one dicarboxylic acid and / or a diol preferably contains aromatic groups so that the glass transition temperature Tg of the polycondensate is at least 0 ° C., preferably at least 10 ° C.
  • Such polyesters are e.g. described in EP-A 0 289 161, EP-A-0 275 319, EP-A 0 261 505, EP-A 0 368 318, JP 86/3796 or JP 269 589.
  • the color acceptor layers currently available do not yet sufficiently meet the requirements for high color density, sufficient image stability and good resolution. It is particularly difficult to achieve high color density and sufficient image stability with minimal lateral diffusion. Furthermore, sticking between the donor ribbon and the acceptor element can occur during the printing process, which leads to blurred images. Therefore, sliding layers or lubricants are often used.
  • the object of the invention was to provide a color acceptor element for the thermal sublimation printing process which does not have the disadvantages mentioned above.
  • the object is achieved by using a special polymer in the color acceptor element.
  • a color acceptor element for the thermal sublimation printing process has now been found, which has very high dyeability, very good sliding properties and good image stability and is based on a specially constructed polyester.
  • the present invention relates to a dye acceptor element for the thermal sublimation printing process with a layer support and an ink acceptor layer thereon, which contains a polyester formed from diols and dicarboxylic acids, characterized in that 0.5 to 60 mol% of the diol component of the polyester consists of a dimer diol.
  • Dimer diols are optionally a saturated, unsaturated or aromatic carbocyclic ring-containing dialkyl-substituted diols with 24 or more carbon atoms, which can be obtained by hydrogenation from so-called dimer fatty acids ("dimer acids").
  • dimerization products from unsaturated aliphatic carboxylic acids (fatty acids) with 12 or more carbon atoms, preferably from unsaturated C18 fatty acids such as oleic acid and linoleic acid. Dimer acids are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A8, p. 535. They are generally present as a mixture.
  • Suitable dimer diols can be described, for example, as mixtures of compounds of the general formulas I, II and III wherein R1 and R2 are alkyl and R3 and R4 are alkylene, with the proviso that R1, R2, R3 and R4 together in formula I 40, 36, 32, 28, 24 or 20 carbon atoms and in formulas II and III contain 36, 32, 28, 24, 20 or 16 carbon atoms.
  • Such diols can be obtained, for example, from unsaturated C22 fatty acids (upper corner value) or unsaturated C12 fatty acids (lower corner value). C16 and C18 fatty acids are preferably used.
  • Such product mixtures are available, for example, from Unichema GmbH, Emmerich, under the product name Pripol® 2033.
  • the polyesters according to the invention can be prepared by condensation reactions of one or more dicarboxylic acids with one or more diols, including dicarboxylic acids and diols containing aromatic groups and the dimer diols.
  • Derivatives of the acids - for example esters, acid chlorides etc. - and diols - for example acetates - can also be used for the condensation.
  • dicarboxylic acids examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, etc.
  • cyclohexanedicarboxylic acid maleic acid, maleic anhydride, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acids, naphthalenedicarboxylic acids, sulfoisophthalic acid, and in particular non-substituted alkyl or dicarboxylic acids 5-C alkenyl acids in the main chain between the carboxyl groups and at least 6 carbon atoms in a side chain.
  • Examples of the last-mentioned alkyl or alkenyl-substituted dicarboxylic acids are Tetradecylmalonklare, hexadecylmalonic, Octadecylmalonklare, Diheptylmalonklare, octylsuccinic acid, Decylbernsteinklare, dodecylsuccinic acid, Tetradecylbernsteinklandre, Hexadecylbernsteinklare, octadecylsuccinic acid, octenylsuccinic acid, isooctenylsuccinic, Decenylbernsteinklare, dodecenylsuccinic acid, tetradecenylsuccinic acid, hexadecenylsuccinic acid, octadecenylsuccinic acid, Docosylbernsteinklad, Docosenylbernstein Acid
  • hexadecylmalonic acid octadecylmalonic acid
  • hexadecylsuccinic acid hexadecylsuccinic acid
  • docosenylsuccinic acid are particularly preferred.
  • diols ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol, 1,6-hexanediol, 1,2-hexanediol, 1,4-cyclohexanediol, 1,4 -Cyclohexanedimethanol, ethoxylated or propoxylated bisphenols such as Dianol® 22 (ethoxylated BPA, Akzo), Dianol® 33 (propoxylated BPA, Akzo) or ethoxylated or propoxylated hydroquinone.
  • Dianol® 22 ethoxylated BPA, Akzo
  • Dianol® 33 propoxylated BPA, Akzo
  • Long-chain diols such as 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol can also be used, and in particular those provided with at least one side chain short-chain diols containing no more than 5 carbon atoms between the two hydroxyl groups and an alkyl or alkenyl radical with at least 6 carbon atoms in the side chain.
  • the long chain alkyl or alkenyl radical of the side chain can be connected to the main chain directly or via links such as aromatic groups, cycloaliphatic groups or heteroatoms (for example -O-, -NH-, -O-CO-, -NH-CO-).
  • Examples of the last-mentioned short-chain diols provided with a side chain are 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-hexadecanediol, 1,4-octadecanediol, N, N-di- (n -decyl) -amino-2,3-propanediol, glycerol and pentaerythritol partial esters such as glycerol monostearate, glycerol monooleate, glycerol monorizin oleate, glycerol monolaurate, glycerol monocaprylate, pentaerythritol distearate and pentadecylresorcinol.
  • 1,2-dodecanediol 1,2-hexadecanediol, glycerol monostearate, glycerol monooleate and pentaerythritol distearate are particularly preferred.
  • the polyester according to the invention formed from dicarboxylic acids and diols can additionally contain built-in residues of hydroxyalkanecarboxylic acids, in particular those which contain a side chain with preferably at least 8 carbon atoms.
  • Suitable examples are hydroxybutyric acid, hydroxydecanoic acid, hydroxydodecanoic acid, hydroxyhexadecanoic acid, hydroxyoctadecanoic acid, methyl-n-hexylglycolic acid, 2,3-dihydroxynonanoic acid, 11-hydroxyundecanoic acid, 2-hydroxy-4,6,6-trimethylheptanoic acid, 16-hydroxyhexadecanoic acid, 12-hydroxyadadanoic acid, 12-hydroxy-9-octadecenoic acid (ricinoleic acid), 12,13-ethoxy-9-octadecenoic acid.
  • the proportion of dimer diol is between 0.5 and 60, preferably between 1 and 30, particularly preferably between 1.5 and 20 mol% of the total diol components.
  • the polyesters according to the invention have molecular weights between 500 and 20,000, preferably between 750 and 15,000, particularly preferably between 1000 and 12,000, each determined by gel permeation chromatography using polystyrene as standard.
  • hydrophilic (polar) groups such as sulfonic acid groups (example: sulfoisophthalic acid)
  • polar solvents or solvent mixtures such as water, water / ethanol or water / MEK
  • the color acceptor layer can e.g. pigments or mixtures of several pigments, such as e.g. Titanium dioxide, zinc oxide, kaolin, clay, calcium carbonate or Aerosil can be added.
  • pigments or mixtures of several pigments such as e.g. Titanium dioxide, zinc oxide, kaolin, clay, calcium carbonate or Aerosil can be added.
  • additives such as UV absorbers, light stabilizers or antioxidants, can be added if necessary.
  • the color acceptor layers of the present invention can contain a lubricant to improve the sliding properties, primarily between the donor and acceptor elements.
  • a lubricant to improve the sliding properties, primarily between the donor and acceptor elements.
