EP0405248B1 - Image-receiving material for thermal dye-transfer - Google Patents

Image-receiving material for thermal dye-transfer Download PDF

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Publication number
EP0405248B1
EP0405248B1 EP19900111315 EP90111315A EP0405248B1 EP 0405248 B1 EP0405248 B1 EP 0405248B1 EP 19900111315 EP19900111315 EP 19900111315 EP 90111315 A EP90111315 A EP 90111315A EP 0405248 B1 EP0405248 B1 EP 0405248B1
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EP
European Patent Office
Prior art keywords
receiving material
material according
image receiving
acrylate copolymer
dye
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.)
Expired - Lifetime
Application number
EP19900111315
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German (de)
French (fr)
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EP0405248A3 (en
EP0405248A2 (en
Inventor
Jahn Reiner
Horst Westfal
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Felex Schoeller Jr and GmbH and Co KG
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Felex Schoeller Jr and GmbH and Co KG
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Publication of EP0405248A3 publication Critical patent/EP0405248A3/en
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5254Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/913Material designed to be responsive to temperature, light, moisture
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/914Transfer or decalcomania
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24934Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including paper layer
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/27Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y10T428/277Cellulosic substrate
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • Y10T428/31895Paper or wood
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • Y10T428/31895Paper or wood
    • Y10T428/31899Addition polymer of hydrocarbon[s] only
    • Y10T428/31902Monoethylenically unsaturated

Definitions

  • the invention relates to an image-receiving material for thermal dye transfer and a method for its production.
  • D2T2 dye diffusion thermal transfer
  • thermal dye transfer The principle of thermal dye transfer is that the digital image is processed with regard to the primary colors cyan, magenta, yellow and black and converted into corresponding electrical signals. These signals are forwarded to a thermal printer and converted into heat. Due to the action of heat, the dye sublimes from the donor layer of an ink ribbon (ink sheet) in contact with the receiving material and diffuses into the receiving layer.
  • ink ribbon ink sheet
  • a receiving material for thermal dye transfer generally consists of a carrier with a receiving layer applied to its front.
  • other layers are often applied to the front of the carrier. These include a. Barrier, separating, adhesive and protective layers.
  • the main component of the receiving layer is usually a thermoplastic resin that has an affinity for the dye from the ribbon.
  • thermoplastic resin that has an affinity for the dye from the ribbon.
  • linear polyesters e.g. B. polyethylene terephthalate, polybutylene terephthalate or acrylic resins, e.g. B. polymethyl methacrylate, polybutyl methacrylate, polymethylacrylate, etc.
  • polystyrene, polycarbonate, polyvinylpyrrolidone, ethyl cellulose, polysulfone and other plastics can be used as the dye-absorbing resin.
  • a polycarbonate receiving layer is applied to a polyethylene-coated base paper.
  • an underlayer is applied between the support and the receiving layer.
  • This underlayer consists of a vinylidene chloride copolymer and serves to improve the adhesion of the receiving layer to the carrier material.
  • a disadvantage of this receiver sheet is that the polycarbonate used here tends to yellow and adversely affect the transferred image over time. Another disadvantage is that both layers are applied from a solvent environment, which poses health and safety problems.
  • Patent application EP 0 261 970 describes a receiving layer which contains a linear saturated polyester as a binder and a silane copolymer coupled with silica as a release agent ("anti-blocking" additive).
  • the present invention is based on the object of proposing an image-receiving material for thermal dye transfer processes which is free from the disadvantages described above, ie is stable to heat and light and is insensitive to pressure, has good flatness and good "anti-blocking" properties.
  • the reception material further improves the color density and gradation compared to the reception sheets available on the market.
  • a receiving layer is applied to the front side of a polyolefin-coated base paper which, as the dye-receiving resin, contains a combination of at least one acrylate copolymer containing polar groups and oxidized polyethylene.
  • Combination creates a receiving sheet that not only meets the requirements listed at the beginning, but also enables a high color density of the transmitted image while increasing the gradation.
  • an acrylate copolymer is used, the polar groups of which are carboxyl, metal-bonded carboxyl and / or nitrile groups.
  • the metal-bonded carboxyl groups zinc-bonded carboxyl groups are particularly preferred.
  • Acrylonitrile and / or methacrylic acid are involved in the construction of the acrylate copolymer contained in the combination according to the invention, and the total proportion of these monomers in the copolymer is 10 to 40 mol%. In a preferred embodiment, the proportion of the monomers mentioned is 25 to 35 mol%.
  • styrene Up to 40 mol% of styrene can also be involved in the construction of the acrylate copolymer.
  • the weight ratio of acrylate copolymer / oxidized polyethylene in the combination according to the invention is 99: 1 to 30:70.
  • the results with regard to color density and color gradation are most favorable when the weight ratio of acrylate copolymer / oxidized polyethylene is from 70:30 to 40:60 (example 2, Table 2).
  • the receiving layer for the receiving sheet according to the invention can in addition to the dye-absorbing resin still finely divided silica or Al2O3 as a matting agent and other additives such as wetting agents, eg. B. fluorosurfactants, dispersants, color couplers, UV stabilizers, pigments and similar auxiliaries.
  • wetting agents eg. B. fluorosurfactants, dispersants, color couplers, UV stabilizers, pigments and similar auxiliaries.
  • the receiving layer can with the help of all common application and dosing procedures such. B. roller application, engraving or nipping process on a substrate, for. B. PE coated paper can be applied.
  • the receiving layer can be applied from an aqueous medium in a single operation.
  • the application amount of the receiving layer is 0.3 - 15 g / m2, preferably 1 to 10 g / m2.
  • the polyolefin layer according to the state of the coating technology has a basis weight of 5 g / m2 or more, preferably 7-25 g / m2.
  • the polyolefin layer can contain pigments and other additives.
  • the front of a polyethylene-coated base paper * was coated with an aqueous dispersion of the following composition: * )
  • a base paper with a polyethylene coating on both sides and a basis weight of 180 g / m2 was used.
  • test conditions - machine speed 130 m / min. - drying temperature 110 ° C - drying time 10 sec.
  • Copolymers were used as acrylate copolymers, in whose construction polar monomers bearing the following proportions are involved: Acrylate copolymer I (e.g. Primal HG-44, Rohm & Haas Comp.) 35 mol% Acrylate copolymer II (e.g. Maincote HG-54 from Rohm & Haas Comp.) 30 mol%
  • Acrylate copolymer I e.g. Primal HG-44, Rohm & Haas Comp.
  • Acrylate copolymer II e.g. Maincote HG-54 from Rohm & Haas Comp.
  • acrylate / styrene copolymer containing zinc-bonded COOH groups eg NeoCryl SR-205, from Polyvinyl Chemie Holland BV
  • NeoCryl SR-205 from Polyvinyl Chemie Holland BV
  • a fluorosurfactant (e.g. FT-248, Bayer AG) was used as the wetting agent.
  • the receiving material obtained was printed using the thermal image transfer method and then analyzed.
  • the results are summarized in Table 1.
  • a layer support according to Example 1 was coated with an aqueous dispersion of the following composition: product Composition,% by weight 3A 3B 3C Acrylate copolymer I, 40% aq. Disp. (like Ex. 1) 53.8 48.4 42.7 oxide. Polyethylene, 30% aq. Disp. (like Ex. 2) 27.6 32.3 28.4 Silica, 15% in water (e.g. Syloid ED 50, Grace GmbH 11.1 - - Al2O3, 63% slurry, (e.g. Martifin OL-008 from Martinswerk) - 15.3 13.5 Titanium dioxide, 40% in water (e.g. Rutil RN 40, from Kronos Titan) 4.1 - - UV absorber, 15% in water (e.g. Tinuvin 213, Ciba-Geigy AG) - - 11.8 Fluorosurfactant, 1% in water (like Ex. 1) 3.4 4.0 3.6 Order quantity, g / m2 5.0 5.0 5.0 5.0
  • the receiving material obtained was subjected to a thermal image transfer process.
  • a Color Video Printer VY - 25 E from Hitachi was used using a Hitachi ribbon.
  • the video printer has the following technical data: Image storage PAL 1 full screen memory Printed image 64 color image Image elements: 540: 620 points Printing time 2 minutes / picture
  • the density measurements were carried out before and after a 24-hour exposure of the images using a xenon lamp.
  • the loss in density caused by the exposure was designated ⁇ d (%) and used to assess the light stability.
  • the device used for this was an original reflection densitometer SOS-45.
  • the measurements were carried out in five color gradations F1 - F5 for the primary colors cyan, magenta, yellow and black, the values for F1, F3 and F5 being given in the tables.
  • the number of possible color gradations from 0 to 7 is also included in the tables.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Thermotherapy And Cooling Therapy Devices (AREA)

