EP0673778B1 - Farbstoffempfangsschicht für thermische Übertragungsaufzeichnung - Google Patents

Farbstoffempfangsschicht für thermische Übertragungsaufzeichnung Download PDF

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Publication number
EP0673778B1
EP0673778B1 EP19950102560 EP95102560A EP0673778B1 EP 0673778 B1 EP0673778 B1 EP 0673778B1 EP 19950102560 EP19950102560 EP 19950102560 EP 95102560 A EP95102560 A EP 95102560A EP 0673778 B1 EP0673778 B1 EP 0673778B1
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EP
European Patent Office
Prior art keywords
thermal
dye
layer
transfer
receiving layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP19950102560
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English (en)
French (fr)
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EP0673778A1 (de
Inventor
Susan K. C/O Minnesota Mining And Jongewaard
Robert A. C/O Minnesota Mining And Manuf. Braun
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GlassBridge Enterprises Inc
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Minnesota Mining and Manufacturing Co
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Priority claimed from US08/217,385 external-priority patent/US5395720A/en
Priority claimed from US08/217,384 external-priority patent/US5395719A/en
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0673778A1 publication Critical patent/EP0673778A1/de
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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
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5272—Polyesters; Polycarbonates
    • 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
    • B41M2205/32—Thermal receivers
    • 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
    • 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
    • B41M5/443—Silicon-containing polymers, e.g. silicones, siloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/529—Macromolecular coatings characterised by the use of fluorine- or silicon-containing organic compounds