  • solid waxes such as polyethylene wax, amidic waxes or Teflon® powder can be used, but also optionally fluorine-containing surfactants, paraffin, silicone or fluorine-containing oils or silicone-containing copolymers such as polysiloxane-polyether copolymers. Reactive, modified silicones can also be used.
  • Such products can contain carboxyl, amino and / or epoxy groups and, with a suitable combination of e.g. Amino and epoxy silicone lead to cross-linked sliding layers.
  • the lubricant mentioned can also be applied as a separate coating, as a dispersion or, if appropriate, from a suitable solvent as a "top coat".
  • the thickness of such a layer is then preferably 0.01 to 5 ⁇ m, particularly preferably between 0.05 and 2 ⁇ m.
  • Various materials can be used as carriers for the color acceptor layers. It is possible to use transparent films such as polyethylene terephthalate, polycarbonate, polyether sulfone, polyolefin, polyvinyl chloride, polystyrene, cellulose or polyvinyl alcohol copolymer films. Of course, reflective documents such as the most varied types of paper such as polyolefin-coated paper or pigmented papers are also used. Also laminates made from the above materials are applicable. Typical combinations are laminates of cellulose paper and synthetic paper or cellulose paper and polymer films or polymer films and synthetic paper or other combinations.
  • the carriers ensure the necessary mechanical stability of the color acceptor element. If the color acceptor layer has sufficient mechanical stability, an additional support can be dispensed with.
  • the color acceptor layers of the present invention preferably have total layer thicknesses of 0.3 to 50 ⁇ m, particularly preferably 0.5 to 10 ⁇ m, if a carrier of the type described above is used or if this is dispensed with, from 3 to 120 ⁇ m.
  • the color acceptor layer can consist of a single layer, but two or more layers can also be applied to the support. When using transparent supports, a double-sided coating can be applied to increase the color intensity, e.g. in the European patent application (EP-A-452 566).
  • the color acceptor element of the present invention may also include various intermediate layers between the backing and the dye-receiving layer.
  • the intermediate layer can act as a resilient element (elastic layer), as a barrier layer for the transferred one Dye or as an adhesive layer depending on the specific application.
  • suitable materials are urethane, acrylate or olefin resins, but also butadiene rubbers or epoxies.
  • the thickness of this intermediate layer is usually between about 1 to 2 and 20 microns.
  • Diffusion barrier layers have the task of preventing the transferred dyes from diffusing into the support. Materials that fulfill this task can be soluble in water or in organic solvents or in mixtures, but preferably in water. Suitable materials are, for example, gelatin, polyacrylic acid, maleic anhydride copolymers, polyvinyl alcohol or cellulose acetate.
  • the optional additional layers such as elastic layer, diffusion barrier layer, adhesive layer etc. as well as the actual color acceptor layer can e.g. Contain silicate, clay, aluminum silicate, calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, aluminum oxide powder.
  • the color acceptor element of the present invention can also be antistatically treated on the front or back in the usual way.
  • the color acceptor layers containing the polyester resins according to the invention are usually produced from solution.
  • Suitable solvents are, for example, water, methyl ethyl ketone (MEK), butyl acetate, acetone, alcohols or solvent mixtures, such as MEK / water, ethanol / water.
  • MEK methyl ethyl ketone
  • the solution can be applied to the carrier by pouring or knife coating.
  • the color acceptor element according to the invention is suitable for producing dye transfer images.
  • a color acceptor element is brought into contact with a color donor element on the coating side and the latter is imagewise heated from the rear.
  • the dye transfer is brought about by heating to approximately 400 ° C. for a few milliseconds.
  • the dye donor layer is usually heated imagewise by means of a commercially available thermal head in a thermal sublimation printer.
  • the thermal energy required for dye transfer can also be supplied by laser light, IR flash exposure or by means of a heated pen, if necessary the dye layer or another layer contains the donor element means that absorb light and convert it into heat, for example, soot.
  • the imagewise heating can also be effected using the known resistive ribbon technology.
  • the carrier of the donor element is, for example, a ribbon-shaped polycarbonate layer loaded with soot and coated with a thin aluminum film, to which electrical current is supplied by electrical control of a print head electrode (print head electrode), as a result of which heat is generated in the resistive ribbon. Since the printhead electrode hardly heats itself up, this technology has an advantageous effect on the printing speed.
  • a multicolor picture can be made by successively bringing the color acceptor element according to the invention into contact with each of three or more donor elements with different dyes, by imagewise heating the donor element from the latter to receive an imagewise dye transfer in the relevant color and then separating it from that.
  • the color acceptor element according to the invention can be made by successively bringing the color acceptor element according to the invention into contact with each of three or more donor elements with different dyes, by imagewise heating the donor element from the latter to receive an imagewise dye transfer in the relevant color and then separating it from that.
  • the color acceptor element and / or donor element can be provided with optically recognizable markings.
  • the color images obtained with the color acceptor element according to the invention are notable for high resolution, high color densities, high brilliance and good long-term stability.
  • polyester resins according to the invention are produced in a conventional condensation apparatus under common reaction conditions.
  • the final condensation takes place over 2 hours at 280 ° C with an oil pump vacuum.
  • the resin is isolated by pouring out the melt.
  • the excess ethanediol corresponding to the stoichiometry indicated above is removed by distillation in the course of the condensation, so that almost equivalent molar amounts of acid and alcohol groups are present.
  • the polyester resins 1-6 were dissolved in water / MEK (8: 2) in accordance with the concentration given in Table 1 and poured onto a paper using a doctor blade in a wet film thickness of 20 ⁇ m or 25 ⁇ m (see Table 1) which was coated on both sides with polyethylene and on one side of which a gelatin layer had additionally been applied over the polyethylene.
  • the polyester solution was applied to this side.
  • the coatings were dried in a forced-air drying cabinet at 70 ° C. for 30 minutes. Each sample (a) was left uncoated (no sliding layer).
  • a 0.5% solution in ethanol from Tego® Glide 410 (Tego Chemie Service GmbH) with a wet film thickness of 24 ⁇ m was applied to each further sample (b) and dried at 70 ° C. in a forced-air drying cabinet.
  • Test images were generated on the dye-receiving elements obtained using a Mitsubishi CP-100 E video printer using the Mitsubishi dye cassette CK-100 S.
  • the dye acceptor layers which are built up from the polyesters according to the invention, are distinguished by very high color densities and greatly reduced tendency to stick.
  • Table 2 lists the color densities, which were determined using a Macbeth RD 919 densitometer, and the adhesive behavior.

