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EP0514631B1 - Thermal transfer multilayered image receiving sheet and production process therefor - Google Patents

Thermal transfer multilayered image receiving sheet and production process therefor Download PDF

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Publication number
EP0514631B1
EP0514631B1 EP19920103825 EP92103825A EP0514631B1 EP 0514631 B1 EP0514631 B1 EP 0514631B1 EP 19920103825 EP19920103825 EP 19920103825 EP 92103825 A EP92103825 A EP 92103825A EP 0514631 B1 EP0514631 B1 EP 0514631B1
Authority
EP
European Patent Office
Prior art keywords
image receiving
intermediate layer
receiving material
material according
radiation
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
EP19920103825
Other languages
German (de)
French (fr)
Other versions
EP0514631A1 (en
Inventor
Reiner Dipl.-Ing. Anthonsen (Fh)
Wieland Dr. Dipl.-Phys. Sack
Dieter Dr. Dipl.-Chem. Becker
Jürgen Dipl.-Ing. Graumann (FH)
Manuela Hesse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Felex Schoeller Jr and GmbH and Co KG
Original Assignee
Felex Schoeller Jr and GmbH and Co KG
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Publication of EP0514631A1 publication Critical patent/EP0514631A1/en
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Publication of EP0514631B1 publication Critical patent/EP0514631B1/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/02—Dye diffusion thermal transfer printing (D2T2)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/405—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by layers cured by radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • the invention relates to an image receiving material for thermal dye transfer processes with an intermediate layer and a color receiving layer and a process for its production.
  • Thermal dye transfer systems (Dye Diffusion Thermal Transfer - D2T2) generate images of originals electronically.
  • the templates are broken down into the basic colors cyan, magenta and yellow and, if necessary, black, and these are converted into electrical impulses. These impulses are forwarded to a thermal printer, where they are converted into heat in the print head.
  • the image-receiving material passes through the thermal printer in contact with a color donor element.
  • a color donor element In the printhead, the back of a color donor element is heated up in accordance with the pulse specifications and a dye is released which diffuses or sublimes into the receiving layer of the image-receiving material. This process is carried out one after the other for all colors and then results in the finished image.
  • thermoplastic high molecular weight materials before the image-receiving layer is applied.
  • These high molecular weight thermoplastics can be polyolefins, polystyrene, polyvinylidene chloride, polyethylene terephthalate, polymethyl methacrylate or ionomer resin. The unevenness of the paper surface is to be leveled out by this intermediate layer of thermoplastics.
  • No. 4,774,224 also describes an image-receiving material for thermal dye transfer with a paper support which is provided with a thermoplastic intermediate layer, which preferably consists of polyolefin.
  • a thermoplastic intermediate layer which preferably consists of polyolefin.
  • the surface roughness of the intermediate layer should be limited to ⁇ 0.2 »m (7.5 Ra» inches).
  • EP 407 613 describes an image receiving material with likewise thermoplastic intermediate layers.
  • the thermoplastics are preferably polyolefins, polyvinyl chloride, polystyrene, polyethylene terephthalate, polymethacrylate or polycarbonate.
  • the surface roughness of the intermediate layer in this patent is between 0.2 and 4.0 »m.
  • thermoplastic intermediate layer between the paper base material and the image-receiving layer.
  • the quality of the transferred image is to be improved by the thermoplastic intermediate layer.
  • the materials used for the intermediate layer are lacquers made from monomers, oligomers or prepolymers, but mostly from mixtures of these groups.
  • the monomers in particular serve as diluents in the paint.
  • Monomers can advantageously be dispensed with if the coating compositions are processed at elevated temperature, preferably 30 ° C. to 60 ° C.
  • the crosslinkable compounds should preferably consist of more than 50% by weight of acrylic acid and / or methacrylic acid esters.
  • the lacquers can advantageously be filled (before crosslinking) with white pigments, such as carbonates, oxides, sulfates or sulfites of the elements calcium, magnesium, barium, strontium, zinc or titanium. Because of its high refractive index, titanium dioxide has proven particularly useful. Varnishes containing up to 70% by weight of titanium dioxide were successfully processed. This gives the background a high level of light reflection and makes the images appear more brilliant.
  • white pigments such as carbonates, oxides, sulfates or sulfites of the elements calcium, magnesium, barium, strontium, zinc or titanium. Because of its high refractive index, titanium dioxide has proven particularly useful. Varnishes containing up to 70% by weight of titanium dioxide were successfully processed. This gives the background a high level of light reflection and makes the images appear more brilliant.
  • the paints can contain up to 20% by weight of auxiliaries, such as non-crosslinkable resins, optical brighteners, matting agents, dyes and photoinitiators.
  • auxiliaries such as non-crosslinkable resins, optical brighteners, matting agents, dyes and photoinitiators.
  • the varnish After the varnish has been applied to the substrate, it is cross-linked by high-energy radiation.
  • This radiation can be electron radiation or UV radiation.
  • UV lamps When UV lamps are used, photoinitiators must be added to the paint to form radicals that trigger the crosslinking reaction.
  • the varnish can be spread onto the carrier material using conventional application units such as doctor or gap metering systems, anilox rollers or multi-roller systems.
  • the paint is cross-linked in contact with high-gloss metal surfaces or high-gloss cylinders by irradiation with high-energy electrons.
  • the irradiation with the accelerated electrons takes place from the rear, i.e. from the uncoated side of the carrier material.
  • the electrons must be accelerated in such a way that their penetration depth exceeds the thickness of the substrate plus the lacquer layer. This technique is described in DE 30 22 709.
  • the carrier material can also be coated on both sides or pre-coated on one or both sides with thermoplastics such as polyolefins.
  • thermoplastic layer which acts as a barrier layer under the interlayer of cross-linked lacquer, prevents the lacquer applied from penetrating (knocking away) into the paper and saves lacquer material.
  • the finished image is resistant to aging and heat thanks to the intermediate layer.
  • the coating composition should be free from organic solvents.
  • pretreatments such as a corona discharge have proven effective.
  • a neutral gummed paper with 175 g / m2 basis weight with alkyl ketene dimer was coated on one side with 25 ⁇ 2 g / m2 according to the following coating formulations (coating material) with a multi-roller application system at a machine speed of 60 m / min. Corona pretreatment of the paper surface was carried out before coating.
  • the coated paper was irradiated by means of accelerated electrons at an energy dose of 40 kJ / kg coating mass. Curing took place in a scanner system with a maximum of 180 kV and 100 mA electron current under nitrogen as the inert gas. The subsequent application of the image receiving layer will be described later.
  • a 135 g / m2 basis weight paper sized with stearic acid, alkyl ketene dimer and epoxidized fatty acid amide was coated on both sides with polyethylene (front 20 g / m2, back 25 g / m2) using the melt extrusion process and after a corona pretreatment on the front with 20 ⁇ 2 g / m2 coated according to the following paint formulations under the conditions as in Example 1.
  • the coated paper was pressed with the layer side against a water-cooled high-gloss cylinder and irradiated from the back of the paper by means of accelerated electrons at an energy dose of 35 kJ / kg of coating material in the system and under the inert gas, as in Example 1.
  • the base paper from Example 2 was extrusion coated on both sides with polyethylene.
  • the machine conditions corresponded to those from example 1.
  • the application weights per shift were 18-20 g / m2. Corona pretreatment was carried out before each coating.
  • the carrier materials from Example 1, Example 2 and Comparative Example V1 provided with an intermediate layer were coated with the following coating composition from aqueous solution using a roller application unit:
  • the machine speed was 130 m / min., The drying temperature was 110 ° C.
  • the application weight after drying was 5 - 7 g / m2.
  • the color density of the individual colors of the images obtained was measured using the original reflection densitometer SOS-45.
  • a line grid was selected for the individual primary colors and the line widths were measured for testing the aging and heat resistance . Since the measurement results of the individual primary colors (cyan, magenta, yellow) were only slightly differentiated, but mostly identical, the following table shows the averaged value of the three primary colors.
  • the imaged image-receiving materials without a cross-linked intermediate layer show significantly lower heat and aging resistance than those according to the invention, which is reflected in an increase in the line width.
  • Cross-linked intermediate layers combined with cross-linked image-receiving layers, result in images with a greatly reduced color density; the lower values of color density mean paler colors.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Description