Definitions

  • This invention relates to thermal transfer printing, and in particular to a novel thermal transfer receptor sheet for such printing using a coated metallized-polymer surface as a receptor surface.
  • thermal dye transfer printing an image is formed on a receptor sheet by selectively transferring a dye to a receptor sheet from a dye donor sheet placed in momentary contact with the receptor sheet.
  • Material to be transferred from the dye donor sheet is directed by a thermal printhead, which consists of small electrically heated elements (print heads). These elements transfer image-forming material from the dye donor sheet to areas of the dye receptor sheet in a image-wise manner.
  • Thermal dye transfer systems have advantages over other thermal transfer systems, such as chemical reaction systems, and thermal mass transfer systems. In general thermal dye transfer systems offer greater control of gray scale than these other systems, but they have problems as well.
  • One problem is release of the dye donor and receptor layers during printing. This has been addressed often by the addition of dye-permeable release coatings applied to the surface of the dye receptor layer. Additionally, materials are required for use in the receptor layer having suitable dye permeability, mordanting properties, adhesion to the substrate, and long term light and thermal stability.
  • imaging systems It is often desirable for imaging systems to be useful on different types of receptor substrates. This is particularly true in imaging systems used in proofing operations where the final image is to give the appearance of the final printed product. Where the final product is to be an image provided on a metal surface, it is difficult for may types of proofing systems to provide a realistic imaging system. Conventional photomechanical proofing systems which operate by using specialized photoresist or phototackifiable elements can not readily provide quality images on metal surfaces as they are not designed for such image productions.
  • Thermal dye transfer and thermal mass transfer often require special receptor surfaces to provide the highest quality images.
  • Thermal mass transfer has been able to provide fairly accurate renditions of images on metallized surfaces by first transfering a metallic thermal mass transfer background and then transfering a colored image on top of or within the borders of the metallic image.
  • Thermal dye transfer can not perform that type of two step image transfer because metallic appearing images or backgrounds are not readily provided by dyes or dye-like materials susceptible to the thermal dye transfer process.
  • thermal dye transfer receptor layers which can be coated out of solution and used on various surfaces to provide a high quality dye receiving layer. Such materials are described in U.S. Patent Nos. 4,914,078 and 4,968,658. These layers are coated out of solution from presently acceptable solvents such as methyl ethyl ketone. These types of coating solutions were, however, not found to be useful on commercially available metallized (e.g., aluminized) polyester film. The most serious problem encountered in the use of these specialized dye receptive coatings was that the coating would not strongly adhere to the metallised surface.
  • U.S. Patent No. 4,968,658 teaches the use of a thermal transfer receptor surface with a receiver coating comprising a dye-receptive material, a dye-permeable release agent, and an alkoxylated Bisphenol A unsaturated polyester. Fumaric acid may also be used in the layer.
  • Japan Patent Abstract No. 2025390 describes an image-receiving material for thermal transfer capable of exhibiting favorably a metallic image with a metallic luster by providing a metallic layer comprising a metallic powder dispersed therein, between a dyeable resin layer and a base.
  • thermoset resin in intimate contact with a dye or thermal mass transfer donor sheet, the receptor comprising a supporting substrate having on at least one surface thereof a dye or thermal mass transfer receptive receiving layer comprising a polymeric substrate having a vapor-deposited metal layer on at least one surface thereof.
  • a primer layer coating comprising: a) a linear saturated thermoplastic polyester, and b) an alkyd thermoset polyester resin.
  • the thermoset resin is preferably cured with a melamine crosslinking agent and/or a para -toluene sulfonic acid.
  • the receptor sheet comprises the described metallized polymer substrate with the primer layer of the present invention thereon and a dye or thermal mass transfer receptor layer coated on the primer.
  • the dye or thermal mass transfer receptive receiving layer is positioned in intimate contact with a dye or thermal mass transfer donor layer during the thermal transfer process.
  • thermal transfer receptor sheets as described above wherein a polysiloxane release layer is coated on the dye or thermal mass transfer receptive receiving layer or a release agent is incorporated into the dye receptor layer.
  • the thermal transfer receptor sheets of the invention have good dye and mass transfer receptivity and excellent dye-image thermal stability properties, and can provide an accurate proofing image which resembles a printed image on a metal surface.