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  • Chemical Kinetics & Catalysis (AREA)
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Description

Die vorliegende Erfindung betrifft ein Farbakzeptorelement für das Thermosublimationsdruckverfahren.The present invention relates to a color acceptor element for the thermal sublimation printing process.

Um von video- oder computergespeicherten Bildern Ausdrucke zu machen, existiert eine Reihe von Methoden, von denen das Thermosublimationsdruckverfahren sich auf Grund seiner Vorteile gegenüber anderen Verfahren bei bestimmten Anforderungen als überlegen erwiesen hat. Bei dieser Aufzeichnungsmethode wird ein blatt- oder bandförmiges Donormaterial, welches einen sublimationsfähigen Farbstoff enthält, mit einer Farb(stoff)akzeptorschicht in Kontakt gebracht und zur Übertragung des Farbstoffes bildmäßig erwärmt.There are a number of methods for printing out video or computer-stored images, of which the thermal sublimation printing process has proven to be superior in certain requirements due to its advantages over other processes. In this recording method, a sheet-like or ribbon-shaped donor material which contains a dye capable of sublimation is brought into contact with a dye (dye) acceptor layer and heated imagewise to transfer the dye.

Entsprechend der gespeicherten Vorlage erfolgt die Ansteuerung des Thermokopfes und die Übertragung des Farbstoffs aus dem Donormaterial auf das Akzeptorelement. Eine ausführliche Beschreibung des Verfahrens ist z.B. in "High Quality Image Recording by Sublimation Transfer Recording Material", Electronic Photography Association Documents 27 (2), 1988, und der dort zitierten Literatur gegeben. Ein besonderer Vorteil dieses Druckverfahrens liegt in der Möglichkeit der Feinabstufung von Farbintensitäten.The thermal head is controlled and the dye is transferred from the donor material to the acceptor element in accordance with the stored template. A detailed description of the process can be found, for example, in "High Quality Image Recording by Sublimation Transfer Recording Material", Electronic Photography Association Documents 27 (2), 1988, and the literature cited therein. A particular advantage of this printing process is the ability to fine-tune color intensities.

Farbakzeptorelemente für den Thermosublimationsdruck umfassen gewöhnlich eine Unterlage, z.B. Papier oder transparente Folien, die mit der eigentlichen Farbakzeptorschicht beschichtet ist. Eine Haftschicht kann zwischen Unterlage und Akzeptorschicht angebracht sein.Color acceptor elements for thermal sublimation printing usually include a backing, e.g. Paper or transparent films that are coated with the actual color acceptor layer. An adhesive layer can be applied between the base and the acceptor layer.

Als Material für die Farbakzeptorschicht können Polymere aus unterschiedlichen Substanzklassen eingesetzt werden.
So sind in EP-A-0 234 563 folgende Beispiele von geeigneten Materialien für die Akzeptorschicht genannt:

  • 1. Synthetische Harze mit Esterverbindungen, wie Polyester, Polyacrylate, Polyvinylacetat, Styrol-Acrylat-Harze und Vinyltoluol-Acrylat-Harze
  • 2. Polyurethane
  • 3. Polyamide
  • 4. Harnstoff-Harze
  • 5. Synthetische Harze mit anderen hochpolaren Bindungen, wie Polycaprolactam, Styrol-Harze, Polyvinylchlorid, Vinylchlorid-Vinylacetat-Copolymere und Polyacrylnitril.
Polymers from different classes of substances can be used as the material for the color acceptor layer.
The following examples of suitable materials for the acceptor layer are mentioned in EP-A-0 234 563:
  • 1. Synthetic resins with ester compounds such as polyesters, polyacrylates, polyvinyl acetate, styrene-acrylate resins and vinyltoluene-acrylate resins
  • 2. Polyurethanes
  • 3. Polyamides
  • 4. urea resins
  • 5. Synthetic resins with other highly polar bonds such as polycaprolactam, styrene resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers and polyacrylonitrile.

(Co)polyester sind ein häufig benutztes Bindemittel. Sie werden gewonnen durch die Reaktion von einer oder mehreren Dicarbonsäuren mit einem oder mehreren Diolen. Bevorzugt enthält wenigstens eine Dicarbonsäure und/oder ein Diol aromatische Gruppen, damit die Glastemperatur Tg des Polykondensates wenigstens 0°C, bevorzugt wenigstens 10°C beträgt. Derartige Polyester sind z.B. beschrieben in EP-A 0 289 161, EP-A-0 275 319, EP-A 0 261 505, EP-A 0 368 318, JP 86/3796 oder JP 269 589.(Co) polyester is a commonly used binder. They are obtained by the reaction of one or more dicarboxylic acids with one or more diols. At least one dicarboxylic acid and / or a diol preferably contains aromatic groups so that the glass transition temperature Tg of the polycondensate is at least 0 ° C., preferably at least 10 ° C. Such polyesters are e.g. described in EP-A 0 289 161, EP-A-0 275 319, EP-A 0 261 505, EP-A 0 368 318, JP 86/3796 or JP 269 589.

Die zur Zeit verfügbaren Farbakzeptorschichten erfüllen die Anforderungen nach großer Farbdichte, ausreichender Bildstabilität und guter Auflösung noch nicht in ausreichendem Maße. Dabei ist es besonders schwierig, große Farbdichte und ausreichende Bildstabilität bei minimaler Lateraldiffusion zu erreichen. Weiterhin können Verklebungen zwischen dem Donorband und dem Akzeptorelement während des Druckvorgangs auftreten, die zu unscharfen Abbildungen führen. Daher werden häufig Gleitschichten oder Gleitmittel verwendet.The color acceptor layers currently available do not yet sufficiently meet the requirements for high color density, sufficient image stability and good resolution. It is particularly difficult to achieve high color density and sufficient image stability with minimal lateral diffusion. Furthermore, sticking between the donor ribbon and the acceptor element can occur during the printing process, which leads to blurred images. Therefore, sliding layers or lubricants are often used.

Aufgabe der Erfindung war die Bereitstellung eines Farbakzeptorelements für das Thermosublimationsdruckverfahren, das die vorstehend genannten Nachteile nicht aufweist. Die Aufgabe wird durch die Verwendung eines speziellen Polymers im Farbakzeptorelement gelöst.The object of the invention was to provide a color acceptor element for the thermal sublimation printing process which does not have the disadvantages mentioned above. The object is achieved by using a special polymer in the color acceptor element.

Es wurde nun ein Farbakzeptorelement für das Thermosublimationsdruckverfahren gefunden, das über sehr hohe Anfärbbarkeit, sehr gute Gleiteigenschaften und gute Bildstabilität verfügt und auf einem speziell aufgebauten Polyester basiert.A color acceptor element for the thermal sublimation printing process has now been found, which has very high dyeability, very good sliding properties and good image stability and is based on a specially constructed polyester.

Gegenstand der vorliegenden Erfindung ist ein Farbakzeptorelement für das Thermosublimationsdruckverfahren mit einem Schichträger und einer darauf befindlichen Farbakzeptorschicht, die einen aus Diolen und Dicarbonsäuren gebildeten Polyester enthält, dadurch gekennzeichnet, daß 0,5 bis 60 mol-% der Diolkomponente des Polyesters aus einem Dimerdiol besteht.The present invention relates to a dye acceptor element for the thermal sublimation printing process with a layer support and an ink acceptor layer thereon, which contains a polyester formed from diols and dicarboxylic acids, characterized in that 0.5 to 60 mol% of the diol component of the polyester consists of a dimer diol.

Dimerdiole sind gegebenenfalls einen gesättigten, ungesättigten oder aromatischen carbocyclischen Ring enthaltende dialkylsubstituierte Diole mit 24 oder mehr C-Atomen, die durch Hydrierung aus sogenannten Dimerfettsäuren ("Dimersäuren") erhältlich sind.Dimer diols are optionally a saturated, unsaturated or aromatic carbocyclic ring-containing dialkyl-substituted diols with 24 or more carbon atoms, which can be obtained by hydrogenation from so-called dimer fatty acids ("dimer acids").

Bei letzteren handelt es sich um Dimerisierungsprodukte aus ungesättigten aliphatischen Carbonsäuren (Fettsäuren) mit 12 oder mehr C-Atomen, vorzugsweise von ungesättigten C₁₈-Fettsäuren, wie Ölsäure und Linolsäure. Dimersäuren sind beispielsweise beschrieben in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A8, S. 535. Sie liegen im allgemeinen als Gemisch vor.The latter are dimerization products from unsaturated aliphatic carboxylic acids (fatty acids) with 12 or more carbon atoms, preferably from unsaturated C₁₈ fatty acids such as oleic acid and linoleic acid. Dimer acids are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A8, p. 535. They are generally present as a mixture.

