EP0554583B1 - Eléments donneurs de colorant pour le transfert thermique de colorants - Google Patents

Eléments donneurs de colorant pour le transfert thermique de colorants Download PDF

Info

Publication number
EP0554583B1
EP0554583B1 EP19920203496 EP92203496A EP0554583B1 EP 0554583 B1 EP0554583 B1 EP 0554583B1 EP 19920203496 EP19920203496 EP 19920203496 EP 92203496 A EP92203496 A EP 92203496A EP 0554583 B1 EP0554583 B1 EP 0554583B1
Authority
EP
European Patent Office
Prior art keywords
dye
donor element
binder
weight
waxes
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
EP19920203496
Other languages
German (de)
English (en)
Other versions
EP0554583A1 (fr
Inventor
Geert Defieuw
Emiel Verdonck
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.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from EP19920200229 external-priority patent/EP0554576B1/fr
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP19920203496 priority Critical patent/EP0554583B1/fr
Publication of EP0554583A1 publication Critical patent/EP0554583A1/fr
Application granted granted Critical
Publication of EP0554583B1 publication Critical patent/EP0554583B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; 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
    • B41M5/42Intermediate, backcoat, or covering layers
    • B41M5/44Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • 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
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382Contact thermal transfer or sublimation processes
    • B41M5/392Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
    • 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
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382Contact thermal transfer or sublimation processes
    • B41M5/392Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
    • B41M5/395Macromolecular additives, e.g. binders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/30Thermal donors, e.g. thermal ribbons
    • 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
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; 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
    • B41M5/42Intermediate, backcoat, or covering layers
    • 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
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; 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
    • B41M5/42Intermediate, backcoat, or covering layers
    • B41M5/423Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
    • 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
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; 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
    • B41M5/42Intermediate, backcoat, or covering layers
    • B41M5/426Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
    • 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
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; 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
    • B41M5/42Intermediate, backcoat, or covering layers
    • B41M5/44Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B41M5/443Silicon-containing polymers, e.g. silicones, siloxanes

Definitions

  • the present invention relates to dye-donor elements for use according to thermal dye sublimation transfer.
  • Thermal dye transfer methods include thermal dye sublimation transfer also called thermal dye diffusion transfer. This is a recording method in which a dye-donor element provided with a dye/binder layer containing sublimating dyes having heat transferability is brought into contact with a receiver sheet and selectively, in accordance with a pattern information signal, heated with a thermal printing head provided with a plurality of juxtaposed heat-generating resistors, whereby dye is transferred from the selectively heated regions of the dye-donor element to the receiver sheet and forms a pattern thereon, the shape and density of which are in accordance with the pattern and intensity of heat applied to the dye-donor element.
  • a dye-donor element for use according to thermal dye sublimation transfer usually comprises a very thin support e.g. a polyester support, one side of which is covered with a dye/binder layer comprising the printing dyes in a form that can be released in varying amounts depending on how much heat is applied to the dye-donor element.
  • a very thin support e.g. a polyester support, one side of which is covered with a dye/binder layer comprising the printing dyes in a form that can be released in varying amounts depending on how much heat is applied to the dye-donor element.
  • the dye in the dye/binder layer is usually carried by a binder.
  • binder resins are cellulose derivatives like ethyl cellulose, hydroxyethyl cellulose, ethylhydroxy cellulose, ethylhydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate formate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate pentanoate, cellulose acetate hexanoate, cellulose acetate heptanoate, cellulose acetate benzoate, cellulose acetate hydrogen phthalate, and cellulose triacetate; vinyl-type resins like polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl acetoacetal, and polyacrylamide ; polymers and copolymers derived from acrylates and acrylate derivatives, such as polyacryl
  • the dye/binder layer comprising dye(s) carried by a binder may be coated from a solution in appropriate solvents on the subbed support, but the known coating techniques are not quite adapted to the discontinuous coating of differently coloured dye/binder areas on said very thin support. It is therefore customary, especially in large-scale manufacturing conditions, to print said dye/binder layer on said support by printing techniques such as a gravure process.