  • the thermal dye and mass transfer receptor sheets used in the invention comprise a supporting organic polymeric substrate having a vapor deposited metal layer, a primer layer comprising a mixture of a linear, saturated thermoplastic polyester adhesive and a thermoset (e.g., cured or crosslinked) polyester alkyd resin, and over said primer layer, a dye receptive layer.
  • the receptive layer is optionally coated with a polysiloxane release layer or may contain release agents therein.
  • the linear, saturated polyester thermoplastic adhesive and polyester alkyd resin can be incorporated within the receiving layer and further contain a crosslinking agent such as a isocyanate.
  • the dye or mass transfer image receptor layer used in the present invention must be compatible as a coating with a number of resins for mass transfer and a number of dyes for thermal dye transfer. Since different dye transfer media manufacturers generally use different dye formulations in their donor sheets, the dye receiving layer should have an affinity for several different dyes. Because the transfer of dye from the dye donor sheet to the dye receptor sheet is essentially a contact process, it is important that there be intimate contact (e.g., no air gaps or folds) between the dye donor sheet and the dye receptor sheet at the instant of heating to effect imaging.
  • dye receptor layer compositions are known in the art and they are generally selected from polymer classes and mixtures thereof such as poly(vinyl chloride), chlorinated poly(vinyl chloride), vinyl acetate/vinyl chloride copolymers, silicone surfaces on polymeric bases, poly(methyl acrylate), polyvinyl acetals (e.g., polyvinyl butyral) and the like, which are preferred classes of polymers for receptor layers.
  • poly(vinyl chloride) chlorinated poly(vinyl chloride), vinyl acetate/vinyl chloride copolymers
  • silicone surfaces on polymeric bases poly(methyl acrylate)
  • polyvinyl acetals e.g., polyvinyl butyral
  • Surface modifying agents and treatments to alter opacity, smoothness, adhesion of subsequent coatings, tint, and dye absorption are also conventionally used.
  • poly(vinyl chloride) is often used with an additional resin, and usually additional or special plasticizers.
  • Chlorinated poly(vinyl chloride) is a homopolymer of poly(vinyl chloride) that has been subjected to a chlorination reaction.
  • CPVC has may of the good dye receptive properties of poly(vinyl chloride) and retains them at higher temperatures than PVC.
  • U.S. Patents 4,990,485; 4,931,423; 4,927,666; 4,914,078; and 4,910,189 show receptor media which have compositions and constructions which could be used in combination with the layers of the present invention.
  • the proper selection of softening temperature (e.g. glass transition temperature, Tg) of the dye receiving layer is important in the preparation of the thermal dye transfer receptor sheet.
  • the dye receiving layer for thermal dye transfer imaging should at least allow or enable increased solubilization of the dye, dye migration, dye permeation, and/or surface release of the dye between the donor and receptor surfaces below the temperatures employed to transfer dye from the dye donor sheet.
  • the softening point must not allow the resin to become distorted, stretched, wrinkled, etc.
  • the mass transfer receptor layer should be readily bonded to by mass transfer resins, and the resins with the pigments therein.
  • the dye receptor sheet is preferably non-tacky and capable of being fed reliably into a thermal printer, and is of sufficient durability that it will remain useful after handling, feeding, and removal from imaging.
  • the dye or mass transfer receptor sheet used in the present invention may be prepared by introducing the various components for making the receiving layer with suitable solvents (e.g., tetrahydrofuran (THF), methyl ethyl ketone (MEK), toluene, and mixtures thereof.
  • suitable solvents e.g., tetrahydrofuran (THF), methyl ethyl ketone (MEK), toluene, and mixtures thereof.
  • the resulting solutions are mixed at room temperature (for example), then the resulting mixture is coated onto the substrate and the resultant coating dried, preferably at elevated temperatures.
  • Suitable coating techniques include knife coating, roll coating, curtain coating, spin coating, extrusion die coating, gravure coating, etc.
  • the receiving layer is preferably free of any observable colorant (e.g., an optical density of less than 0.2, preferably less than 0.1 absorbance units).
  • the thickness of the receiving layer is from about 0.001 mm to about 0.1 mm,
  • Materials that have been found to be particularly useful for forming the receiving layer include sulfonated hydroxy epoxy functional vinyl chloride copolymers as described in U.S. Patent No. 4,910,189 and in another embodiment blends of sulfonated hydroxy epoxy functional vinyl chloride copolymers with other polymers. Any of the well known and/or commercially available materials known in the art as dye or thermal mass transfer receptor polymeric compositions may be used in the practice of the present invention. Polyvinyl resins, and especially polyvinyl chloride polymers and copolymers are widely used in the art. Chlorinated polyvinyl chlorides and their blends have also found wide acceptance. Other vinyl polymers and copolymers are also used in the art.
  • Blends of resins are often used to achieve a appropriate balance of properties in the receiving layers of the art.