Die Erfindung betrifft ein Bildempfangsmaterial für thermische Farbstoffübertragungsverfahren mit einer Zwischenschicht und einer Farbempfangsschicht und ein Verfahren zu seiner Herstellung.The invention relates to an image receiving material for thermal dye transfer processes with an intermediate layer and a color receiving layer and a process for its production.

Thermische Farbstoffübertragungssysteme (Dye Diffusion Thermal Transfer - D2T2) erzeugen auf elektronischem Weg Bilder von Vorlagen. Dabei werden die Vorlagen in die Grundfarben Cyan, Magenta und Gelb und gegebenenfalls in Schwarz zerlegt und diese in elektrische Impulse umgewandelt. Diese Impulse werden zu einem Thermodrucker weitergeleitet und dort im Druckkopf in Wärme umgesetzt.Thermal dye transfer systems (Dye Diffusion Thermal Transfer - D2T2) generate images of originals electronically. The templates are broken down into the basic colors cyan, magenta and yellow and, if necessary, black, and these are converted into electrical impulses. These impulses are forwarded to a thermal printer, where they are converted into heat in the print head.

Das Bildempfangsmaterial durchläuft im Kontakt mit einem Farb-Donorelement den Thermodrucker. Im Druckkopf wird entsprechend den Impulsvorgaben die Rückseite eines Farb-Donorelements aufgeheizt und ein Farbstoff freigesetzt, der in die Empfangsschicht des Bildempfangsmaterials diffundiert bzw. sublimiert. Dieser Prozeß wird nacheinander für alle Farben durchlaufen und ergibt dann das fertige Bild.The image-receiving material passes through the thermal printer in contact with a color donor element. In the printhead, the back of a color donor element is heated up in accordance with the pulse specifications and a dye is released which diffuses or sublimes into the receiving layer of the image-receiving material. This process is carried out one after the other for all colors and then results in the finished image.

Es ist aus der JP-OS 60-236794 bekannt, Trägermaterialien aus Papier mit thermoplastischen, hochmolekularen Materialien zu beschichten, bevor die Bildempfangsschicht aufgetragen wird. Diese hochmolekularen Thermoplaste können Polyolefine, Polystyrol, Polyvinylidenchlorid, Polyethylen-terephthalat, Polymethylmethacrylat oder Ionomerharz sein. Durch diese Zwischenschicht aus Thermoplasten soll die Unebenheit der Papieroberfläche egalisiert werden.It is known from JP-OS 60-236794 to coat paper substrates with thermoplastic, high molecular weight materials before the image-receiving layer is applied. These high molecular weight thermoplastics can be polyolefins, polystyrene, polyvinylidene chloride, polyethylene terephthalate, polymethyl methacrylate or ionomer resin. The unevenness of the paper surface is to be leveled out by this intermediate layer of thermoplastics.