Geeignete Dimerdiole lassen sich beispielsweise beschreiben als Gemische aus Verbindungen der allgemeinen Formeln I, II und III

Figure imgb0001
Figure imgb0002
Figure imgb0003
worin R¹ und R² für Alkyl und R³ und R⁴ für Alkylen stehen, mit der Maßgabe, daß R¹, R², R³ und R⁴ zusammen in Formel I 40, 36, 32, 28, 24 oder 20 C-Atome und in den Formeln II und III 36, 32, 28, 24, 20 oder 16 C-Atome enthalten. Derartige Diole können z.B. aus ungesättigten C₂₂-Fettsäuren (oberer Eckwert) oder ungesättigten C₁₂-Fettsäuren (unterer Eckwert) erhalten werden. Bevorzugt werden C₁₆- und C₁₈-Fettsäuren eingesetzt.Suitable dimer diols can be described, for example, as mixtures of compounds of the general formulas I, II and III
Figure imgb0001
Figure imgb0002
Figure imgb0003
wherein R¹ and R² are alkyl and R³ and R⁴ are alkylene, with the proviso that R¹, R², R³ and R⁴ together in formula I 40, 36, 32, 28, 24 or 20 carbon atoms and in formulas II and III contain 36, 32, 28, 24, 20 or 16 carbon atoms. Such diols can be obtained, for example, from unsaturated C₂₂ fatty acids (upper corner value) or unsaturated C₁₂ fatty acids (lower corner value). C₁₆ and C₁₈ fatty acids are preferably used.

Derartige Produktgemische sind beispielsweise von der Firma Unichema GmbH, Emmerich, unter der Produktbezeichnung Pripol® 2033 erhältlich.Such product mixtures are available, for example, from Unichema GmbH, Emmerich, under the product name Pripol® 2033.

Die erfindungsgemäßen Polyester können durch Kondensationsreaktionen von einer oder mehreren Dicarbonsäuren mit einem oder mehreren Diolen unter Einbeziehung von aromatische Gruppen enthaltenden Dicarbonsäuren und Diolen und den Dimerdiolen hergestellt werden. Zur Kondensation können auch Derivate der Säuren - z.B. Ester, Säurechloride usw. - und Diole - z.B. Acetate - eingesetzt werden.The polyesters according to the invention can be prepared by condensation reactions of one or more dicarboxylic acids with one or more diols, including dicarboxylic acids and diols containing aromatic groups and the dimer diols. Derivatives of the acids - for example esters, acid chlorides etc. - and diols - for example acetates - can also be used for the condensation.

Als Beispiele für Dicarbonsäuren seien Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Azelainsäure, Sebacinsäure, 1,10-Dekandicarbonsäure, 1,11-Undekandicarbonsäure, 1,12-Dodekandicarbonsäure, 1,13-Tridekandicarbonsäure, 1,14-Tetradekandicarbonsäure usw. oder Dimerfettsäuren bzw. deren Derivate (Unichema), Cyclohexandicarbonsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure, Phthalsäure, Isophthalsäure, Terephthalsäure, Toluoldicarbonsäuren, Naphthalindicarbonsäuren, Sulfoisophthalsäure genannt, sowie insbesondere Alkyl- oder Alkenyl-substituierte Dicarbonsäuren mit nicht mehr als 5 C-Atomen in der Hauptkette zwischen den Carboxylgruppen und mindestens 6 C-Atomen in einer Seitenkette. Beispiele für die zuletzt genannten Alkyl- oder Alkenyl-substituierten Dicarbonsäuren sind Tetradecylmalonsäure, Hexadecylmalonsäure, Octadecylmalonsäure, Diheptylmalonsäure, Octylbernsteinsäure, Decylbernsteinsäure, Dodecylbernsteinsäure, Tetradecylbernsteinsäure, Hexadecylbernsteinsäure, Octadecylbernsteinsäure, Octenylbernsteinsäure, Isooctenylbernsteinsäure, Decenylbernsteinsäure, Dodecenylbernsteinsäure, Tetradecenylbernsteinsäure, Hexadecenylbernsteinsäure, Octadecenylbernsteinsäure, Docosylbernsteinsäure, Docosenylbernsteinsäure, Tetrapropenylbernsteinsäure, Triacontenylbernsteinsäure, Polyisobutenylbernsteinsäure, 1-Dodecylglutarsäure, 1-Tetradecylglutarsäure, 1-Hexadecylglutarsäure und 1-Decyladipinsäure. Hiervon sind Hexadecylmalonsäure, Octadecylmalonsäure, Hexadecylbernsteinsäure, Octadecylbernsteinsäure und Docosenylbernsteinsäure besonders bevorzugt.Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, etc. or dimer fatty acids or their derivatives (Unichema), cyclohexanedicarboxylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acids, naphthalenedicarboxylic acids, sulfoisophthalic acid, and in particular non-substituted alkyl or dicarboxylic acids 5-C alkenyl acids in the main chain between the carboxyl groups and at least 6 carbon atoms in a side chain. Examples of the last-mentioned alkyl or alkenyl-substituted dicarboxylic acids are Tetradecylmalonsäure, hexadecylmalonic, Octadecylmalonsäure, Diheptylmalonsäure, octylsuccinic acid, Decylbernsteinsäure, dodecylsuccinic acid, Tetradecylbernsteinsäure, Hexadecylbernsteinsäure, octadecylsuccinic acid, octenylsuccinic acid, isooctenylsuccinic, Decenylbernsteinsäure, dodecenylsuccinic acid, tetradecenylsuccinic acid, hexadecenylsuccinic acid, octadecenylsuccinic acid, Docosylbernsteinsäure, Docosenylbernsteinsäure , Tetrapropenyl succinic acid, triacontenyl succinic acid, polyisobutenyl succinic acid, 1-dodecyl glutaric acid, 1-tetradecyl glutaric acid, 1-hexadecyl glutaric acid and 1-decyladipic acid. Of these, hexadecylmalonic acid, octadecylmalonic acid, hexadecylsuccinic acid, octadecylsuccinic acid and docosenylsuccinic acid are particularly preferred.

Als Diole können Ethylenglykol, Diethylenglykol, Triethylenglykol, Neopentylglykol, 1,4-Butandiol, 1,2-Propandiol, 1,3-Propandiol, 1,6-Hexandiol, 1,2-Hexandiol, 1,4-Cyclohexandiol, 1,4-Cyclohexandimethanol, ethoxylierte oder propoxylierte Bisphenole wie Dianol® 22 (ethoxyliertes BPA, Akzo), Dianol® 33 (propoxyliertes BPA, Akzo) oder ethoxyliertes bzw. propoxyliertes Hydrochinon verwendet werden. Auch langkettige Diole wie 1,8-Octandiol, 1,9-Nonandiol, 1,10-Dekandiol, 1,11-Undecandiol, 1,12-Dodekandiol, 1,13-Tridekandiol können verwendet werden, sowie insbesondere mit mindestens einer Seitenkette versehene kurzkettige Diole, die zwischen den beiden Hydroxylgruppen nicht mehr als 5 C-Atome und in der Seitenkette einen Alkyl- oder Alkenylrest mit mindestens 6 C-Atomen enthalten. Der langkettige Alkyl- oder Alkenylrest der Seitenkette kann mit der Hauptkette unmittelbar oder über Bindeglieder wie aromatische Gruppen cycloaliphatische Gruppen oder Heteroatome (beispielsweise -O-, -NH-, -O-CO-, -NH-CO-) verbunden sein. Beispiele für die zuletzt genannten mit einer Seitenkette versehenen kurzkettigen Diole sind 1,2-Octandiol, 1,2-Decandiol, 1,2-Dodecandiol, 1,2-Hexadecandiol, 1,4-Octadecandiol, N,N-Di-(n-decyl)-amino-2,3-propandiol, Glycerin- und Pentaerythritpartialester wie Glycerinmonostearat, Glycerinmonooleat, Glycerinmonorizinoleat, Glycerinmonolaurat, Glycerinmonocaprylat, Pentaerythritdistearat und Pentadecylresorcin. Hiervon sind 1,2-Dodecandiol, 1,2-Hexadecandiol, Glycerinmonostearat, Glycerinmonooleat und Pentaerythritdistearat besonders bevorzugt.As diols, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol, 1,6-hexanediol, 1,2-hexanediol, 1,4-cyclohexanediol, 1,4 -Cyclohexanedimethanol, ethoxylated or propoxylated bisphenols such as Dianol® 22 (ethoxylated BPA, Akzo), Dianol® 33 (propoxylated BPA, Akzo) or ethoxylated or propoxylated hydroquinone. Long-chain diols such as 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol can also be used, and in particular those provided with at least one side chain short-chain diols containing no more than 5 carbon atoms between the two hydroxyl groups and an alkyl or alkenyl radical with at least 6 carbon atoms in the side chain. The long chain alkyl or alkenyl radical of the side chain can be connected to the main chain directly or via links such as aromatic groups, cycloaliphatic groups or heteroatoms (for example -O-, -NH-, -O-CO-, -NH-CO-). Examples of the last-mentioned short-chain diols provided with a side chain are 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-hexadecanediol, 1,4-octadecanediol, N, N-di- (n -decyl) -amino-2,3-propanediol, glycerol and pentaerythritol partial esters such as glycerol monostearate, glycerol monooleate, glycerol monorizin oleate, glycerol monolaurate, glycerol monocaprylate, pentaerythritol distearate and pentadecylresorcinol. Of these, 1,2-dodecanediol, 1,2-hexadecanediol, glycerol monostearate, glycerol monooleate and pentaerythritol distearate are particularly preferred.