Abstract

There is described an image-receiving material for thermal dye transfer, comprising a polyolefin-coated base paper and, applied to the face thereof, a receiving layer which as dye-receiving resin contains a combination of an acrylate copolymer with polar groups on the one hand and oxidised polyethylene on the other.

Description

Die Erfindung betrifft ein Bildempfangsmaterial für thermische Farbstoffübertragung sowie ein Verfahren zu dessen Herstellung.The invention relates to an image-receiving material for thermal dye transfer and a method for its production.

In den letzten Jahren wurde ein System der thermischen Farbstoffübertragung (Dye Diffusion Thermal Transfer - "D2T2") entwickelt, welches die Wiedergabe eines elektronisch erzeugten Bildes in Form einer "Hardcopy" ermöglicht.A dye diffusion thermal transfer ("D2T2") system has been developed in recent years, which enables the reproduction of an electronically generated image in the form of a "hard copy".

Das Prinzip der thermischen Farbstoffübertragung besteht darin, daß das digitale Bild hinsichtlich der Grundfarben Cyan, Magenta, Gelb und Schwarz aufbereitet und in entsprechende elektrische Signale umgewandelt wird. Diese Signale werden zu einem Thermodrucker weitergeleitet und in Wärme umgesetzt.
Durch die Wärmeeinwirkung sublimiert der Farbstoff aus der Donorschicht eines im Kontakt mit dem Empfangsmaterial stehenden Farbbandes (Farbblattes) und diffundiert in die Empfangsschicht hinein.
The principle of thermal dye transfer is that the digital image is processed with regard to the primary colors cyan, magenta, yellow and black and converted into corresponding electrical signals. These signals are forwarded to a thermal printer and converted into heat.
Due to the action of heat, the dye sublimes from the donor layer of an ink ribbon (ink sheet) in contact with the receiving material and diffuses into the receiving layer.

Ein Empfangsmaterial für thermische Farbstoffübertragung besteht in der Regel aus einem Träger mit auf dessen Vorderseite aufgebrachter Empfangsschicht. Außer der Empfangsschicht werden oft noch andere Schichten auf die Vorderseite des Trägers aufgebracht. Dazu gehören u. a. Sperr-, Trenn-, Haft-, und Schutzschichten.A receiving material for thermal dye transfer generally consists of a carrier with a receiving layer applied to its front. In addition to the receiving layer, other layers are often applied to the front of the carrier. These include a. Barrier, separating, adhesive and protective layers.