Auch die US 4,774,224 beschreibt ein Bildempfangsmaterial für thermische Farbstoffübertragung mit einem Papierträger, der mit einer thermoplastischen Zwischenschicht versehen ist, die vorzugsweise aus Polyolefin besteht. Gemäß dieser Patentschrift soll die Oberflächenrauhigkeit der Zwischenschicht auf <0,2 »m (7,5 Ra »inch) begrenzt werden.No. 4,774,224 also describes an image-receiving material for thermal dye transfer with a paper support which is provided with a thermoplastic intermediate layer, which preferably consists of polyolefin. According to this patent, the surface roughness of the intermediate layer should be limited to <0.2 »m (7.5 Ra» inches).

Die EP 407 613 beschreibt ein Bildempfangsmaterial mit ebenfalls thermoplastischen Zwischenschichten. Die Thermoplaste sind vorzugsweise Polyolefine, Polyvinylchlorid, Polystyrol, Polyethylenterephthalat, Polymethacrylat oder Polycarbonat. Die Oberflächenrauhigkeit der Zwischenschicht liegt in dieser Patentschrift zwischen 0,2 und 4,0 »m.EP 407 613 describes an image receiving material with likewise thermoplastic intermediate layers. The thermoplastics are preferably polyolefins, polyvinyl chloride, polystyrene, polyethylene terephthalate, polymethacrylate or polycarbonate. The surface roughness of the intermediate layer in this patent is between 0.2 and 4.0 »m.

Alle drei Patentanmeldungen beschreiben Bildempfangsmaterialien für die thermische Farbstoffübertragung, die zwischen dem Papierträgermaterial und der Bildempfangsschicht eine thermoplastische Zwischenschicht aufweisen. Durch die thermoplastische Zwischenschicht soll die Qualität des übertragenen Bildes verbessert werden.All three patent applications describe image-receiving materials for thermal dye transfer which have a thermoplastic intermediate layer between the paper base material and the image-receiving layer. The quality of the transferred image is to be improved by the thermoplastic intermediate layer.

Die Bildempfangsmaterialien dieser drei oben genannten Veröffentlichungen weisen jedoch einen deutlichen Mangel des fertigen Bildes hinsichtlich seiner Wärme- und Alterungsbeständigkeit auf. Die Bildschärfe verringert sich mehr und mehr, Linien verbreitern sich und fransen aus. Texte können bis zur Unleserlichkeit verlaufen.However, the image-receiving materials of these three publications mentioned above have a marked deficiency in the finished image in terms of its heat and aging resistance. The image sharpness decreases more and more, lines widen and fray. Texts can be illegible.

Die Alterungs- und auch die Wärmebeständigkeit von Bildmaterialien sind jedoch wichtige Kriterien für ihren Einsatz bzw. für ihre Verwendungsfähigkeit.However, the aging and heat resistance of image materials are important criteria for their use or their usability.

Es ist deshalb Aufgabe dieser Erfindung, ein Bildempfangsmaterial für thermische Farbstoffübertragungsverfahren zur Verfügung zu stellen, das Bilder hoher Farbdichte ermöglicht, die altungs- und wärmebeständig sind, ihre gute Bildqualität also weitestgehend beibehalten.It is therefore an object of this invention to provide an image-receiving material for thermal dye transfer processes which enables high-color density images which are resistant to aging and heat and therefore largely retain their good image quality.

Gelöst wird diese Aufgabe durch ein Bildempfangsmaterial mit einer Zwischenschicht aus vernetztem Material und einer darauf befindlichen Bildempfangsschicht aus unvernetztem Material, wobei beide Schichten aus Beschichtungsmassen erzeugt werden, die frei von organischen Lösungsmitteln sind.This object is achieved by an image-receiving material with an intermediate layer made of cross-linked material and an image-receiving layer thereon made of uncross-linked material, both layers being produced from coating compositions which are free from organic solvents.

Es war überraschend, daß durch die Kombination dieser beiden Schichten eine hohe Farbdichte und eine ausgezeichnete Wärme- und Alterungsbeständigkeit des Bildes erzielt werden konnte, denn die guten Ergebnisse ließen sich weder durch zwei nicht vernetzte Schichten, noch durch zwei vernetzte Schichten erreichen.It was surprising that the combination of these two layers made it possible to achieve a high color density and excellent heat and aging resistance of the image, since the good results could not be achieved by two non-crosslinked layers, nor by two crosslinked layers.

Die für die Zwischenschicht verwendeten Materialien sind Lacke aus Monomeren, Oligomeren oder Prepolymeren, meist jedoch aus Gemischen dieser Gruppen. Dabei dienen vor allem die Monomere als Verdünnungsmittel im Lack. Auf Monomere kann vorteilhaft verzichtet werden, wenn die Beschichtungsmassen bei erhöhter Temperatur, vorzugsweise 30°C bis 60°C, verarbeitet werden.The materials used for the intermediate layer are lacquers made from monomers, oligomers or prepolymers, but mostly from mixtures of these groups. The monomers in particular serve as diluents in the paint. Monomers can advantageously be dispensed with if the coating compositions are processed at elevated temperature, preferably 30 ° C. to 60 ° C.