Der erfindungsgemäße aus Dicarbonsäuren und Diolen gebildete Polyester kann darüber hinaus eingebaute Reste von Hydroxyalkancarbonsäuren enthalten, insbesondere von solchen, die eine Seitenkette mit vorzugsweise mindestens 8 C-Atomen enthalten. Geeignete Beispiele hierfür sind Hydroxybuttersäure, Hydroxydecansäure, Hydroxydodecansäure, Hydroxyhexadecansäure, Hydroxyoctadecansäure, Methyl-n-hexylglykolsäure, 2,3-Dihydroxynonansäure, 11-Hydroxyundecansäure, 2-Hydroxy-4,6,6-trimethylheptansäure, 16-Hydroxyhexadecansäure, 12-Hydroxystearinsäure, 12-Hydroxy-9-octadecensäure (Ricinolsäure), 12,13-Ethoxy-9-octadecensäure.The polyester according to the invention formed from dicarboxylic acids and diols can additionally contain built-in residues of hydroxyalkanecarboxylic acids, in particular those which contain a side chain with preferably at least 8 carbon atoms. Suitable examples are hydroxybutyric acid, hydroxydecanoic acid, hydroxydodecanoic acid, hydroxyhexadecanoic acid, hydroxyoctadecanoic acid, methyl-n-hexylglycolic acid, 2,3-dihydroxynonanoic acid, 11-hydroxyundecanoic acid, 2-hydroxy-4,6,6-trimethylheptanoic acid, 16-hydroxyhexadecanoic acid, 12-hydroxyadadanoic acid, 12-hydroxy-9-octadecenoic acid (ricinoleic acid), 12,13-ethoxy-9-octadecenoic acid.

Der Anteil des Dimerdiols liegt zwischen 0,5 und 60, vorzugsweise zwischen 1 und 30, besonders bevorzugt zwischen 1,5 und 20 mol-% der gesamten Diolkomponenten.The proportion of dimer diol is between 0.5 and 60, preferably between 1 and 30, particularly preferably between 1.5 and 20 mol% of the total diol components.

Die erfindungsgemäßen Polyester haben Molekulargewichte zwischen 500 und 20 000, vorzugsweise zwischen 750 und 15 000, besonders bevorzugt zwischen 1000 und 12 000, jeweils bestimmt durch Gelpermeationschromatographie mit Polystyrol als Standard.The polyesters according to the invention have molecular weights between 500 and 20,000, preferably between 750 and 15,000, particularly preferably between 1000 and 12,000, each determined by gel permeation chromatography using polystyrene as standard.

Durch die Verwendung von Bausteinen, die über hydrophile (polare) Gruppen verfügen, wie z.B. Sulfonsäuregruppen (Beispiel : Sulfoisophthalsäure), läßt sich eine bessere Löslichkeit in polaren Lösungsmitteln oder Lösungsmittelgemischen wie z.B. Wasser, Wasser/Ethanol oder Wasser/MEK erreichen.By using building blocks that have hydrophilic (polar) groups, such as sulfonic acid groups (example: sulfoisophthalic acid), a better solubility in polar solvents or solvent mixtures such as water, water / ethanol or water / MEK can be achieved.

Die erfindungsgemäßen Polyesterharze bilden den wesentlichen Bestandteil in der erfindungsgemäßen Farbakzeptorschicht. Sie können auch in Abmischung mit anderen bekannten Harzen für Farbakzeptorschichten eingesetzt werden und sind in diesem Fall in der Farbakzeptorschicht in einer Menge von mindestens 2 Gew.-%, vorzugsweise mindestens 5 Gew.-% enthalten; als zugemischte Polymere können die nachstehenden Polymere a) bis f) alleine oder als Mischung von mehreren verwendet werden.

  • a) Polymere, die Esterbindungen enthalten: z.B. Polyester, Polyacrylester, Polycarbonate, Polyvinylacetat, Polyvinylpropionat, Styrol-Acrylate, Methylstyrol-Acrylate.
  • b) Polymere, die Urethanbindungen enthalten: z.B. Polyurethane, Polyesterurethane.
  • c) Polymere, die Amidbindungen enthalten: z.B. Polyamide, Polyesteramide.
  • d) Polymere, die Harnstoffbindungen enthalten: z.B. Polyharnstoffe.
  • e) Polymere, die andere hochpolare Bindungen enthalten, wie z.B. Polycaprolacton, Polystyrole, Polyvinylalkohol, Polyvinylchlorid, Polyacrylnitril, Polyether, Polysulfone, Polyetherketone, Polyhydantoin, Polyimide, Styrol-MSA-Copolymere, Cellulosederivate.
  • f) Polymere, die funktionelle, gegebenenfalls zu Vernetzungsreaktionen befähigte Gruppen enthalten wie z.B. -OH, -NH₂, -NHR, -COOH, -SH, -NCO,
    Figure imgb0004
     sowie Polymere, die durch Vernetzungsreaktionen aus solche Gruppen erhaltenden Präpolymeren erhalten worden sind.
The polyester resins according to the invention form the essential constituent in the color acceptor layer according to the invention. They can also be used in a mixture with other known resins for color acceptor layers and in this case are contained in the color acceptor layer in an amount of at least 2% by weight, preferably at least 5% by weight; the following polymers a) to f) can be used alone or as a mixture of several as admixed polymers.
  • a) Polymers containing ester bonds: for example polyester, polyacrylic ester, polycarbonate, polyvinyl acetate, polyvinyl propionate, styrene acrylates, methyl styrene acrylates.
  • b) Polymers containing urethane bonds: eg polyurethanes, polyester urethanes.
  • c) Polymers containing amide bonds: eg polyamides, polyesteramides.
  • d) Polymers containing urea bonds: eg polyureas.
  • e) polymers which contain other highly polar bonds, such as, for example, polycaprolactone, polystyrenes, polyvinyl alcohol, polyvinyl chloride, polyacrylonitrile, Polyethers, polysulfones, polyether ketones, polyhydantoin, polyimides, styrene-MSA copolymers, cellulose derivatives.
  • f) polymers which contain functional groups which may be capable of crosslinking reactions, such as, for example, -OH, -NH₂, -NHR, -COOH, -SH, -NCO,
    Figure imgb0004
     and polymers obtained by crosslinking reactions from prepolymers containing such groups.