Die Notwendigkeit der zusätzlichen Schichten ist durch die an das Empfangsmaterial gestellten Anforderungen begründet, wie:

  • glatte Oberfläche
  • Hitze- und Druckstabilität
  • Lichtstabilität, kein Vergilben
  • gute Farbstofflöslichkeit
  • gute Kratz- und Abriebfestigkeit
  • "anti-blocking"-Eigenschaften (kein Kleben)
Als Träger kann eine Kunststoffolie, z. B. Polyesterfilm oder ein beschichtetes Papier dienen.The need for additional layers is due to the requirements placed on the receiving material, such as:
  • smooth surface
  • Heat and pressure stability
  • Light stability, no yellowing
  • good dye solubility
  • good scratch and abrasion resistance
  • "anti-blocking" properties (no sticking)
A plastic film, e.g. B. polyester film or coated paper.

Die Hauptkomponente der Empfangsschicht ist in der Regel ein thermoplastisches Harz, das eine Affinität zum Farbstoff aus dem Farbband aufweist. Dazu gehören lineare Polyester, z. B. Polyethylenterephthalat, Polybutylenterephthalat oder Acrylharze, z. B. Polymethylmethacrylat, Polybutylmethacrylat, Polymethylacrylat usw.. Weiterhin können Polystyrol, Polycarbonat, Polyvinylpyrrolidon, Ethylcellulose, Polysulfon und andere Kunststoffe als farbstoffaufnehmendes Harz verwendet werden.The main component of the receiving layer is usually a thermoplastic resin that has an affinity for the dye from the ribbon. These include linear polyesters, e.g. B. polyethylene terephthalate, polybutylene terephthalate or acrylic resins, e.g. B. polymethyl methacrylate, polybutyl methacrylate, polymethylacrylate, etc. Furthermore, polystyrene, polycarbonate, polyvinylpyrrolidone, ethyl cellulose, polysulfone and other plastics can be used as the dye-absorbing resin.

Aus den Patentschriften US 4 748 150 und US 4 774 224 ist bekannt, daß auf ein polyethylenbeschichtetes Basispapier eine Empfangsschicht aus Polycarbonat aufgetragen wird. Außerdem wird eine Unterschicht zwischen dem Träger und der Empfangsschicht aufgebracht. Diese Unterschicht besteht aus einem Vinylidenchlorid-Copolymer und dient zur Verbesserung der Haftung der Empfangsschicht auf dem Trägermaterial.From US Pat. Nos. 4,748,150 and 4,774,224 it is known that a polycarbonate receiving layer is applied to a polyethylene-coated base paper. In addition, an underlayer is applied between the support and the receiving layer. This underlayer consists of a vinylidene chloride copolymer and serves to improve the adhesion of the receiving layer to the carrier material.

Nachteilig an diesem Empfangsblatt ist, daß das hier verwendete Polycarbonat stark zur Vergilbung neigt und im Laufe der Zeit das übertragene Bild negativ beeinflußt. Ein weiterer Nachteil liegt darin, daß das Auftragen beider Schichten aus einem Lösungsmittelmilieu geschieht, was Gesundheits- und Sicherheitsprobleme mit sich bringt.A disadvantage of this receiver sheet is that the polycarbonate used here tends to yellow and adversely affect the transferred image over time. Another disadvantage is that both layers are applied from a solvent environment, which poses health and safety problems.

Das Problem der Druckempfindlichkeit des Empfangsblattes beim Kontakt mit dem Heizkopf wird in der europäischen Patentanmeldung EP 0 288 193 behandelt. Die Druckempfindlichkeit äußert sich durch eine Verminderung des Oberflächenglanzes der Schicht oder durch das Phänomen "strike-through", bei dem der Abdruck des Bildes auf der Rückseite des Empfangsblattes zu beobachten ist.
Das Problem wird dadurch gelöst, daß auf ein Polyesterträgermaterial mit einer aufcoextrudierten Polyesterempfangsschicht eine Trennschicht auf Silikonbasis mit einem SiO₂-Zusatz aufgebracht wird. Nachteilig an diesem Empfangsblatt ist, daß wahrscheinlich infolge einer Reaktion zwischen den reaktiven Gruppen der Silikon-Verbindungen und dem in die Empfangsschicht hineindiffundierenden Farbstoff das erhaltene Bild verwischt ist. Außerdem fehlt die auf dem Markt gewünschte Fotoähnlichkeit des auf diese Weise erzeugten Bildes.
The problem of the pressure sensitivity of the receiver sheet when it comes into contact with the heating head is dealt with in European patent application EP 0 288 193. The pressure sensitivity is manifested by a reduction in the surface gloss of the layer or by the "strike-through" phenomenon, in which the impression of the image on the back of the receiver sheet can be observed.
The problem is solved in that a release layer on a silicone basis with an SiO₂ additive is applied to a polyester carrier material with a coextruded polyester receiving layer. A disadvantage of this receiving sheet is that the image obtained is probably blurred due to a reaction between the reactive groups of the silicone compounds and the dye diffusing into the receiving layer. In addition, the desired photographic similarity of the image produced in this way is missing on the market.

Es ist weiterhin bekannt, daß die aus dem Donor-Farbband stammenden und in die Empfangsschicht hineindiffundierten Farbstoffe unter Lichteinwirkung zum Verblassen neigen. Dieses Problem wurde in der Patentschrift US 4 775 657 gelöst, indem auf die aus Polycarbonat bestehende Empfangsschicht eine Schutzschicht aus Polyester oder Polyurethan aufgetragen wird. Nachteilig dabei ist die Druckempfindlichkeit des auf diese Weise hergestellten Empfangsblattes, sowie die hierfür erforderlichen mehreren Arbeitsstufen und das Auftragen der Schichten aus organischen Lösungsmitteln.It is also known that the dyes originating from the donor ink ribbon and diffused into the receiving layer tend to fade when exposed to light. This problem was solved in US Pat. No. 4,775,657 by applying a protective layer made of polyester or polyurethane to the polycarbonate receiving layer. The disadvantage here is the pressure sensitivity of the receiver sheet produced in this way, as well as the several work steps required for this and the application of the layers of organic solvents.