Die Monomere, Oligomere und Prepolymere enthalten als Acryl, Methacryl-, Allyl- oder Vinylverbindungen Kohlenstoff-Doppelbindungen (>c=c<). Sie können zusätzlich Hydroxyl-, Carboxyl- und andere polare Gruppen enthalten, z. B. zur Verbesserung der Haftung der Bildempfangsschicht.The monomers, oligomers and prepolymers contain carbon double bonds (> c = c <) as acrylic, methacrylic, allyl or vinyl compounds. They can additionally contain hydroxyl, carboxyl and other polar groups, e.g. B. to improve the adhesion of the image receiving layer.

Vorzugsweise sollen die vernetzbaren Verbindungen zu mehr als 50 Gew.-% aus Acrylsäure- und/oder Methacrylsäureestern bestehen.The crosslinkable compounds should preferably consist of more than 50% by weight of acrylic acid and / or methacrylic acid esters.

Vorteilhaft lassen sich die Lacke (vor der Vernetzung) mit Weißpigmenten, wie Carbonate, Oxide, Sulfate oder Sulfite der Elemente Calcium, Magnesium, Barium, Strontium, Zink oder Titan füllen. Wegen seines hohen Brechnungsindex hat sich Titandioxid besonders bewährt. Es wurden Lacke erfolgreich verarbeitet, die bis zu 70 Gew.-% Titandioxid enthielten. Dadurch ergibt der Bilduntergrund eine hohe Lichtreflexion und läßt die Bilder brillanter erscheinen.The lacquers can advantageously be filled (before crosslinking) with white pigments, such as carbonates, oxides, sulfates or sulfites of the elements calcium, magnesium, barium, strontium, zinc or titanium. Because of its high refractive index, titanium dioxide has proven particularly useful. Varnishes containing up to 70% by weight of titanium dioxide were successfully processed. This gives the background a high level of light reflection and makes the images appear more brilliant.

Zusätzlich können die Lacke noch bis zu 20 Gew.-% an Hilfsmitteln, wie nichtvernetzbare Harze, optische Aufheller, Mattierungsmittel, Farbstoffe und Photoinitiatoren enthalten.In addition, the paints can contain up to 20% by weight of auxiliaries, such as non-crosslinkable resins, optical brighteners, matting agents, dyes and photoinitiators.

Nach dem Auftragen des Lackes auf das Trägermaterial wird er durch energiereiche Strahlung vernetzt. Diese Strahlung kann eine Elektronenbestrahlung sein oder eine UV-Strahlung. Beim Einsatz von UV-Lampen müssen dem Lack Photoinitiatoren zugesetzt werden zur Bildung von Radikalen, die die Vernetzungsreaktion in Gang setzen.After the varnish has been applied to the substrate, it is cross-linked by high-energy radiation. This radiation can be electron radiation or UV radiation. When UV lamps are used, photoinitiators must be added to the paint to form radicals that trigger the crosslinking reaction.

Der Lack kann mit üblichen Auftragsaggregaten wie Schaber- oder Spaltdosiersysteme, Rasterwalzen oder Mehrwalzen-Systeme auf das Trägermaterial aufgestrichen werden.The varnish can be spread onto the carrier material using conventional application units such as doctor or gap metering systems, anilox rollers or multi-roller systems.

Zur Erzeugung besonders brillanter Bilder wird der Lack in Kontakt mit hochglänzenden Metalloberflächen, bzw. Hochglanzzylindern, durch Bestrahlung mit energiereichen Elektronen vernetzt. Dabei erfolgt die Bestrahlung mit den beschleunigten Elektronen von der Rückseite, d.h. von der nicht beschichteten Seite des Trägermaterials her. Die Elektronen müssen derart beschleunigt werden, daß ihre Eindringtiefe die Dicke des Trägermaterials plus Lackschicht übertrifft. Beschrieben ist diese Technik in der DE 30 22 709.To produce particularly brilliant images, the paint is cross-linked in contact with high-gloss metal surfaces or high-gloss cylinders by irradiation with high-energy electrons. The irradiation with the accelerated electrons takes place from the rear, i.e. from the uncoated side of the carrier material. The electrons must be accelerated in such a way that their penetration depth exceeds the thickness of the substrate plus the lacquer layer. This technique is described in DE 30 22 709.

Zur besseren Planlage oder Dimensionsstabilität kann das Trägermaterial auch beidseitig lackiert oder mit Thermoplasten wie Polyolefinen ein- oder beidseitig vorbeschichtet werden.For better flatness or dimensional stability, the carrier material can also be coated on both sides or pre-coated on one or both sides with thermoplastics such as polyolefins.

Eine thermoplastische Schicht, die die Funktion einer Sperrschicht unter der Zwischenschicht aus vernetztem Lack hat, verhindert das Eindringen (Wegschlagen) des aufgetragenen Lackes in das Papierinnere und erspart Lackmaterial.A thermoplastic layer, which acts as a barrier layer under the interlayer of cross-linked lacquer, prevents the lacquer applied from penetrating (knocking away) into the paper and saves lacquer material.

Für die Bildempfangsschicht können alle geeigneten Materialien eingesetzt werden, wie sie aus der Literatur bekannt sind. Das fertige Bild wird durch die Zwischenschicht alterungs- und wärmebeständig. Die Beschichtungsmasse soll jedoch frei von organischen Lösungsmitteln sein.All suitable materials known from the literature can be used for the image receiving layer. The finished image is resistant to aging and heat thanks to the intermediate layer. However, the coating composition should be free from organic solvents.