  • binders have one or more disadvantages. For instance, some binders have a low viscosity and thus form a dye/binder composition that does not have an ink-like nature and as a consequence is not printable. Other binders have a suitable viscosity, but are soluble only in solvents such as chlorinated hydrocarbon solvents, which are rejected nowadays from an ecological standpoint.
  • Another disadvantage of some binders is that when heat is supplied by the thermal printing head to the dye-donor element, the dye/binder layer melts and consequently starts sticking to the receiver sheet. This sticking eventually results in the tearing off of the dye/binder layer.
  • binders cause dye crystallization, which is to be avoided since it prevents effective thermal dye transfer and consequently produces erratic print densities and printing fog on the receiver sheet.
  • Copolymers of styrene and acrylonitrile are indeed binders that are excellent for preventing crystallization of the dye(s) present in the dye/binder layer, especially when a high ratio of dye(s) is used in respect of the binder.
  • dye-donor elements comprising a dye/binder layer containing such copolymers of styrene and acrylonitrile as binders have the disadvantage that - when stored or kept in rolled-up condition on reels or spools in cartridges - the side showing the dye/binder layer tends to stick to the contacting rear side of the dye-donor element. This sticking may result in tearing off of parts of the dye/binder layer.
  • EP-A-334323 discloses a dye layer that may contain a styrene-acrylonitrile copolymer as a binder.
  • the dye layer further comprises polypropylene wax particles distributed therein. These particles have an average size of less than 30»m.
  • EP-A-334323 further discloses a method for making an image using a dye donor element having such a dye layer and wherein the dye donor element is image-wise heated to cause image-wise transfer of dye to a receiving element.
  • DE-C-3635141 discloses a thermal dye-transfer system in which polystyrene, polyamide and/or polyamide particles are distributed in a styrene-acrylonitrile copolymer binder.
  • EP-A-307819 discloses a thermal transfer ink composition
  • a thermal transfer ink composition comprising a polystyrene-acrylic copolymer resin, colouring matter and resin particles having a size of between 0.05 and 2.0 »m.
  • solid waxes as used herein waxes are meant, which are in solid state at room temperature, which in the liquid state have a viscosity under 8000 mPa s, and which preferably do not dissolve in the solvents e.g. ethyl methyl ketone used for dissolving the dye(s) and the binder comprising said copolymer comprising styrene units and acrylonitrile units.
  • solvents e.g. ethyl methyl ketone used for dissolving the dye(s) and the binder comprising said copolymer comprising styrene units and acrylonitrile units.
  • the present invention further provides a method of forming an image having substantially faultless high densities by :
  • the dye/binder layer in one winding of the roll faces the rear face of the adjacent winding of the dye-donor element.
  • the dye and the binder comprising a copolymer comprising styrene units and acrylonitrile units would be in direct contact with the back layer of the dye-donor element and as mentioned above would tend to stick to the back layer if the protruding particles according to the present invention were not used.
  • the solid particles are uniformly distributed throughout the dye/binder layer and have an average particle size exceeding the thickness of said dye/binder layer so as to protrude from the surface of said layer.
  • the image-wise heating of the dye-donor element they may remain fixed in the dye/binder layer or they may transfer to the reveiver sheet.
  • the solid particles used in accordance with the present invention preferably have an average particle size ranging from 0.3 to 40 »m, and more preferably from 1.5 to 8 »m.
  • the wax used for the purpose of the present invention can be any of the water-insoluble thermoplastic wax-like materials of the known six classes of waxes i.e. vegetable waxes, insect waxes, animal waxes, mineral waxes, petroleum waxes, synthetic waxes, as well as the water-insoluble wax-like components that occur individually in these waxes, more particularly long-chain hydrocarbons, saturated, unsaturated, branched, and unbranched fatty acids and alcohols, as well as the ethers and esters of aliphatic monohydric alcohols.
  • waxes i.e. vegetable waxes, insect waxes, animal waxes, mineral waxes, petroleum waxes, synthetic waxes
  • water-insoluble wax-like components that occur individually in these waxes, more particularly long-chain hydrocarbons, saturated, unsaturated, branched, and unbranched fatty acids and alcohols, as well as the ethers and esters of aliphatic monohydric alcohols.