Beispiele für solche Harze sind z.B. beschrieben in EP-A-0 227 094, EP-A-0 228 066, EP-A-0 133 011, EP-A-0 133 012, EP-A-0 144 247 oder EP-A-0 368 320.Examples of such resins are e.g. described in EP-A-0 227 094, EP-A-0 228 066, EP-A-0 133 011, EP-A-0 133 012, EP-A-0 144 247 or EP-A-0 368 320.

Der Farbakzeptorschicht können z.B. zur Erhöhung der Bildschärfe oder zur Verbesserung des Weißheitsgrades Pigmente oder Mischungen mehrerer Pigmente, wie z.B. Titandioxid, Zinkoxid, Kaolin, Ton, Calciumcarbonat oder Aerosil, zugegeben werden.The color acceptor layer can e.g. pigments or mixtures of several pigments, such as e.g. Titanium dioxide, zinc oxide, kaolin, clay, calcium carbonate or Aerosil can be added.

Zur weiteren Steigerung der Lichtstabilität des übertragenen Bildes können, falls notwendig, verschiedene Arten von Additiven, wie z.B. UV-Absorber, Lichtstabilisatoren oder Antioxidantien, zugesetzt werden.To further increase the light stability of the transferred image, various types of additives, such as UV absorbers, light stabilizers or antioxidants, can be added if necessary.

Die Farbakzeptorschichten der vorliegenden Erfindung können ein Gleitmittel zur Verbesserung der Gleiteigenschaften, vornehmlich zwischen Donor- und Akzeptorelement, enthalten. Beispielsweise können feste Wachse wie Polyethylenwachs, amidische Wachse oder Teflon®-Pulver eingesetzt werden, aber auch gegebenenfalls fluorhaltige Tenside, Paraffin-, Silicon- oder fluorhaltige Öle oder siliconhaltige Copolymere wie Polysiloxanpolyethercopolymere. Es können auch reaktive, modifizierte Silicone eingesetzt werden. Derartige Produkte können Carboxyl-, Amino- und/oder Epoxidgruppen enthalten und bei entsprechender Kombination von z.B. Amino- und Epoxysilicon zu vernetzten Gleitschichten führen.The color acceptor layers of the present invention can contain a lubricant to improve the sliding properties, primarily between the donor and acceptor elements. For example, solid waxes such as polyethylene wax, amidic waxes or Teflon® powder can be used, but also optionally fluorine-containing surfactants, paraffin, silicone or fluorine-containing oils or silicone-containing copolymers such as polysiloxane-polyether copolymers. Reactive, modified silicones can also be used. Such products can contain carboxyl, amino and / or epoxy groups and, with a suitable combination of e.g. Amino and epoxy silicone lead to cross-linked sliding layers.

Das genannte Gleitmittel kann auch als separate Beschichtung, als Dispersion oder aus einem geeigneten Lösemittel gegebenenfalls als "Topcoat" aufgebracht werden. Die Dicke einer solchen Schicht beträgt dann vorzugsweise 0,01 bis 5 µm, besonders bevorzugt zwischen 0,05 und 2 µm.The lubricant mentioned can also be applied as a separate coating, as a dispersion or, if appropriate, from a suitable solvent as a "top coat". The thickness of such a layer is then preferably 0.01 to 5 μm, particularly preferably between 0.05 and 2 μm.

Als Träger für die Farbakzeptorschichten können verschiedene Materialien verwendet werden. Es ist möglich, transparente Filme wie z.B. Polyethylenterephthalat-, Polycarbonat-, Polyethersulfon-, Polyolefin-, Polyvinylchlorid-, Polystyrol-, Cellulose- oder Polyvinylalkoholcopolymer-Filme einzusetzen. Natürlich kommen auch reflektierende Unterlagen wie die verschiedensten Arten von Papieren wie z.B. Polyolefinbeschichtetes Papier oder pigmentierte Papiere zum Einsatz. Auch Laminate aus den obengenannten Materialien sind anwendbar. Typische Kombinationen stellen Laminate aus Cellulosepapier und synthetischem Papier oder Cellulosepapier und Polymerfilme oder Polymerfilme und synthetischem Papier oder auch weitere Kombinationen dar.Various materials can be used as carriers for the color acceptor layers. It is possible to use transparent films such as polyethylene terephthalate, polycarbonate, polyether sulfone, polyolefin, polyvinyl chloride, polystyrene, cellulose or polyvinyl alcohol copolymer films. Of course, reflective documents such as the most varied types of paper such as polyolefin-coated paper or pigmented papers are also used. Also laminates made from the above materials are applicable. Typical combinations are laminates of cellulose paper and synthetic paper or cellulose paper and polymer films or polymer films and synthetic paper or other combinations.

Die Träger sorgen für die notwendige mechanische Stabilität des Farbakzeptorelements. Wenn die Farbakzeptorschicht über eine ausreichende mechanische Stabilität verfügt, kann auf einen zusätzlichen Träger verzichtet werden.The carriers ensure the necessary mechanical stability of the color acceptor element. If the color acceptor layer has sufficient mechanical stability, an additional support can be dispensed with.

Die Farbakzeptorschichten der vorliegenden Erfindung haben vorzugsweise Gesamtschichtdicken von 0,3 bis 50 µm, besonders bevorzugt von 0,5 bis 10 µm, wenn ein Träger der oben beschriebenen Art verwendet wird bzw. wenn auf diesen verzichtet wird, von 3 bis 120 µm. Die Farbakzeptorschicht kann aus einer Einzelschicht bestehen, es können aber auch zwei oder mehrere Lagen auf den Träger aufgebracht werden. Bei der Verwendung von transparenten Trägern kann eine beidseitige Beschichtung zur Erhöhung der Farbintensität vorgenommen wrden, wie z.B. in der europäischen Patentanmeldung (EP-A-452 566) beschrieben.The color acceptor layers of the present invention preferably have total layer thicknesses of 0.3 to 50 μm, particularly preferably 0.5 to 10 μm, if a carrier of the type described above is used or if this is dispensed with, from 3 to 120 μm. The color acceptor layer can consist of a single layer, but two or more layers can also be applied to the support. When using transparent supports, a double-sided coating can be applied to increase the color intensity, e.g. in the European patent application (EP-A-452 566).

Das Farbakzeptorelement der vorliegenden Erfindung kann auch verschiedene Zwischenschichten zwischen Unterlage und Farbstoffempfangsschicht enthalten. Abhängig von den spezifischen Eigenschaften des verwendeten Materials kann die Zwischenschicht als federndes Element (elastische Schicht), als Sperrschicht für den übertragenen Farbstoff oder auch als Haftschicht jeweils abhängig von der speziellen Anwendung wirken. Als Material kommen z.B. Urethan-, Acrylat- oder Olefinharze, aber auch Butadienkautschuke oder Epoxide in Frage. Die Dicke dieser Zwischenschicht liegt üblicherweise zwischen etwa 1 bis 2 und 20 µm. Diffusionssperrschichten haben die Aufgabe, die Diffusion der übertragenen Farbstoffe in den Träger zu verhindern. Materialien, die diese Aufgabe erfüllen, können in Wasser oder in organischen Lösungsmitteln oder in Mischungen löslich sein, vorzugsweise jedoch in Wasser. Geeignete Materialien sind z.B. Gelatine, Polyacrylsäure, Maleinsäureanhydridcopolymere, Polyvinylalkohol oder Celluloseacetat.The color acceptor element of the present invention may also include various intermediate layers between the backing and the dye-receiving layer. Depending on the specific properties of the material used, the intermediate layer can act as a resilient element (elastic layer), as a barrier layer for the transferred one Dye or as an adhesive layer depending on the specific application. Examples of suitable materials are urethane, acrylate or olefin resins, but also butadiene rubbers or epoxies. The thickness of this intermediate layer is usually between about 1 to 2 and 20 microns. Diffusion barrier layers have the task of preventing the transferred dyes from diffusing into the support. Materials that fulfill this task can be soluble in water or in organic solvents or in mixtures, but preferably in water. Suitable materials are, for example, gelatin, polyacrylic acid, maleic anhydride copolymers, polyvinyl alcohol or cellulose acetate.