In der Patentanmeldung EP 0 261 970 ist eine Empfangsschicht beschrieben, die einen linearen gesättigten Polyester als Bindemittel und ein mit Kieselsäure gekoppeltes Silan-Copolymer als Trennmittel ("anti-blocking"-Zusatz) enthält.Patent application EP 0 261 970 describes a receiving layer which contains a linear saturated polyester as a binder and a silane copolymer coupled with silica as a release agent ("anti-blocking" additive).

Der vorliegenden Erfindung liegt nun die Aufgabe zugrunde, ein Bildempfangsmaterial für thermische Farbstoffübertraungsverfahren vorzuschlagen, das frei von den oben beschriebenen Nachteilen ist, d. h. hitze- und lichtstabil sowie druckunempfindlich ist, eine gute Planlage und gute "anti-blocking"-Eigenschaften aufweist. Außerdem wird mit dem Empfangsmaterial eine weitere Verbesserung der Farbdensität und der Farbabstufung (Gradation) im Vergleich zu den auf dem Markt verfugbaren Empfangsblättern erzielt.The present invention is based on the object of proposing an image-receiving material for thermal dye transfer processes which is free from the disadvantages described above, ie is stable to heat and light and is insensitive to pressure, has good flatness and good "anti-blocking" properties. In addition, the reception material further improves the color density and gradation compared to the reception sheets available on the market.

Diese Aufgabe wird gelöst, indem auf die Vorderseite eines polyolefinbeschichteten Basispapiers eine Empfangsschicht aufgetragen wird, die als farbstoffaufnehmendes Harz eine Kombination aus wenigstens einem, polare Gruppen enthaltenden Acrylat-Copolymer und oxydiertem Polyethylen enthält.This object is achieved in that a receiving layer is applied to the front side of a polyolefin-coated base paper which, as the dye-receiving resin, contains a combination of at least one acrylate copolymer containing polar groups and oxidized polyethylene.

Überrraschend wurde gefunden, daß die Verwendung der o. a. Kombination ein Empfangsblatt schafft, welches nicht nur die anfangs aufgezählten Anforderungen erfüllt, sondern auch eine hohe Farbdensität des übertragenen Bildes ermöglicht bei gleichzeitiger Erhöhung der Gradation.It was surprisingly found that the use of the above. Combination creates a receiving sheet that not only meets the requirements listed at the beginning, but also enables a high color density of the transmitted image while increasing the gradation.

In bevorzugter Ausführung wird ein Acrylat-Copolymer verwendet, dessen polare Gruppen Carboxyl-, metallgebundene Carboxyl- und/oder Nitrilgruppen sind.
Bei den metallgebundenen Carboxylgruppen werden Zink-gebundene Carboxylgruppen besonders bevorzugt.
In a preferred embodiment, an acrylate copolymer is used, the polar groups of which are carboxyl, metal-bonded carboxyl and / or nitrile groups.
In the case of the metal-bonded carboxyl groups, zinc-bonded carboxyl groups are particularly preferred.

Am Aufbau des in der erfindungsgemäßen Kombination enthaltenen Acrylat-Copolymers sind Acrylnitril und/oder Methacrylsäure beteiligt, und der Anteil dieser Monomere im Copolymer beträgt in der Summe 10 bis 40 Mol.-%. In einer bevorzugten Ausführung beträgt der Anteil der genannten Monomere 25 bis 35 Mol.-%.Acrylonitrile and / or methacrylic acid are involved in the construction of the acrylate copolymer contained in the combination according to the invention, and the total proportion of these monomers in the copolymer is 10 to 40 mol%. In a preferred embodiment, the proportion of the monomers mentioned is 25 to 35 mol%.

Am Aufbau des Acrylat-Copolymers kann auch zusätzlich Styrol in einer Menge bis 40 Mol.-% beteiligt sein.Up to 40 mol% of styrene can also be involved in the construction of the acrylate copolymer.

Das Gewichtsverhältnis Acrylat-Copolymer/oxydiertes Polyethylen in der erfindungsgemäßen Kombination beträgt 99 : 1 bis 30 : 70. Die Ergebnisse hinsichtlich der Farbdensität und Farbabstufung sind bei einem Gewichtsverhältnis Acrylat-Copolymer/oxydiertes Polyethylen von 70 : 30 bis 40 : 60 am günstigsten (Beispiel 2, Tabelle 2).The weight ratio of acrylate copolymer / oxidized polyethylene in the combination according to the invention is 99: 1 to 30:70. The results with regard to color density and color gradation are most favorable when the weight ratio of acrylate copolymer / oxidized polyethylene is from 70:30 to 40:60 (example 2, Table 2).

Die Empfangsschicht für das erfindungsgemäße Empfangsblatt kann außer dem farbstoffaufnehmenden Harz noch feinteilige Kieselsäure oder Al₂O₃ als Mattierungsmittel sowie weitere Zusätze, wie Netzmittel, z. B. Fluortenside, Dispergierhilfsmittel, Farbkuppler, UV-Stabilisatoren, Pigmente und ähnliche Hilfsstoffe enthalten.The receiving layer for the receiving sheet according to the invention can in addition to the dye-absorbing resin still finely divided silica or Al₂O₃ as a matting agent and other additives such as wetting agents, eg. B. fluorosurfactants, dispersants, color couplers, UV stabilizers, pigments and similar auxiliaries.

Die Empfangsschicht kann mit Hilfe aller gebräuchlichen Auftrags- und Dosierungsverfahren z. B. Walzenauftrags-, Gravur- oder Nipp-Verfahren auf ein Substrat, z. B. PE-beschichtetes Papier aufgebracht werden.The receiving layer can with the help of all common application and dosing procedures such. B. roller application, engraving or nipping process on a substrate, for. B. PE coated paper can be applied.