  • the solid waxes used in accordance with the present invention are selected from the group consisting of polyolefin waxes, ester waxes, and amide waxes.
  • the solid polyolefin wax is a polyethylene wax.
  • the amide wax is an ethylene-bis-stearamide wax such as Ceridust 3910 (trade name) Hoechst, Germany.
  • the wax used according to the present invention should, of course, be chemically inert towards the other ingredients of the dye/binder layer. Preferably, it does not dissolve together with the binder and the dye(s) in the solvent or solvent mixture used to form a coating or printing composition that is applied to a support, which may have been provided first with an adhesive or subbing layer.
  • solid wax particles that can be used according to the present invention in combination with the binder comprising a copolymer comprising styrene units and at least 15% by weight of acrylonitrile units are the following :
  • Polyolefin wax particles consisting of or comprising :
  • Amide wax particles consisting of or comprising :
  • Examples of calcium carbonate particles that can be used according to the present invention in combination with the binder comprising a copolymer comprising styrene units and at least 15% by weight of acrylonitrile units are the following :
  • polymethylsilylsesquioxan particles that can be used according to the present invention in combination with the binder comprising a copolymer comprising styrene units and at least 15% by weight of acrylonitrile units are the following : - Tospearl 120, Tospearl 145, Tospearl 240, Tospearl 108, and Tospearl 130, all being supplied by General Electric, The Netherlands. Tospearl 120 and Tospearl 145 are highly preferred for use according to the present invention. (Tospearl is a tradename)
  • the polymethylsilylsesquioxan particles are also effective in reducing the sticking tendency of dye/binder layers comprising other binders known in the art such as e.g. polyvinyl acetal, cellulose acetate propionate, cellulose acetate butyrate, and ethylcellulose. Even though the latter binders may cause more crystallization of the dye(s) in the dye/binder layer, they can still be used for dyes or dye mixtures that exhibit a lower intrinsic degree of crystallization.
  • the polymethylsilylsesquioxan particles are especially useful for obtaining uniform densities over the whole density scale when combined with the above-mentioned known binders.
  • the binder comprising a copolymer comprising styrene units and acrylonitrile units for use in the dye/binder layer according to the present invention comprises at least 60% by weight of styrene units and at least 25% by weight of acrylonitrile units binder.
  • the binder copolymer may, of course, comprise other comonomers than styrene units and acrylonitrile units provided that a sufficient number of acrylonitrile units are present. Suitable other comonomers are e.g. butadiene, butyl acrylate, and methyl methacrylate.
  • the binder copolymer preferably has a glass transition temperature of at least 50°C.
  • a binder that can be used advantageously in admixture with said binder copolymer is a toluene sulfonamide formaldehyde condensation product as described in the European patent application no. EP-A-573080.
  • Such condensation products are e.g. the commercially available Ketjenflex MH and Ketjenflex MS-80 (tradename of Akzo, The Netherlands).
  • the dye/binder layer comprises at least 35% by weight of sublimable dyes.
  • the dye/binder layer generally has a thickness of about 0.2 to 5.0 »m, preferably 0.4 to 2.0 »m, and the amount ratio of dye to binder generally ranges from 9:1 to 1:3 weight, preferably from 3:1 to 1:2 by weight.
  • Any dye or mixture of dyes can be used in the dye/binder layer provided it is easily transferable to the dye-image-receiving layer of the receiver sheet by the action of heat.
  • the coating composition for the dye/binder layer may also contain other additives, such as curing agents, preservatives, dispersing agents, antistatic agents, defoaming agents, viscosity-controlling agents, these and other ingredients having been described more fully in EP 133,011, EP 133,012, EP 111,004, and EP 279,467.
  • additives such as curing agents, preservatives, dispersing agents, antistatic agents, defoaming agents, viscosity-controlling agents, these and other ingredients having been described more fully in EP 133,011, EP 133,012, EP 111,004, and EP 279,467.
  • any material can be used as the support for the dye-donor element provided it is dimensionally stable and capable of withstanding the temperatures involved, up to 400°C over a period of up to 20 ms, and is yet thin enough to transmit heat applied on one side through to the dye on the other side to effect transfer to the receiver sheet within such short periods, typically from 1 to 10 ms.