Um eine gute Haftung der Bildempfangsschicht auf der vernetzten Zwischenschicht zu gewährleisten, haben sich Vorbehandlungen wie beispielsweise eine Corona-Entladung bewährt.In order to ensure good adhesion of the image-receiving layer to the cross-linked intermediate layer, pretreatments such as a corona discharge have proven effective.

Die folgenden Beispiele sollen die Erfindung verdeutlichen, aber nicht eingrenzen:The following examples are intended to illustrate but not limit the invention:

Beispiel 1:Example 1:

Ein mit Alkylketendimer neutral geleimtes Papier von 175 g/m² Flächengewicht wurde einseitig mit 25 ± 2 g/m² nach folgenden Lackrezepturen (Beschichtungsmasse) mit einem Mehrwalzenauftragssystem beschichtet bei einer Maschinengeschwindigkeit von 60 m/min. Vor der Beschichtung erfolgte eine Corona-Vorbehandlung der Papieroberfläche.A neutral gummed paper with 175 g / m² basis weight with alkyl ketene dimer was coated on one side with 25 ± 2 g / m² according to the following coating formulations (coating material) with a multi-roller application system at a machine speed of 60 m / min. Corona pretreatment of the paper surface was carried out before coating.

Das beschichtete Papier wurde mittels beschleunigter Elektronen bei einer Energiedosis von 40 kJ/kg Beschichtungsmasse bestrahlt. Die Aushärtung erfolgte in einer Scanner-Anlage von maximal 180 kV und 100 mA Elektronenstrom unter Stickstoff als Inertgas. Der sich anschließende Auftrag der Bildempfangsschicht wird später beschrieben.The coated paper was irradiated by means of accelerated electrons at an energy dose of 40 kJ / kg coating mass. Curing took place in a scanner system with a maximum of 180 kV and 100 mA electron current under nitrogen as the inert gas. The subsequent application of the image receiving layer will be described later.

Die ausgehärteten Zwischenschichten haben die folgende Zusammensetzung: (alle Angaben in Gew.-%). 1a 1b 1c Epoxyacrylat 1 20 fettsäuremodifiziertes Epoxyacrylat 2 10 Polyesteracrylat 3 60 Oligotriacrylat 4 20 Pentaerythritoltriacrylat 10 Trimethylolpropantriethoxytriacrylat 25 25 Tetraethylenglykoldiacrylat 10 Hexandioldiacrylat 20 10 Hydroxyethylacrylat 15 Titandioxid (Rutil) 40 Titandioxid (Anatas) 35

Epoxyacrylat 1 =
Derakane XD 8008.04 von Dow Chemical
2 Doppelbindungen im Molekül 6000 Pas Viskosität bei 25° C
fettsäuremodifiziertes Epoxyacrylat 2 =
Derakane XD 9127 von Dow Chemical
2 Doppelbindungen im Molekül 1900 Pas Viskosität bei 25° C
Polyesteracrylat 3 =
Ebecryl 810 von UCB-Chemie
4 Doppelbindungen im Molekül MG ≈ 1000
Oligotriacrylat 4 =
OTA 480 von UCB-Chemie
3 Doppelbindungen im Molekül MG ≈ 480
The cured intermediate layers have the following composition: (all figures in% by weight). 1a 1b 1c Epoxy acrylate 1 20th fatty acid modified epoxy acrylate 2 10th Polyester acrylate 3 60 Oligotria acrylate 4 20th Pentaerythritol triacrylate 10th Trimethylolpropane triethoxytriacrylate 25th 25th Tetraethylene glycol diacrylate 10th Hexanediol diacrylate 20th 10th Hydroxyethyl acrylate 15 Titanium dioxide (rutile) 40 Titanium dioxide (anatase) 35
Epoxy acrylate 1 =
Derakane XD 8008.04 from Dow Chemical
2 double bonds in the molecule 6000 Pas viscosity at 25 ° C
fatty acid modified epoxy acrylate 2
Derakane XD 9127 from Dow Chemical
2 double bonds in the molecule 1900 Pas viscosity at 25 ° C
Polyester acrylate 3 =
Ebecryl 810 from UCB-Chemie
4 double bonds in the molecule MG ≈ 1000
Oligotria acrylate 4 =
OTA 480 from UCB-Chemie
3 double bonds in the molecule MG ≈ 480

Beispiel 2:Example 2:

Ein mit Stearinsäure, Alkylketendimer und epoxidiertem Fettsäureamid geleimtes Papier von 135 g/m² Flächengewicht wurde beidseitig mit Polyethylen (Vorderseite 20 g/m², Rückseite 25 g/m²) im Schmelzextrusionsverfahren beschichtet und nach einer Corona-Vorbehandlung auf der Vorderseite mit 20 ± 2 g/m² nach folgenden Lackrezepturen unter den Bedingungen wie in Beispiel 1 beschichtet.A 135 g / m² basis weight paper sized with stearic acid, alkyl ketene dimer and epoxidized fatty acid amide was coated on both sides with polyethylene (front 20 g / m², back 25 g / m²) using the melt extrusion process and after a corona pretreatment on the front with 20 ± 2 g / m² coated according to the following paint formulations under the conditions as in Example 1.

Das beschichtete Papier wurde mit der Schichtseite gegen einen mit Wasser gekühlten Hochglanzzylinder gedrückt und von der Papierrückseite her mittels beschleunigter Elektronen bei einer Energiedosis von 35 kJ/kg Beschichtungsmasse in der Anlage und unter dem Inertgas, wie in Beispiel 1, bestrahlt.The coated paper was pressed with the layer side against a water-cooled high-gloss cylinder and irradiated from the back of the paper by means of accelerated electrons at an energy dose of 35 kJ / kg of coating material in the system and under the inert gas, as in Example 1.