Die Empfangsschicht kann aus wäßrigem Milieu in einem einzigen Arbeitsgang aufgetragen werden.The receiving layer can be applied from an aqueous medium in a single operation.

Die Auftragsmenge der Empfangsschicht beträgt 0,3 - 15 g/m², vorzugsweise 1 bis 10 g/m².The application amount of the receiving layer is 0.3 - 15 g / m², preferably 1 to 10 g / m².

Als Unterlage wird ein mindestens von einer Seite mit Polyolefin, z. B. Polyethylen beschichtetes Papier bevorzugt, wobei die Polyolefinschicht entsprechend dem Stand der Beschichtungstechnik ein Flächengewicht von 5 g/m² oder mehr, vorzugsweise 7 - 25 g/m² hat.As a base, at least one side with polyolefin, e.g. B. polyethylene coated paper is preferred, the polyolefin layer according to the state of the coating technology has a basis weight of 5 g / m² or more, preferably 7-25 g / m².

Die Polyolefinschicht kann Pigmente und andere Zusatzstoffe enthalten.The polyolefin layer can contain pigments and other additives.

Die Erfindung wird mit Hilfe der nachfolgenden Beispiele näher erläutert, jedoch nicht eingeschränkt.The invention is explained in more detail with the aid of the following examples, but is not restricted.

BeispieleExamples Beispiel 1example 1

Die Vorderseite eines polyethylenbeschichteten Basispapiers *) wurde mit einer wäßrigen Dispersion folgender Zusammensetzung beschichtet:
*) Als Unterlage diente ein beidseitig polyethylenbeschichtetes Basispapier mit einem Flächengewicht von 180 g/m².
Die Rückseite des Rohpapiers wurde mit klarem Polyethylen, welches eine Mishung aus LDPE und HDPE ist (35 % HDPE mit einer Dichte ρ = 0,959 g/cm3, MFI = 8; 28 % HDPE mit ρ = 0,950 g/cm3, MFI = 7; 20 % LDPE mit ρ = 0,934 g/cm3, MFI = 3; 17 % LDPE mit ρ = 0,915 g/cm3, MFI = 8), in einer Auftragsmenge von 14 - 15 g/m² beschichtet.
Die Vorderseite wurde mit pigmentiertem Polyethylengemisch (19 % HDPE mit ρ = 0,959 g/cm3, MFI = 8; 20 % LDPE mit ρ = 0,934 g/cm3, MFI = 3; 13,3 % LDPE mit ρ = 0,915 g/cm3, MFI = 8; 26,7 % LDPE mit ρ = 0,924 g/cm3, MFI = 4,5; 21 % TiO₂-Masterbatch mit 50 %-igem TiO₂-Anteil) in einer Auftragsmenge von 15 g/m² bescichtet.
The front of a polyethylene-coated base paper * ) was coated with an aqueous dispersion of the following composition:
* ) A base paper with a polyethylene coating on both sides and a basis weight of 180 g / m² was used.
The back of the base paper was covered with clear polyethylene, which is a mixture of LDPE and HDPE (35% HDPE with a density ρ = 0.995 g / cm3, MFI = 8; 28% HDPE with ρ = 0.950 g / cm3, MFI = 7; 20% LDPE with ρ = 0.934 g / cm3, MFI = 3; 17% LDPE with ρ = 0.915 g / cm3, MFI = 8), coated in a quantity of 14 - 15 g / m².
The front was covered with pigmented polyethylene mixture (19% HDPE with ρ = 0.959 g / cm3, MFI = 8; 20% LDPE with ρ = 0.934 g / cm3, MFI = 3; 13.3% LDPE with ρ = 0.915 g / cm3, MFI = 8; 26.7% LDPE with ρ = 0.924 g / cm3, MFI = 4.5; 21% TiO₂ masterbatch with 50% TiO₂ content) coated in an order quantity of 15 g / m².

Produktproduct Zusammensetzung,Gew.-%Composition,% by weight 1A1A 1B1B 1C1C 1D**) 1D **) Acrylat-Copolymer I, 40 % -ige wäßr. Disp.Acrylate copolymer I, 40% aq. Disp. 96,096.0 96,096.0 Acrylat-Copolymer II, 40 %-ige wäßr. Disp.Acrylate copolymer II, 40% aq. Disp. 96,096.0 Acrylat-Copolymer III, 38 %-ige wäßr. Disp.Acrylate copolymer III, 38% aq. Disp. 96,096.0 Fluortensid, 1 %-ig in WasserFluorosurfactant, 1% in water 4,04.0 4,04.0 4,04.0 4,04.0 Auftragsmenge, g/m²Order quantity, g / m² 5,05.0 5,05.0 5,05.0 5,05.0 **) kein TiO₂ in der PE-Beschichtung**) no TiO₂ in the PE coating

Sonstige Versuchsbedingungen:Other test conditions: - Maschinengeschwindigkeit- machine speed 130 m/min.130 m / min. - Trocknungstemperatur- drying temperature 110° C110 ° C - Trocknungszeit- drying time 10 sek.10 sec.