  • the limiting factors to the resins chosen for the blend vary only to the extent of compounding necessary to achieve the property desired.
  • Preferred blendable additives include, but are not limited to polyvinyl chloride, acrylonitrile, styrene-acrylonitrile copolymers, polyesters (especially bisphenol A fumaric acid polyester), acrylate and methacrylate polymers (especially polymethyl methacrylate), epoxy resins, and polyvinyl pyrrolidone.
  • an additional polymer, copolymer, or resin is used (as with an epoxidized, sulfonated polyvinyl chloride resin as in U.S.
  • the additional polymer is usually added in a amount of 75 percent by weight or less of the resinous composition of the dye or thermal mass transfer receiving layer, preferably in the amount of 25 to 75 percent by weight for non-release polymers, or 0.01 to 15% for release polymers.
  • Release polymers are characterized by low surface energy and include silicone and fluorinated polymers.
  • Non-limiting examples of release polymers are poly dimethyl siloxanes, perfluorinated polyethers, etc.
  • Other conventional additives include, but are not limited to, surfactants, plasticizers, UV stabilizers, coating aids, and the like.
  • Suitable substrate materials may be any flexible material, optionally on which a metal layer may be vapor depositied. Suitable substrates may be smooth (preferably) or rough, transparent, opaque, and continuous or sheetlike. They may be porous or essentially non-porous. Preferred backings are white-filled or transparent polyethylene terephthalate or other temperature stable thermoplastic organic film forming polymers (e.g., polycarbonates, polyolefins, etc.) Non-limiting examples of materials that are suitable for use as a substrate include polyesters, especially polyethylene terephthalate, polyethylene naphthalate, polysulfones, polystyrenes, polycarbonates, polyimides, polyamides, cellulose esters, such as cellulose acetate and cellulose butyrate, polyvinyl chlorides and derivatives, polyethylenes, polypropylenes, etc.
  • polyesters especially polyethylene terephthalate, polyethylene naphthalate, polysulfones, polystyrenes, polycarbonates, poly
  • the substrate generally has a thickness of 0.02 to 1.5 mm, preferably 0.025 mm to 0.40 mm. If the substrate is supported by a liner or other supporting backing, then the preferred range for the substrate alone would be 0.0006 to 0.8 mm.
  • the receptor substrate may be porous or non-porous, and individual layers of the receptor or donor sheet may be porous or non-porous so as to adjust thermal properties in the sheets and the transfer process.
  • non-porous in the description of the invention it is meant that ink, paints or other liquid coloring media will not readily flow through the substrate (e.g., less than 0.05 ml per second at 7 torr applied vacuum, preferably less than 0.02 ml per second at 7 torr applied vacuum).
  • the lack of significant porosity prevents absorption of the heated receptor layer into the substrate.
  • porosity has also been found to be beneficial in localizing thermal events to the region of dye transfer and thereby increasing transfer efficiency and quality.
  • the substrates used in the present invention may also have a supporting backing to help in transporting the media through the printer and the imaging device. This is essentially a non-critical, additional and optional structural feature. Such backings may be directly or adhesively adhered to the substrate.
  • the metals which may be used as the vapor deposited material may be essentially any metal which is capable of being vapor deposited. In practice, aluminum is the most clearly preferred material, but other metals such as tin, steel, iron, copper, brass, bronze, silver, gold, titanium, and the like may also have specialty applications.
  • the metals may be coated with dyes, as part of the metal layer or as a separate layer(s) to improve tone, tint, or other visual aspects of coloration.
  • the thermal dye or mass transfer receptor layers used in the invention are used in combination with a dye donor sheet wherein a dye image is transferred from the dye donor sheet to the receptor sheet by the application of heat.
  • the heat may be applied by printheads, lasers, laser diodes, focused radiation, and the like, as is understood in the art. The finer the resolution of the applied heat, the finer the resolution of the image, within reasonable limits.
  • the dye donor layer is placed in contact with the receiving layer of the receptor sheet and selectively heated according to a pattern of information signals whereby the dyes (or in the case of thermal mass transfer, the dyes or pigment in a binder) are transferred from the donor sheet to the receptor sheet.
  • a pattern is formed thereon in a shape and density according to the intensity of heat applied to the donor sheet.
  • the heating source may be an electrical resistive element, a laser (preferably an infrared laser diode), a infrared flash, a heated pen, or the like.
  • the quality of the resulting image can be improved by readily adjusting the size of the heat source that is used to supply the heat energy, the contact position of the donor sheet and the receptor sheet, and the heat energy.
  • the applied heat energy is controlled to give light and dark gradation of the image and for the efficient diffusion of the dye from the donor sheet to ensure continuous gradation of the image as in a photograph.