Der sich anschließende Auftrag der Bildempfangsschicht wird später beschrieben.The subsequent application of the image receiving layer will be described later.

Die ausgehärteten Zwischenschichten haben die folgende Zusammensetzung: (alle Angaben in Gew.-%). 2a 2b 2c Bisphenol-A-Derivat-Acrylat 5 15 alifatisches Urethanacrylat 6 50 Polyesteracrylat 3 30 Pentaerythritoltriacrylat 15 10 Trimethylolpropantetraethylenoxidtriacrylat 25 25 N-Vinylpyrrolidon 10 10 acryliertes Sojabohnenöl 7 10 Allylglycidyläther 5 Glycerylpropoxytriacrylat 15 15 Titandioxid Rutil 25 40

Bisphenol-A-Derivat-Acrylat 5 =
Ebecryl 150 von UCB-Chemie
2 Doppelbindungen im Molekül 1000 Pas Viskosität bei 25° C
alifatisches Urethanacrylat 6 =
Ebecryl 230 von UCB-Chemie
2 Doppelbindungen im Molekül MG ≈ 5000
acryliertes Sojabohnenöl 7 =
Synocure 3110 von Cray Valley
1 Doppelbindung/500 Äquivalentgewicht
The cured intermediate layers have the following composition: (all figures in% by weight). 2a 2 B 2c Bisphenol A derivative acrylate 5 15 aliphatic urethane acrylate 6 50 Polyester acrylate 3 30th Pentaerythritol triacrylate 15 10th Trimethylolpropane tetraethylene oxide triacrylate 25th 25th N-vinyl pyrrolidone 10th 10th acrylated soybean oil 7 10th Allyl glycidyl ether 5 Glyceryl propoxy triacrylate 15 15 Titanium dioxide rutile 25th 40
Bisphenol A derivative acrylate 5 =
Ebecryl 150 from UCB-Chemie
2 double bonds in the molecule 1000 Pas viscosity at 25 ° C
aliphatic urethane acrylate 6
Ebecryl 230 from UCB-Chemie
2 double bonds in the molecule MG ≈ 5000
acrylated soybean oil 7 =
Synocure 3110 from Cray Valley
1 double bond / 500 equivalent weight

Vergleichsbeispiel V1Comparative Example V1

Das Rohpapier aus Beispiel 2 wurde beidseitig mit Polyethylen extrusionsbeschichtet.
Die Rückseite wurde mit 28 g/m² einer Mischung aus 35 Gew.-% HDPE, g = 0,959 g/cm³, MFI = 8 28 Gew.-% HDPE, g = 0,950 g/cm³, MFI = 7 20 Gew.-% LDPE, g = 0,934 g/cm³, MFI = 3 17 Gew.-% LDPE, g = 0,915 g/cm³, MFI = 8
beschichtet.The base paper from Example 2 was extrusion coated on both sides with polyethylene.
The back became one with 28 g / m² Mixture of 35% by weight HDPE, g = 0.959 g / cm³, MFI = 8 28% by weight HDPE, g = 0.950 g / cm³, MFI = 7 20% by weight LDPE, g = 0.934 g / cm³, MFI = 3 17% by weight LDPE, g = 0.915 g / cm³, MFI = 8
coated.

Die Vorderseite wurde mit 22 g/m² einer Mischung aus 42 Gew.-% HDPE, g = 0,959 g/cm³, MFI = 8 10 Gew.-% LDPE, g = 0,934 g/cm³, MFI = 3 10,3 Gew.-% DPE, g = 0,915 g/cm³, MFI = 8 16,7 Gew.-% LDPE, g = 0,924 g/cm³, MFI = 4,5 21 Gew.-% Titandioxid-Masterbatch mit 50 Gew.-% TiO₂
beschichtet.The front was made with a 22 g / m² mixture out 42% by weight of HDPE, g = 0.959 g / cm³, MFI = 8 10% by weight LDPE, g = 0.934 g / cm³, MFI = 3 10.3% by weight DPE, g = 0.915 g / cm³, MFI = 8 16.7% by weight LDPE, g = 0.924 g / cm³, MFI = 4.5 21 wt .-% titanium dioxide masterbatch with 50 wt .-% TiO₂
coated.

Der sich anschließende Auftrag der Bildempfangsschicht wird später beschrieben.The subsequent application of the image receiving layer will be described later.

Vergleichsbeispiel V2:Comparative example V2:

Das Rohpapier aus Beispiel 1 wurde mit den Rezepturen der Beispiele 1c (= V2a) und 2b (= V2b) jeweils zweifach beschichtet, wobei die erste Schicht als Zwischenschicht und die zweite Schicht als Bildempfangsschicht diente.The base paper from Example 1 was coated twice with the formulations of Examples 1c (= V2a) and 2b (= V2b), the first layer serving as an intermediate layer and the second layer as the image-receiving layer.

Die Maschinenbedingungen entsprachen denen aus Beispiel 1. Die Auftragsgewichte betrugen pro Schicht 18 - 20 g/m². Vor jeder Beschichtung erfolgte eine Corona-Vorbehandlung.The machine conditions corresponded to those from example 1. The application weights per shift were 18-20 g / m². Corona pretreatment was carried out before each coating.