Als Acrylat-Copolymere wurden Copolymere verwendet, an deren Aufbau polare Gruppen tragende Monomere mit folgenden Anteilen beteiligt sind: Acrylat-Copolymer I (z. B. Primal HG-44, Fa. Rohm & Haas Comp.) 35 Mol.-% Acrylat-Copolymer II (z. B. Maincote HG-54 Fa. Rohm & Haas Comp.) 30 Mol.-% Copolymers were used as acrylate copolymers, in whose construction polar monomers bearing the following proportions are involved: Acrylate copolymer I (e.g. Primal HG-44, Rohm & Haas Comp.) 35 mol% Acrylate copolymer II (e.g. Maincote HG-54 from Rohm & Haas Comp.) 30 mol%

Als Acrylat-Copolymer III wurde ein Zink-gebundene COOH-Gruppen enthaltendes Acrylat/Styrol-Copolymer (z. B. NeoCryl SR-205, Fa. Polyvinyl Chemie Holland BV) verwendet.An acrylate / styrene copolymer containing zinc-bonded COOH groups (eg NeoCryl SR-205, from Polyvinyl Chemie Holland BV) was used as the acrylate copolymer III.

Als Netzmittel wurde ein Fluortensid (z. B. FT-248, Fa. Bayer AG) verwendet.A fluorosurfactant (e.g. FT-248, Bayer AG) was used as the wetting agent.

Das erhaltene Empfangsmaterial wurde unter Anwendung des thermischen Bildübertragungsverfahrens bedruckt und anschließend analysiert. Die Ergebnisse sind in Tabelle 1 zusammengestellt.The receiving material obtained was printed using the thermal image transfer method and then analyzed. The results are summarized in Table 1.

Dieses Beispiel soll die besondere Eignung der o. g. Acrylat-Copolymere als Komponenten der erfindungsgemäßen Empfangsschicht darstellen.This example is intended to demonstrate the particular suitability of the above. Represent acrylate copolymers as components of the receiving layer according to the invention.

Beispiel 2Example 2

Ein Schichtträger gemäß Beispiel 1, jedoch mit einer Polyethylenbeschichtung von 7 g/m² auf der Vorderseite versehen, wurde mit wäßriger Dispersion folgender Zusammensetzung beschichtet: Produkt Zusammensetzung, Gew. - % 2A 2B 2C 2D 2E 2F 2G Acrylat-Copolymer I 40 %-ige wäßr. Disp. (wie Beisp. 1) 91,7 61,4 41,4 - 41,4 41,4 - Acrylat-Copolymer III 38 %-ige wäßr. Disp. (wie Beisp. 1) - - - - - - 42,4 oxyd. Polyethylen 30 %-ige wäßr. Disp. (z. B. Südranol 340, Fa. Süddeutsche Emulsions-Chemie GmbH 5,1 35,0 55,2 96,0 55,2 55,2 53,7 Fluortensid, 1 %-ig in Wasser (wie Beisp. 1) 3,2 3,6 3,4 4,0 3,4 3,4 3,9 Auftragsmenge, g/m² 5,0 5,0 5,0 5,0 10,0 0,5 5,0 A support according to Example 1, but provided with a polyethylene coating of 7 g / m² on the front, was coated with an aqueous dispersion of the following composition: product Composition,% by weight 2A 2 B 2C 2D 2E 2F 2G Acrylate copolymer I 40% aq. Disp. (like Ex. 1) 91.7 61.4 41.4 - 41.4 41.4 - Acrylate copolymer III 38% aq. Disp. (like Ex. 1) - - - - - - 42.4 oxide. Polyethylene 30% aq. Disp. (e.g. Südranol 340, Süddeutsche Emulsions-Chemie GmbH 5.1 35.0 55.2 96.0 55.2 55.2 53.7 Fluorosurfactant, 1% in water (like Ex. 1) 3.2 3.6 3.4 4.0 3.4 3.4 3.9 Order quantity, g / m² 5.0 5.0 5.0 5.0 10.0 0.5 5.0

Sonstige Versuchsbedingungen waren wie im Beispiel 1.Other test conditions were as in Example 1.

Die Ergebnisse der Untersuchung der anschließend erhaltenen Druckbilder sind in Tabelle 2 aufgeführt.The results of the examination of the print images subsequently obtained are listed in Table 2.

Beispiel 3Example 3

Ein Schichtträger gemäß Beispiel 1 wurde mit wäßriger Dispersion folgender Zusammensetzung beschichtet: Produkt Zusammensetzung, Gew. -% 3A 3B 3C Acrylat-Copolymer I, 40 %-ige wäßr. Disp. (wie Beisp. 1 ) 53,8 48,4 42,7 oxyd. Polyethylen, 30 %-ige wäßr. Disp. (wie Beisp. 2) 27,6 32,3 28,4 Kieselsäure, 15 %-ig in Wasser (z. B. Syloid ED 50, Fa. Grace GmbH 11,1 - - Al₂O₃, 63 %-ige Slurry, ( z. B. Martifin OL-008 Fa. Martinswerk) - 15,3 13,5 Titandioxid, 40 %-ig in Wasser (z. B. Rutil RN 40, Fa. Kronos Titan) 4,1 - - UV-Absorber, 15 %-ig in Wasser (z. B. Tinuvin 213, Fa. Ciba-Geigy AG) - - 11,8 Fluortensid, 1 %-ig in Wasser (wie Beisp. 1) 3,4 4,0 3,6 Auftragsmenge, g/m² 5,0 5,0 5,0 A layer support according to Example 1 was coated with an aqueous dispersion of the following composition: product Composition,% by weight 3A 3B 3C Acrylate copolymer I, 40% aq. Disp. (like Ex. 1) 53.8 48.4 42.7 oxide. Polyethylene, 30% aq. Disp. (like Ex. 2) 27.6 32.3 28.4 Silica, 15% in water (e.g. Syloid ED 50, Grace GmbH 11.1 - - Al₂O₃, 63% slurry, (e.g. Martifin OL-008 from Martinswerk) - 15.3 13.5 Titanium dioxide, 40% in water (e.g. Rutil RN 40, from Kronos Titan) 4.1 - - UV absorber, 15% in water (e.g. Tinuvin 213, Ciba-Geigy AG) - - 11.8 Fluorosurfactant, 1% in water (like Ex. 1) 3.4 4.0 3.6 Order quantity, g / m² 5.0 5.0 5.0

Sonstige Versuchsbedingungen waren wie im Beispiel 1.Other test conditions were as in Example 1.