  • Mass transfer imaging would give more limited gradation, but providing solid blocks (as in half tone imaging systems) for graphics, lettering borders, and the like.
  • the dye receptor sheet of the invention can be utilized in the print preparation of a photograph by printing, facsimile, or magnetic recording systems wherein various printers of thermal printing systems are used, or print preparation for a television picture, or cathode ray tube picture by operation of a computer, or a graphic pattern or fixed image for suitable means such as a Video camera, and in the production of progressive patterns from an original by an electronic scanner that is used in photomechanical processes of printing.
  • Suitable thermal dye transfer donor sheets for use in the invention are well known in the thermal imaging art. Some examples are described in U.S. Patent No. 4,853,365 which is hereby incorporated by reference.
  • additives and modifying agents that may be added to the dye or mass transfer receiving layer include UV stabilizers, heat stabilizers, suitable plasticizers, surfactants, release agents, antistatic agents, etc., used in the receptor sheet of the present invention.
  • mass transfer receptor layers will contain additives that will facilitate the bonding and transfer of the mass transfer donor materials onto the receptor sheet.
  • the dye or mass transfer receiving layer of the invention is overcoated with a release layer or may contain release ingredients therein.
  • the release layer must be permeable to the dyes used under normal transfer conditions in order for dye to be transferred to the receiving layer.
  • Release materials suitable for this layer may be fluorinated polymers such as polytetrafluoroethylene, and vinylidene fluoride/vinylidene chloride copolymers, and the like, as well as dialkylsiloxane based polymers such as polydimethylsiloxane, modified organopolysiloxanes, polyvinyl butyral/siloxane copolymers such as Dai-AllomerTM SP-711 (manufactured by Daicolor Pope, Inc., Rock Hill, SC) and urea-polysiloxane polymers.
  • improved release properties may be achieved by addition of a silicone or mineral oil to the receiving layer during formulation.
  • the primer layer compositions used in the present invention comprises a linear, saturated thermoplastic polyester and a thermoset alkyd polyester.
  • Many different types and classes of polymer solutions were evaluated before identifying the primer compositions of the present invention as uniquely beneficial materials.
  • the adhesive could be coated out of ketone solutions (e.g., methyl ethyl ketone, methyl isobutyl ketone, etc.). This provides the element with a highly compatible solvent system which does not adversely affect other layers in the receptor element.
  • the preferred linear, saturated thermoplastic polyester adhesive present in the dye receiving element used in the present invention is a polyethylene terephthalate adhesive having a molecular weight in the range of 10,000 to 40,000, preferably 15,000 to 30,000.
  • polyesters are available from Bostik Chemical group, Emhart Corporation (e.g., Bostik 7695, 7651, 7614, and 7660) or from Goodyear Corp. (Vitel 3200, 3300, and 3550).
  • the Vitel resins are solids.
  • An alkyd polyester is used in combination with the thermoplastic polyester, and the alkyd polyester is crosslinked, as with a melamine crosslinking agent.
  • Such materials are also individually available (e.g., HKR 180®, HydroKinetics Corp.)
  • the alkyd polyester may be further crosslinked with materials such as para-toluene sulfonic acid and its salts.
  • a primer layer consisting of only the HKR 180 resin and para-toluene sulfonic acid as a crosslinker provided adequate adhesion for a vapor coated film initially. However, after the metal layer was overcoated with a thermal dye receiving layer, very poor adhesion was observed for both layers.
  • the linear polyester adhesive e.g., Bostik 7695
  • Bostik 7695 Bostik 7695
  • the linear polyester adhesive was coated by itself as a primer layer, it provided both good initial adhesion and good adhesion after application of a dye receptor layer.
  • the linear polyester was too tacky and caused blocking of the coated film before application of the receptor layer. This made the intermediate difficult to work with, because it is desirable to coat the layers separately and then dry them after each coating.
  • PVC polyvinyl chloride
  • PET polyethylene terephthalate
  • the term "Meyer bar” refers to a wire wound rod such as that sold by R & D Specialties, Webster, NY.
  • Butyl Magenta may be prepared as described in U.S. Patent 4,977,134 (Smith et al.); HSR-31 was purchased from Mitsubishi Kasel Corp., Tokyo, Japan; AQ-1 was purchased from Alfred Bader Chemical (Aldrich Chemical Co., Milwaukee, WI); Foron Brilliant Blue was obtained from Sandoz Chemicals, Charlotte, NC; Heptyl Cyan and Octyl Cyan were prepared according to the procedures described in Japanese published application 60-172,591.
  • thermal receptor material is a 10% solvent mixture of VYNS-3® (a vinyl chloride/vinyl acetate copolymer available from Union Carbide) and a multi-functionalized polyvinyl chloride (MR-120® available from Nippon Zeon). These two polymers are made into solutions with methyl ethyl ketone at a 12/1 ratio of VYNS-3® to MR-120®.
  • VYNS-3® a vinyl chloride/vinyl acetate copolymer available from Union Carbide