Die gegebenenfalls vorhandenen zusätzlichen Schichten wie elastische Schicht, Diffusionssperrschicht, Haftschicht usw. sowie die eigentliche Farbakzeptorschicht können z.B. Silikat-, Ton-, Aluminiumsilicat-, Calciumcarbonat-, Calciumsulfat-, Bariumsulfat-, Titandioxid-, Aluminiumoxidpulver enthalten.The optional additional layers such as elastic layer, diffusion barrier layer, adhesive layer etc. as well as the actual color acceptor layer can e.g. Contain silicate, clay, aluminum silicate, calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, aluminum oxide powder.

Das Farbakzeptorelement der vorliegenden Erfindung kann auch vorder- oder rückseitig auf die übliche Art und Weise antistatisch ausgerüstet sein.The color acceptor element of the present invention can also be antistatically treated on the front or back in the usual way.

Die Herstellung der die erfindungsgemäßen Polyesterharze enthaltenden Farbakzeptorschichten erfolgt üblicherweise aus Lösung. Geeignete Lösungsmittel sind beispielsweise Wasser, Methylethylketon (MEK), Butylacetat, Aceton, Alkohole oder Lösungsmittelgemische, wie z.B. MEK/Wasser, Ethanol/Wasser. Die Lösung kann durch Gießen oder Rakeln auf den Träger ausgebracht werden.The color acceptor layers containing the polyester resins according to the invention are usually produced from solution. Suitable solvents are, for example, water, methyl ethyl ketone (MEK), butyl acetate, acetone, alcohols or solvent mixtures, such as MEK / water, ethanol / water. The solution can be applied to the carrier by pouring or knife coating.

Das erfindungsgemäße Farbakzeptorelement eignet sich zur Herstellung von Farbstoffübertragungsbildern. Hierzu wird ein Farbakzeptorelement mit einem Farbdonorelement beschichtungsseitig in Kontakt gebracht und letzteres von der Rückseite her bildmäßig erwärmt, Durch Erwärmung auf ca, 400°C während einiger Millisekunden wird der Farbstoffübertrag bewirkt.The color acceptor element according to the invention is suitable for producing dye transfer images. For this purpose, a color acceptor element is brought into contact with a color donor element on the coating side and the latter is imagewise heated from the rear. The dye transfer is brought about by heating to approximately 400 ° C. for a few milliseconds.

Die bildmäßige Erwärmung der Farbdonorschicht erfolgt üblicherweise mittels eines handelsüblichen Thermodruckkopfes (thermal head) in einem Thermosublimationsdrucker, Die für den Farbstoffübertrag erforderliche Wärmeenergie kann aber auch durch Laserlicht, IR-Blitzbelichtung oder mittels eines erwärmten Stiftes zugeführt werden, Erforderlichenfalls enthält die Farbstoffschicht oder eine andere Schicht des Donorelementes Mittel, die Licht absorbieren und in Wärme umwandeln, z,B, Ruß. Die bildmäßige Erwarmung kann auch mittels der bekannten resistive-ribbon-Technologie bewirkt werden. Hierbei ist der Träger des Donorelementes beispielsweise eine bandförmige mit Ruß beladene und mit einem dünnen Aluminiumfilm beschichtete Polycarbonatschicht, der durch elektrische Ansteuerung einer Druckkopfelektrode (print head electrode) bildmäßig elektrischer Strom zugeführt wird, wodurch Wärme in dem resistive-ribbon erzeugt wird. Da die Druckkopfelektrode sich hierbei selbst kaum erwärmt, wirkt sich diese Technologie vorteilhaft auf die Druckgeschwindigkeit aus.The dye donor layer is usually heated imagewise by means of a commercially available thermal head in a thermal sublimation printer.However, the thermal energy required for dye transfer can also be supplied by laser light, IR flash exposure or by means of a heated pen, if necessary the dye layer or another layer contains the donor element means that absorb light and convert it into heat, for example, soot. The imagewise heating can also be effected using the known resistive ribbon technology. Here, the carrier of the donor element is, for example, a ribbon-shaped polycarbonate layer loaded with soot and coated with a thin aluminum film, to which electrical current is supplied by electrical control of a print head electrode (print head electrode), as a result of which heat is generated in the resistive ribbon. Since the printhead electrode hardly heats itself up, this technology has an advantageous effect on the printing speed.

Ein mehrfarbiges Bild kann kann hergestellt werden, indem das erfindungsgemäße Farbakzeptorelement nacheinander mit jedem von drei oder mehr Donorelementen mit unterschiedlichen Farbstoffen in Kontakt gebracht wird, durch bildmäßige Erwärmung des Donorelementes von jenem einen bildmäßigen Farbstoffübertrag in der betreffenden Farbe empfängt und von jenem wieder abgetrennt wird. Anstelle mehrerer unterschiedlich eingefärbter Donorelemente kann auch ein einziges Donorelement verwendet werden, das die verschiedenen Farbstoffe in unterschiedlichen Bereichen enthält.A multicolor picture can be made by successively bringing the color acceptor element according to the invention into contact with each of three or more donor elements with different dyes, by imagewise heating the donor element from the latter to receive an imagewise dye transfer in the relevant color and then separating it from that. Instead of several differently colored donor elements, it is also possible to use a single donor element which contains the different dyes in different areas.

Um die hierbei erforderliche genaue Positionierung während des Druckvorganges zu gewährleisten, können Farbakzeptorelement und/oder Donorelement mit optisch erkennbaren Markierungen versehen sein.In order to ensure the precise positioning required here during the printing process, the color acceptor element and / or donor element can be provided with optically recognizable markings.

Die mit dem erfindungsgemäßen Farbakzeptorelement erhaltenen Farbbilder zeichnen sich durch hohe Auflösung, hohe Farbdichten, hohe Brillanz und gute Langzeitstabilität aus.The color images obtained with the color acceptor element according to the invention are notable for high resolution, high color densities, high brilliance and good long-term stability.

BeispieleExamples

Die erfindungsgemäßen Polyesterharze werden in einer üblichen Kondensationsapparatur bei gängigen Reaktionsbedingungen hergestellt.The polyester resins according to the invention are produced in a conventional condensation apparatus under common reaction conditions.

Die Herstellungsweise wird durch nachfolgendes Beispiel näher erläutert.The production method is explained in more detail by the following example.