Die Untersuchungsergebnisse sind in Tabelle 3 zusammengestellt.The test results are summarized in Table 3.

VergleichsbeispieleComparative examples


V1. Die Durchführung erfolgte wie im Beispiel 1. Die Empfangsschicht wurde aus wäßrigem Milieu in folgender Zusammensetzung aufgetragen: Produkt Zusammensetzung,Gew.-% V1 A V1 B Acrylat-Copolymer IV, 50 % -ige wäßr. Disp. 96,0 - Acrylat-Copolymer V, 40 %-ige wäßr. Disp. - 96,0 Fluortensid, 1 %-ig in Wasser (wie Beisp. 1) 4,0 4,0 Auftragsmenge, g/m² 5,0 5,0
Als Acrylat-Copolymere wurden Copolymere verwendet, an deren Aufbau polare Gruppen tragende Monomere mit folgenden Anteilen beteiligt sind: Acrylat-Copolymer IV (z. B. Primal P 376, Fa. Rohm & Haas Comp.) 9 Mol.-% Acrylat-Copolymer V (z. B. Primal WL 91 k, Fa. Rohm & Haas Comp.) 7 Mol.-%
Das erhaltene Empfangsmaterial wurde mit Hilfe des thermischen Bildübertragungsverfahrens bedruckt und anschließend analysiert. Die Ergebnisse sind in Tabelle 4 zusammengestellt.
V2. Die Durchführung erfolgte wie im Beispiel 1.
Als farbstoffaufnehmendes Harz wurde ein Acrylharz wie Polyethylacrylat (z. B. Plextol B 408, Fa. Röhm GmbH) verwendet.
Die anschließend erhaltenen Druckbilder (Hardcopy) wurden untersucht. Die Ergebnisse sind in Tabelle 4 aufgeführt.
V3. Zum Vergleich wurde ein auf dem Markt verfügbares Bildempfangsblatt der Fa. Hitachi herangezogen.
Die Ergebnisse sind in Tabelle 4 angegeben.

V1. The procedure was as in Example 1. The receiving layer was applied from an aqueous medium in the following composition: product Composition,% by weight V1 A V1 B Acrylate copolymer IV, 50% aq. Disp. 96.0 - Acrylate copolymer V, 40% aq. Disp. - 96.0 Fluorosurfactant, 1% in water (like Ex. 1) 4.0 4.0 Order quantity, g / m² 5.0 5.0
Copolymers were used as acrylate copolymers, in whose construction polar monomers bearing the following proportions are involved: Acrylate copolymer IV (e.g. Primal P 376, Rohm & Haas Comp.) 9 mol% Acrylate copolymer V (e.g. Primal WL 91 k, Rohm & Haas Comp.) 7 mol%
The receiving material obtained was printed using the thermal image transfer method and then analyzed. The results are summarized in Table 4.
V2. The procedure was as in Example 1.
An acrylic resin such as polyethylacrylate (e.g. Plextol B 408, Röhm GmbH) was used as the dye-absorbing resin.
The print images (hard copy) subsequently obtained were examined. The results are shown in Table 4.
V3. A Hitachi image-receiving sheet available on the market was used for comparison.
The results are shown in Table 4.

Prüfung des gemäß Beispiel 1 - 4 erhaltenen BildempfangsmaterialsExamination of the image-receiving material obtained according to Examples 1-4

Das erhaltene Empfangsmaterial wurde einem thermischen Bildübertragungsverfahren unterzogen.
Hierzu wurde ein Colour Video Printer VY - 25 E der Fa. Hitachi eingesetzt unter Anwendung eines Hitachi-Farbbandes. Der Video-Printer hat folgende technische Daten: Bildspeicher PAL 1-Vollbild-Speicher Druckbild 64 Farbton-Bild Bildelemente: 540 : 620 Punkte Druckzeit 2 Minuten/Bild
The receiving material obtained was subjected to a thermal image transfer process.
For this purpose, a Color Video Printer VY - 25 E from Hitachi was used using a Hitachi ribbon. The video printer has the following technical data: Image storage PAL 1 full screen memory Printed image 64 color image Image elements: 540: 620 points Printing time 2 minutes / picture

Bei den erhaltenen Druckbildern (Hardcopy) wurden die Farbdensität und die "anti-blocking"-Eigenschaften untersucht.The color density and the "anti-blocking" properties were investigated in the print images obtained (hard copy).

Die Densitätsmessungen erfolgten vor und nach einer 24 h-Belichtung der Bilder mittels Xenon-Lampe. Der durch die Belichtung verursachte Densitätsverlust wurde mit Δ d (%) bezeichnet und zur Beurteilung der Lichtstabilität herangezogen.The density measurements were carried out before and after a 24-hour exposure of the images using a xenon lamp. The loss in density caused by the exposure was designated Δ d (%) and used to assess the light stability.

Das hierzu verwendete Gerät war ein Original Reflecion Densitometer SOS-45. Die Messungen erfolgten in fünf Farbabstufungen F1 - F5 für die Grundfarben Cyan, Magenta, Gelb, und Schwarz, wobei in den Tabellen die Werte für F1, F3 und F5 angegeben sind. Die Anzahl möglicher Farbabstufungen (Gradation) von 0 - 7 ist ebenfalls in den Tabellen enthalten.The device used for this was an original reflection densitometer SOS-45. The measurements were carried out in five color gradations F1 - F5 for the primary colors cyan, magenta, yellow and black, the values for F1, F3 and F5 being given in the tables. The number of possible color gradations from 0 to 7 is also included in the tables.