  • MR-120® multi-functionalized polyvinyl chloride
  • Vitel PE 2200® a copolyester resin made by Goodyear
  • Cyastat LS® a quaternary ammonium 3-lauramidopropyl triamethylammonium methylsulfate compound
  • This solution was knife coated onto 0.05 mm (2 mil) PET film which has been coated with vapor-deposited aluminum and the primer composition of the present invention, the thermal receptor coating being applied at a 0.025 mm (1 mil) wet film thickness. This was a coating of about 24.75 mg/m 2 (275 mg/square foot) dry coating weight.
  • a donor sheet was used to transfer the dye to the receptor using a thermal printer.
  • One useful printer used in the practice of the present invention was a Kyocera raised glare thin film thermal print head (Kyocera Corp., Kyoto, Japan) with 8 dots per mm and 0.3 watts per dot.
  • the electrical energy varies from 0 to 16 joules/cm 2 , which corresponds to head voltages from 0 to 14 volts with a 23 ms burn time.
  • the 3M RainbowTM DeskTop Color Proofing system with 3M supplied donor ribbon was used.
  • polyester additives within this invention were identified by studying a series of thermoplastic copolyesters having both aromatic and aliphatic groups. We also looked at resins with only aromatic groups and resins with only aliphatic groups and just aliphatic polymers.
  • oligomers present on the surface of the vapor-deposited film can not be washed off or readily penetrated by common solvents such as ketones, alcohols, acetones, tetrahydrofuran, or toluene. These oligomers, however, have been removed with the use of chlorinated solvents such as 1,2-dichloroethane. Since the use of chlorinated solvents is usually considered to be hazardous, the option of washing aluminum coated polyester is impractical.
  • polyester additive must contribute to the dye receptive composition, comprising at least 50 percent polyvinyl chloride, Chlorinated polyvinyl chloride, or polyvinyl chloride/polyvinyl acetate copolymers, include:
  • polyester plasticizers such as Paraplex H-25® from Rohm and Haas (a sebacic acid polyester), Paraplex H-50® (an adipic acid polyester) and Plastolein 9750® from Emery Industries (an azalaic acid polyester). All aliphatic polyesters in this study failed to perform adequately in the dye receptor surface because of their inability to provide a adequate mass transfer surface due to the plasticizer's lower glass transition temperature, which produced a oily/liquid film surface. The aliphatic polyester plasticizers were generally mobile in the coated film ad hindered dye stability and dye transfer uniformity. Due also to the characteristics of aliphatic polyester resins, poor adhesion to metallic substrates was observed.
  • polyester polymers derived from aromatic groups such as those found in thermoplastic polyester films (e.g., Vitel 2200®) fail to perform adequately as the dye receptor surface because of their low acceptance of dye image density and usually poorer dye stability to heat and light.
  • Aromatic resins, aliphatic resins, and the aromatic/aliphatic copolyester resin blends are all compatible with dye receptive vinyl chloride/vinyl acetate copolymer formulations. Results indicate that aliphatic aromatic copolyester resin blends (as mixtures of aliphatic and aromatic polymers and/or copolymers of aromatic and aliphatic monomeric units) impart better adhesion to metallic surfaces without detrimental side effects to the dye receptivity and stability.
  • the polyester resin should contain 5-95% by weight of aliphatic plus aromatic groups. The combination of aliphatic and aromatic groups in the polyester resin provides the unique properties of hardness and flexibility necessary for the thermal receptive film to function properly while maintaining adequate adhesion.
  • Polyester resins like Vitel 2200® are too hard (high tensile strength and low elongation) and are unable to wet solvent insensitive substrates (metallic film). While aliphatic polyesters, like Plastolein 9750® have excellent wetting properties, they are too soft (low tensile strrength and elongation) which inhibits adhesion.
  • Vitel 2200® which contains only aromatic groups is included as a reference material (see the table below).
  • Raw Materials Type Bostik 7695 Bostik 7660 Bostik 7651 Bostik 7614 Vitel 2200 Vitel 3200 Vitel 3300 Vitel 3550 Vitel 3800 Terephthalic Acid A 1,4 24% 14% 25% 33% 24% 15% Isophthalic Acid A 1,3 20% 24% 9% 10%
  • Vitel 3800® has a higher aliphatic to aromatic ratio than the other Vitel resins shown in the table.
  • Bostik 7651 and Bostik 7614 have a higher aromatic to aliphatic ratio than do the other Bostik resins.
  • polyester resins containing both aromatic and aliphatic groups provide the receptive layers of the present invention with improved adhesion to metal surfaces, uninhibited mass transfer and dye receptivity, minimal, negative, effects on dye image stability to heat and light, and good film forming characteristics.
  • the linear, saturated thermoplastic polyester adhesive can be incorporated within the dye or mass transfer receiving layer and additionally contain crosslinking agents such as isocyanates.
  • This alternative embodiment does not require a prime layer and can be coated directly onto a metallized base without damaging the adhesion between the layers.
  • Such a composition may have a formulation such as the following, which has been found to be effective in this practice:

Claims (7)

  1. System für den thermischen Transfer, umfassend ein Donorelement für den thermischen Transfer in Berührung mit einem Empfängerelement für den thermischen Transfer, wobei das Empfängerelement für den thermischen Farbstofftransfer ein Substrat umfaßt, das eine aus der Dampfphase abgeschiedene Metallschicht, eine Grundierschicht auf der Metallschicht, wobei die Grundierschicht dadurch gekennzeichnet ist, daß sie einen thermoplastischen, linearen, gesättigten Polyester mit aliphatischen und aromatischen Gruppen und einen wärmegehärteten Alkydpolyester umfaßt, und auf der Grundierschicht eine Empfängerschicht aufweist, wobei die Empfängerschicht in Kontakt mit dem Donorelement für den thermischen Transfer ist.
  2. System nach Anspruch 1, wobei die Empfängerschicht eine Empfängerschicht für den thermischen Farbstoff-Transfer ist und ein Vinylchlorid-Copolymer mit einer Glasübergangstemperatur der Zusammensetzung zwischen 50 und 85 °C, einem Massenmittel der Molmasse zwischen 10 000 und 100 000 g/mol, einem Hydroxyl-Äquivalenzgewicht zwischen 1000 und 7000 g/mol, einem Sulfonat-Äquivalenzgewicht zwischen 5000 und 40 000 g/mol und einem Epoxy-Äquivalenzgewicht zwischen 500 und 7000 g/mol umfaßt.
  3. System für den thermischen Transfer nach Anspruch 1, wobei die Empfängerschicht eine Empfängerschicht für den thermischen Farbstoff-Transfer ist, wobei eine Polysiloxan-Trennschicht auf die oder in der Empfängerschicht aufgetragen ist.
  4. System für den thermischen Transfer nach Anspruch 1, wobei die thermische Donorfolie ein Substrat umfaßt, das nur auf einer seiner Oberflächen eine Schicht aufweist, die einen thermisch übertragbaren Farbstoff umfaßt.
  5. Verfahren zur Übertragung eines Bildes unter Verwendung des Systems des thermischen Transfers nach Anspruch 1, wobei Wärme in einer bildweisen Verteilung auf die Seite der thermischen Donorfolie einwirken gelassen wird, die sich am weitesten entfernt von dem Empfängerelement befindet, wobei die Wärme in einem Umfang einwirken gelassen wird, der ausreichend ist, um Material thermisch von dem Donorelement zu übertragen.
  6. System für den thermischen Farbstoff-Transfer, umfassend ein Empfängerelement für den thermischen Transfer im innigen Kontakt mit einer Folie für den thermischen Transfer, wobei das Empfängerelement ein Substrat umfaßt, bei dem sich auf wenigstens einer seiner Oberflächen in Kontakt mit der Folie für den thermischen Transfer eine aus der Dampfphase abgeschiedene Metallschicht befindet, wobei sich eine Grundierschicht auf der Metallschicht befindet und sich auf der Grundierschicht eine Schicht für den thermischen Massentransfer oder für die Farbstoffaufnahme befindet, wobei die Grundierschicht dadurch gekennzeichnet ist, daß sie einen linearen, gesättigten, thermoplastischen Polyester mit aliphatischen und aromatischen Gruppen und ein wärmegehärtetes Alkydpolyester-Harz umfaßt.
  7. System nach Anspruch 6, wobei die Aufnahmeschicht eine thermischen Farbstoff aufnehmende Schicht ist, die ein Vinylchlorid-Copolymer mit einer Glasübergangstemperatur der Zusammensetzung zwischen 55 und 70 °C, einem Massenmittel der Molmasse zwischen 20 000 und 60 000 g/mol, einem Hydroxyl-Äquivalenzgewicht zwischen 1500 und 4000 g/mol, einem Sulfonat-Äquivalenzgewicht zwischen 9000 und 23 000 g/mol und einem Epoxy-Äquivalenzgewicht zwischen 500 und 7000 g/mol umfaßt.
EP19950102560 1994-03-24 1995-02-23 Farbstoffempfangsschicht für thermische Übertragungsaufzeichnung Expired - Lifetime EP0673778B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US217384 1994-03-24
US08/217,385 US5395720A (en) 1994-03-24 1994-03-24 Dye receptor sheet for thermal dye and mass transfer imaging
US08/217,384 US5395719A (en) 1994-03-24 1994-03-24 Dye receptor sheet for thermal transfer imaging
US217385 1994-03-24