Vergleichsbeispiel V3:Comparative Example V3:

Zum Vergleich wurde ein auf dem Markt verfügbares Bildempfangsmaterial der Firma Hitachi eingesetzt.For comparison, an image receiving material from Hitachi available on the market was used.

Auftrag der BildempfangsschichtApplication of the image receiving layer

Die mit einer Zwischenschicht versehenen Trägermaterialien aus Beispiel 1, Beispiel 2 und Vergleichsbeispiel V1 wurden nach einer Corona-Vorbehandlung zur Bildung der Bildempfangsschicht mit der folgenden Beschichtungsmasse aus wäßriger Lösung mit einem Walzenauftragsaggregat beschichtet:After a corona pretreatment to form the image-receiving layer, the carrier materials from Example 1, Example 2 and Comparative Example V1 provided with an intermediate layer were coated with the following coating composition from aqueous solution using a roller application unit:

Rezeptur:Recipe:

Acrylat-Copolymer (Primal HG 44) 40 Gew.-%ige wäßrige DispersionAcrylate copolymer (Primal HG 44) 40% by weight aqueous dispersion 53,8 Gew.-%53.8% by weight Oxidiertes Polyethylen (Südranol 340) 30 Gew.-%ige wäßrige DispersionOxidized polyethylene (Südranol 340) 30% by weight aqueous dispersion 27,6 Gew.-%27.6% by weight Kieselsäure (Syloid ED50) 15 Gew.-% in WasserSilicic acid (Syloid ED50) 15% by weight in water 11,1 Gew.-%11.1% by weight Titandioxid (Rutil RN40) 40 Gew.-% in WasserTitanium dioxide (rutile RN40) 40% by weight in water 4,1 Gew.-%4.1% by weight Fluortensid (FT-248)Fluorosurfactant (FT-248) 3,4 Gew.-%3.4% by weight

Die Maschinengeschwindigkeit war 130 m/Min., die Trocknungstemperatur betrug 110 ° C. Das Auftragsgewicht nach der Trocknung lag bei 5 - 7 g/m².The machine speed was 130 m / min., The drying temperature was 110 ° C. The application weight after drying was 5 - 7 g / m².

PrüfergebnisseTest results

Alle Bildempfangsmaterialien wurden einem thermischen Bildübertragungsverfahren unterzogen. Hierzu wurde der Colour-Video-Printer VY-25E der Fa. Hitachi eingesetzt unter Verwendung der Hitachi-Farbbänder.All image receiving materials were subjected to a thermal image transfer process. For this purpose, the color video printer VY-25E from Hitachi was used, using the Hitachi ribbons.

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 video printer has the following technical data:
Image storage
: PAL 1 full screen memory
Printed image
: 64 color image elements: 540: 620 points
Printing time
: 2 minutes / picture

Die Farbdichte der einzelnen Farben der erhaltenen Bilder wurde mit dem Original-Reflection-Densitometer SOS-45 gemessen.The color density of the individual colors of the images obtained was measured using the original reflection densitometer SOS-45.

Für die Prüfung der Alterungs- und Wärmebeständigkeit wurde ein Linienraster für die einzelnen Grundfarben gewählt und die Linienbreiten ausgemessen. Da die Meßergebnisse der einzelnen Grundfarben (cyan, magenta, gelb) nur geringfügig differenzierten, meist jedoch identisch waren, wird in der nachfolgenden Tabelle jeweils der gemittelte Wert der drei Grundfarben angegeben.

Figure imgb0001
A line grid was selected for the individual primary colors and the line widths were measured for testing the aging and heat resistance . Since the measurement results of the individual primary colors (cyan, magenta, yellow) were only slightly differentiated, but mostly identical, the following table shows the averaged value of the three primary colors.
Figure imgb0001

Resumé:Resumé:

Wie die Prüfergebnisse belegen, zeigen die bebilderten Bildempfangsmaterialien ohne vernetzte Zwischenschicht (Vergleichsbeispiele V1 und V3) deutlich geringere Wärme- und Alterungsbeständigkeit als die erfindungsgemäßen, was in einer Zunahme der Strichbreite zum Ausdruck kommt.As the test results prove, the imaged image-receiving materials without a cross-linked intermediate layer (comparative examples V1 and V3) show significantly lower heat and aging resistance than those according to the invention, which is reflected in an increase in the line width.

Vernetzte Zwischenschichten, kombiniert mit vernetzten Bildempfangsschichten, ergeben Bilder mit stark verringerter Farbdichte; die niedrigeren Werte der Farbdichte bedeuten blassere Farben.Cross-linked intermediate layers, combined with cross-linked image-receiving layers, result in images with a greatly reduced color density; the lower values of color density mean paler colors.