Gleichzeitig wurden Vergleichsmessungen mit den auf dem Markt verfügbaren Empfangsmaterialien angestellt.At the same time, comparative measurements were made with the receiving materials available on the market.

Die in den Tabellen 1 - 4 aufgeführten Ergebnisse zeigen, daß mit dem erfindungsgemäß hergestellten Bildempfangsmaterial Druckbilder mit in jedem Farbbereich höheren Werten der Farbdensität und der Gradation erzielt werden.
Auch hinsichtlich der Lichtstabilität (Δ d-Werte) weisen die auf erfindungsgemäß hergestelltem Bildempfangsmaterial gedruckten Bilder bessere Werte als das Vergleichsmaterial auf.

Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
The results listed in Tables 1-4 show that with the image-receiving material produced according to the invention Print images can be achieved with higher values of color density and gradation in each color range.
Also with regard to light stability (Δ d values), the images printed on the image-receiving material produced according to the invention have better values than the comparison material.
Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005

Claims (13)

  1. Image receiving material for dye diffusion thermal transfer, consisting of a resin-coated base paper and a receiving coating containing dye-receiving resin applied onto its front face, characterized in that the dye-receiving resin is a combination of at least one acrylate copolymer containing polar groups and oxidized polyethylene.
  2. Image receiving material according to Claim 1, characterized in that the polar groups contained in the acrylate copolymer are carboxyl groups, metal-bound carboxyl groups and/or nitrile groups.
  3. Image receiving material according to Claim 2, characterized in that the metal-bound carboxyl groups are zinc-bound carboxyl groups.
  4. Image receiving material according to Claims 1 to 3, characterized in that the monomers participating in the forming of the acrylate copolymer and carrying polar groups include acrylonitrile and/or methacrylic acid and that the proportion of these monomers in the copolymer in total amounts to 10-40 mol %.
  5. Image receiving material according to Claim 4, characterized in that the proportion of the monomers is 25-35 mol %.
  6. Image receiving material according to Claims 1 to 5, characterized in that the acrylate copolymer additionally contains styrene as monomer and the content of this amounts to 0-40 mol %.
  7. Image receiving material according to Claim 1, characterized in that the ratio by weight of acrylate copolymer/oxidized polyethylene is 99:1 to 30:70.
  8. Image receiving material according to Claim 7, characterized in that the ratio by weight of acrylate copolymer/oxidized polyethylene is 70:30 to 40:60.
  9. Image receiving material according to Claims 1 to 8, characterized in that the receiving coating additionally contains pigments, matting agents, wetting agents and other auxiliary substances.
  10. Image receiving material according to Claims 1 to 9, characterized in that the application rate of the receiving coating is 0.3 to 15 g/m².
  11. Image receiving material according to Claim 10, characterized in that the application rate of the receiving coating is 1 to 10 g/m².
  12. Image receiving material according to Claims 1 to 11, characterized in that the resin coating is a polyolefin coating in a quantity of at least 5 g/m².
  13. Method of making an image receiving material for dye diffusion thermal transfer having a receiving coating containing a dye-receiving resin applied onto the front side of a resin-coated base paper, characterized in that the receiving coating containing, as dye-receiving resin, a combination of at least one acrylate copolymer containing polar groups and oxidized polyethylene, is applied from an aqueous medium in a single operation onto the front face of a polyethylene-coated base paper.
EP19900111315 1989-09-28 1990-06-15 Image-receiving material for thermal dye-transfer Expired - Lifetime EP0405248B1 (en)

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EP0543441B1 (en) * 1991-11-19 1995-09-20 Agfa-Gevaert N.V. Thermal dye transfer printing method for obtaining a hard copy of a medical diagnostic image
JP3177294B2 (en) * 1992-04-30 2001-06-18 フジコピアン株式会社 Thermal transfer ink ribbon and image forming method using the same
US5457081A (en) * 1992-05-15 1995-10-10 Dai Nippon Printing Co., Ltd. Thermal transfer image receiving sheet
US5776604A (en) * 1995-02-03 1998-07-07 Mobil Oil Corporation Coating for printable plastic films
US5716900A (en) * 1995-05-01 1998-02-10 Kimberly-Clark Worldwide, Inc. Heat transfer material for dye diffusion thermal transfer printing
JP3605453B2 (en) * 1995-09-19 2004-12-22 大日本印刷株式会社 Thermal transfer image receiving sheet
US5891552A (en) * 1996-01-04 1999-04-06 Mobil Oil Corporation Printed plastic films and method of thermal transfer printing
JPH11334202A (en) * 1998-05-22 1999-12-07 Sony Corp Transfer type laminate film for protecting image and thermal transfer ink sheet
WO2001025856A1 (en) * 1999-10-01 2001-04-12 Foto-Wear, Inc. Image transfer material with image receiving layer and heat transfer process using the same
US6964722B2 (en) * 2002-08-07 2005-11-15 Trio Industries Holdings, L.L.C. Method for producing a wood substrate having an image on at least one surface
US6939602B2 (en) 2002-12-31 2005-09-06 Exxonmobil Oil Corporation Coating for the adhesive-receiving surface of polymeric labels
CN103174060B (en) * 2013-03-18 2015-10-21 浙江佳维康特种纸有限公司 A kind of preparation method of Anti-counterfeiting transfer paper

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JP2732831B2 (en) * 1986-05-30 1998-03-30 大日本印刷株式会社 Heat transfer sheet
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EP0405248A3 (en) 1991-12-18
HUT59975A (en) 1992-07-28
EP0405248A2 (en) 1991-01-02
ATE111033T1 (en) 1994-09-15
US5096876A (en) 1992-03-17
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JPH03132393A (en) 1991-06-05
AU5994290A (en) 1991-04-11

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