Publications (2)

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EP0673778A1 EP0673778A1 (de) 1995-09-27
EP0673778B1 true EP0673778B1 (de) 1997-10-22

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EP (1) EP0673778B1 (de)
JP (1) JPH07276832A (de)
DE (1) DE69500902T2 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013107773A1 (de) 2012-01-19 2013-07-25 Bayer Intellectual Property Gmbh Kunststofffolie zum bedrucken mittels dye diffusion thermal transfer druck
WO2013107777A1 (de) 2012-01-19 2013-07-25 Bayer Intellectual Property Gmbh Kunststofffolie zum bedrucken mittels dye diffusion thermal transfer druck

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3592567A4 (de) 2018-05-25 2020-02-12 Evonik Operations GmbH Kunststoffmaterial zum bedrucken durch farbstoffdiffusions-thermotransferdruck

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8709800D0 (en) * 1987-04-24 1987-05-28 Ici Plc Thermal transfer receiver
JPH0225390A (ja) * 1988-07-15 1990-01-26 Nitto Denko Corp 熱転写用受像体
GB8826457D0 (en) * 1988-11-11 1988-12-14 Ici Plc Thermal transfer receiver

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013107773A1 (de) 2012-01-19 2013-07-25 Bayer Intellectual Property Gmbh Kunststofffolie zum bedrucken mittels dye diffusion thermal transfer druck
WO2013107777A1 (de) 2012-01-19 2013-07-25 Bayer Intellectual Property Gmbh Kunststofffolie zum bedrucken mittels dye diffusion thermal transfer druck
US9375968B2 (en) 2012-01-19 2016-06-28 Covestro Deutschland Ag Plastic film for printing by dye diffusion thermal transfer printing
US9446619B2 (en) 2012-01-19 2016-09-20 Covestro Deutschland Ag Plastic film for printing by dye diffusion thermal transfer printing

Also Published As

Publication number Publication date
JPH07276832A (ja) 1995-10-24
EP0673778A1 (de) 1995-09-27
DE69500902D1 (de) 1997-11-27
DE69500902T2 (de) 1999-01-21

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