Claims (15)

  1. Image receiving material for dye diffusion thermal transfer processes consisting of a carrier material, an intermediate layer and an image receiving layer and optionally other layers, characterized in that the intermediate layer consists of a crosslinked material produced without using organic solvents and the image receiving layer consists of an uncrosslinked material produced without using organic solvents.
  2. Image receiving material according to Claim 1, characterized in that the crosslinked material of the intermediate layer is a crosslinked lacquer crosslinking is accomplished through the use of high-energy radiation, which is an electron beam or UV radiation.
  3. Image receiving material according to Claims 1 and 2, characterized in that the intermediate layer is produced at least from monomers, oligomers, and/or prepolymers.
  4. Image receiving material according to Claims 1 and 2, characterized in that the intermediate layer is produced without using monomers.
  5. Image receiving material according to Claims 1 to 4, characterized in that the intermediate layer is crosslinked by means of one or more crosslinkable vinyl, allyl, acryl and/or methacryl compounds.
  6. Image receiving material according to Claim 5, characterized in that the crosslinkable compounds consist of more than 50 wt% (meth)acrylate esters.
  7. Image receiving material according to Claims 1 to 6, characterized in that the intermediate layer consists of up to 80 wt% white pigments from the group of carbonates, oxides, sulfates or sulfites of the elements calcium, magnesium, barium, strontium, zinc or titanium.
  8. Image receiving material according to Claim 7, characterized in that the white pigment is titanium dioxide.
  9. Image receiving material according to Claims 1 to 8, characterized in that the intermediate layer also contains additional additives such as optical brighteners, delustering agents, dyes, uncrosslinkable resins and photoinitiators in amounts of less than 20 wt%.
  10. Image receiving material according to Claims 1 to 9, characterized in that a barrier layer is applied beneath the intermediate layer.
  11. Image receiving material according to Claim 10, characterized in that the barrier layer consists of polyolefin.
  12. Process for producing an image receiving material for dye diffusion thermal transfer processes consisting of a carrier material, an intermediate layer and an image receiving layer and optionally other layers, characterized in that the carrier material is subject to the following process steps:
    1. Corona pretreatment of the surface;
    2. Coating with a radiation crosslinkable solvent free lacquer; and
    3. Crosslinking the lacquer by means of high energy radiation to form the intermediate layer;
    4. Corona treatment of the crosslinked intermediate layer;
    5. Coating the intermediate layer with an aqueous solvent free coating composition; and
    6. Drying the aqueous coating composition to form the image receiving layer.
  13. Process according to Claim 12, characterized in that the high energy radiation is electron radiation or UV radiation.
  14. Process according to Claims 12 and 13, characterized in that the coating is applied with a radiation crosslinkable solvent free, monomer free lacquer at an elevated temperature of the coating composition, preferably between 30°C and 60°C.
  15. Process according to Claims 12 to 14, characterized in that the crosslinking of the lacquer is accomplished by means of high energy radiation when the lacquer is in contact with a high gloss metal surface.
EP19920103825 1991-05-24 1992-03-06 Thermal transfer multilayered image receiving sheet and production process therefor Expired - Lifetime EP0514631B1 (en)

Applications Claiming Priority (2)

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DE4116994 1991-05-24
DE4116994A DE4116994A1 (en) 1991-05-24 1991-05-24 MULTILAYER IMAGE RECEIVING MATERIAL FOR THERMAL COLOR TRANSFER METHOD AND METHOD FOR THE PRODUCTION THEREOF

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EP0514631B1 true EP0514631B1 (en) 1995-06-21

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US5318943A (en) * 1991-05-27 1994-06-07 Dai Nippon Printing Co., Ltd. Thermal transfer image receiving sheet
DE69527266T2 (en) 1994-07-26 2003-03-06 Sony Corp., Tokio/Tokyo IMAGE TRANSFER METHOD
NL1006663C2 (en) * 1997-07-25 1999-01-26 Oce Tech Bv Image receiving paper for color inkjet printing with aqueous inks.
US6610388B2 (en) * 2001-05-23 2003-08-26 Arkwright, Inc. Ink-jet recording media comprising a radiation-cured coating layer and a continuous in-line process for making such media
ES2886358T3 (en) 2012-04-24 2021-12-17 At Promotions Ltd Antimicrobial container for drinking or eating
GB2525624A (en) 2014-04-29 2015-11-04 At Promotions Ltd Drinking or eating vessel
US10947011B2 (en) 2014-12-22 2021-03-16 At Promotions Ltd Drinking or eating vessel
GB201700408D0 (en) 2017-01-10 2017-02-22 A T Promotions Ltd Vacuum decoration of a drinking or eating vessel

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JPS5985792A (en) * 1982-11-10 1984-05-17 Matsushita Electric Ind Co Ltd Dye thermal transfer recording receptor
JPS59164187A (en) * 1983-03-09 1984-09-17 Honshu Paper Co Ltd Thermal transfer recording medium
JPS6398494A (en) * 1986-10-15 1988-04-28 Nikon Corp Image-receiving sheet for thermal transfer
US4837200A (en) * 1987-07-24 1989-06-06 Kanzaki Paper Manufacturing Co., Ltd. Image-receiving sheet for thermal transfer printing
JP2768468B2 (en) * 1988-04-25 1998-06-25 王子製紙株式会社 Melt type thermal transfer ink image receiving sheet
JPH02164593A (en) * 1988-12-19 1990-06-25 Kanzaki Paper Mfg Co Ltd Image receiving sheet for thermal transfer recording
JPH02223484A (en) * 1989-02-23 1990-09-05 Mitsubishi Paper Mills Ltd Image receiving paper for thermal transfer and its manufacturing method
JPH02305688A (en) * 1989-05-19 1990-12-19 Mitsubishi Paper Mills Ltd Image receiving sheet for thermal transfer recording
DE69015720T2 (en) * 1989-07-21 1995-05-24 Ici Plc Receiver layer for heat transfer.
DE4117317C2 (en) * 1990-05-28 1993-12-16 Mitsubishi Paper Mills Ltd Recording sheet for heat transfer recording by sublimation and method for its production

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DE4116994A1 (en) 1992-11-26
EP0514631A1 (en) 1992-11-25

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