Polyester IPolyester I

96,48 g (45 mol-%) Terephthalsäuredimethylester, 96,48 g (45 mol-%) Isophthalsäuredimethylester, 34,43 g (10 mol-%) Sulfoisophthalsäuredimethylester-Na-Salz, 71,95 g (105 mol-%) Ethylenglykol, 69,86 g (20 mol-%) Dianol 22, 30,81 g (5 mol-%) Dimerdiol 2033 sowie 0,1 g Titantetrabutylat werden vorgelegt und unter N₂ von Raumtemperatur auf 220°C erhitzt und 1 h unter Rückfluß gekocht. Anschließend wird während 1 h Destillat abgenommen und die Badtemperatur stufenweise auf 280°C erhöht und 1 h bei dieser Temperatur nachgerührt. Die abschließende Kondensation erfolgt über 2 h bei 280°C unter Anlegen eines Ölpumpenvakuums. Das Harz wird durch Ausgießen der Schmelze isoliert. Das entsprechend der oben angegebenen Stöchiometrie überschüssige Ethandiol wird im Laufe der Kondensation destillativ abgetrennt, so daß nahezu äquivalente molare Mengen an Säure- und Alkoholgruppen vorliegen.96.48 g (45 mol%) dimethyl terephthalate, 96.48 g (45 mol%) dimethyl isophthalate, 34.43 g (10 mol%) dimethyl sulfoisophthalate sodium salt, 71.95 g (105 mol%) Ethylene glycol, 69.86 g (20 mol%) Dianol 22, 30.81 g (5 mol%) dimer diol 2033 and 0.1 g titanium tetrabutylate are introduced and heated under N₂ from room temperature to 220 ° C and 1 h under reflux cooked. The distillate is then removed over a period of 1 h and the bath temperature is gradually increased to 280 ° C. and the mixture is subsequently stirred at this temperature for 1 h. The final condensation takes place over 2 hours at 280 ° C with an oil pump vacuum. The resin is isolated by pouring out the melt. The excess ethanediol corresponding to the stoichiometry indicated above is removed by distillation in the course of the condensation, so that almost equivalent molar amounts of acid and alcohol groups are present.

Entsprechend der oben beschriebenen Herstellungsweise wurden die Polyester 1-6 hergestellt, wie in Tabelle 1 angegeben (Angaben in mol-%, bezogen auf die Summe Dicarbonsäurekomponente = 100 mol-%).

Figure imgb0005
According to the production method described above, the polyesters 1-6 were prepared as indicated in Table 1 (data in mol%, based on the total dicarboxylic acid component = 100 mol%).
Figure imgb0005

Die Polyesterharze 1-6 wurden in Wasser/MEK (8:2) entsprechend der in Tab. 1 angegebenen Konzentration gelöst und mit Hilfe einer Rakel in einer Naßfilmdicke von 20 µm bzw. 25 µm (s. Tab. 1) auf ein Papier gegossen, das beidseitig mit Polyethylen beschichtet war und auf dessen eine Seite über das Polyethylen zusätzlich eine Gelatineschicht aufgebracht worden war. Auf diese Seite wurde die Polyesterlösung aufgetragen. Die Beschichtungen wurden im Umlufttrockenschrank bei 70°C 30 min getrocknet. Jeweils eine Probe (a) wurde unbeschichtet gelassen (keine Gleitschicht). Auf jeweils eine weitere Probe (b) wurde eine 0,5 %ige Lösung in Ethanol von Tego® Glide 410 (Firma Tego Chemie Service GmbH) mit einer Naßfilmdicke von 24 µm aufgebracht und im Umlufttrockenschrank bei 70°C getrocknet. Auf die erhaltenen Farbstoffempfangselemente wurden mit einem Mitsubishi CP-100 E Videoprinter unter Verwendung der Mitsubishi-Farbstoffkassette CK-100 S Testbilder erzeugt.The polyester resins 1-6 were dissolved in water / MEK (8: 2) in accordance with the concentration given in Table 1 and poured onto a paper using a doctor blade in a wet film thickness of 20 µm or 25 µm (see Table 1) which was coated on both sides with polyethylene and on one side of which a gelatin layer had additionally been applied over the polyethylene. The polyester solution was applied to this side. The coatings were dried in a forced-air drying cabinet at 70 ° C. for 30 minutes. Each sample (a) was left uncoated (no sliding layer). A 0.5% solution in ethanol from Tego® Glide 410 (Tego Chemie Service GmbH) with a wet film thickness of 24 μm was applied to each further sample (b) and dried at 70 ° C. in a forced-air drying cabinet. Test images were generated on the dye-receiving elements obtained using a Mitsubishi CP-100 E video printer using the Mitsubishi dye cassette CK-100 S.

Die Farbstoffakzeptorschichten, die aus den erfindungsgemäßen Polyestern aufgebaut sind, zeichnen sich durch sehr hohe Farbdichten und stark verringerte Klebeneigung aus. In Tabelle 2 sind Farbdichten, die mit einem Macbeth RD 919 Densitometer bestimmt worden sind, sowie das Klebeverhalten, aufgeführt.

Figure imgb0006
The dye acceptor layers, which are built up from the polyesters according to the invention, are distinguished by very high color densities and greatly reduced tendency to stick. Table 2 lists the color densities, which were determined using a Macbeth RD 919 densitometer, and the adhesive behavior.
Figure imgb0006

Claims (4)

  1. Dye acceptor element for the thermosublimation printing process, comprising a layer support and, on this support, a dye acceptor layer containing a polyester formed from diols and dicarboxylic acids, characterised in that from 0.5 to 60 mol-% of the diol component of the polyester consists of one or more dialkyl substituted diols having 24 or more carbon atoms, optionally containing a saturated, unsaturated or aromatic ring.
  2. Dye acceptor element according to Claim 1, characterised in that the polyester is formed from aromatic dicarboxylic acids.
  3. Dye acceptor element according to Claim 2, characterised in that the aromatic dicarboxylic acid used is terephthalic acid, isophthalic acid and/or sulphoisophthalic acid, optionally in the form of a derivative (salt, acid chloride, ester) and in that the diol used (with the exclusion of the dimer diol) is ethylene glycol.
  4. Dye acceptor element according to one of the Claims 1 to 3, characterised in that the polyester contains solubilizing groups.
EP19910114420 1990-10-17 1991-08-28 Dye-acceptor element for thermal sublimation printing process Expired - Lifetime EP0481200B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US07/773,036 US5250494A (en) 1990-10-17 1991-10-08 Dye acceptor element for the thermal sublimation printing process
JP3296629A JPH04263991A (en) 1990-10-17 1991-10-17 Dye acceptor element for heat subliming and printing method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19900202759 EP0481129B1 (en) 1990-10-17 1990-10-17 Thermal dye sublimation transfer receiving element
EP90202759 1990-10-17

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EP0481200A1 EP0481200A1 (en) 1992-04-22
EP0481200B1 true EP0481200B1 (en) 1993-11-24

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EP19910114420 Expired - Lifetime EP0481200B1 (en) 1990-10-17 1991-08-28 Dye-acceptor element for thermal sublimation printing process

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DE69222995T2 (en) * 1991-02-15 1998-03-19 Toyo Boseki COLORABLE RESIN FOR SUBLIMATION TYPE TRANSFER RECEIVERS AND IMAGE RECEIVERS IN WHICH THIS RESIN IS USED
EP0627662B1 (en) * 1993-05-24 1999-07-07 Agfa-Gevaert N.V. A photographic material comprising a copolyester support
TW558522B (en) * 2001-07-30 2003-10-21 Kiwa Chemical Ind Co Ltd Laminated body for printing with temporary display layer and printing method using the same

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GB8709798D0 (en) * 1987-04-24 1987-05-28 Ici Plc Receiver sheet
DE68926900T2 (en) * 1988-10-17 1997-03-06 Dainippon Printing Co Ltd Heat sensitive transfer recording process.

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JP2623181B2 (en) 1997-06-25
JPH04282293A (en) 1992-10-07
DE69009057D1 (en) 1994-06-23
EP0481129A1 (en) 1992-04-22
EP0481200A1 (en) 1992-04-22
DE59100636D1 (en) 1994-01-05
DE69009057T2 (en) 1994-11-10
EP0481129B1 (en) 1994-05-18

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