  • Such materials include polyesters such as polyethylene terephthalate, polyamides, polyacrylates, polycarbonates, cellulose esters, fluorinated polymers, polyethers, polyacetals, polyolefins, polyimides, glassine paper and condenser paper.
  • Preference is given to a support comprising polyethylene terephthalate. In general, the support has a thickness of 2 to 30 »m.
  • the support may also be coated with an adhesive or subbing layer, if desired.
  • the dye/binder layer of the dye-donor element can be coated on the support or printed thereon by a printing technique such as a gravure process.
  • a dye-barrier layer comprising a hydrophilic polymer may also be employed between the support and the dye/binder layer of the dye-donor element to enhance the dye transfer densities by preventing wrong-way transfer of dye backwards to the support.
  • the dye barrier layer may contain any hydrophilic material that is useful for the intended purpose.
  • gelatin polyacrylamide, polyisopropyl acrylamide, butyl methacrylate-grafted gelatin, ethyl methacrylate-grafted gelatin, ethyl acrylate-grafted gelatin, cellulose monoacetate, methylcellulose, polyvinyl alcohol, polyethyleneimine, polyacrylic acid, a mixture of polyvinyl alcohol and polyvinyl acetate, a mixture of polyvinyl alcohol and polyacrylic acid, or a mixture of cellulose monoacetate and polyacrylic acid.
  • Suitable dye barrier layers have been described in e.g. EP 227,091 and EP 228,065.
  • Certain hydrophilic polymers e.g.
  • the reverse side of the dye-donor element has been coated with a heat-resistant layer to prevent the printing head from sticking to the dye-donor element.
  • a heat-resistant layer would comprise a lubricating material such as a surface-active agent, a liquid lubricant, a solid lubricant or mixtures thereof, with or without a polymeric binder.
  • the surface-active agents may be any agents known in the art such as carboxylates, sulfonates, phosphates, aliphatic amine salts, aliphatic quaternary ammonium salts, polyoxyethylene alkyl ethers, polyethylene glycol fatty acid esters, fluoroalkyl C2-C20 aliphatic acids.
  • liquid lubricants include silicone oils, synthetic oils, saturated hydrocarbons, and glycols.
  • solid lubricants include various higher alcohols such as stearyl alcohol, fatty acids and fatty acid exters.
  • Suitable heat-resistant layers have been described in e.g. EP 138,483, EP 227,090, US 4,567,113, US 4,572,860, US 4,717,711.
  • the heat-resistant layer comprises a polycarbonate derived from a bis-(hydroxyphenyl)-cycloalkane (diphenol), e.g. 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, as described in European patent application no.
  • EP-A-527520 as binder and a slipping agent comprising polydimethylsiloxane as lubricant in an amount of 0.1 to 10% by weight of the binder or binder mixture.
  • Other binders for the heat-resistant layer that can be used advantageously for improving the non-stickiness of the dye-donor element in rolled-up state are i.a. cellulose acetate butyrate, cellulose acetate propionate, and cellulose nitrate.
  • Suitable heat-resistant layers may also comprise cross-linked polymers for improving the non-stickiness of the dye-donor element in rolled-up state.
  • the slipping agent may be coated in the form of a separate topcoat on top of said heat-resistant layer as described in the above-mentioned European patent application no. EP-A-527520.
  • the support for the receiver sheet that is used with the dye-donor element may be a transparent film of e.g. polyethylene terephthalate, a polyether sulfone, a polyimide, a cellulose ester or a polyvinyl alcohol-co-acetal.
  • the support may also be a reflective one such as a baryta-coated paper, polyethylene-coated paper or white polyester i.e. white-pigmented polyester. Blue-coloured polyethylene terephthalate film can also be used as support.
  • the dye-image-receiving layer may comprise e.g. a polycarbonate, a polyurethane, a polyester, a polyamide, polystyrene-co-acrylonitrile, polycaprolactone, preferably polyvinyl chloride, or mixtures thereof.
  • the dye-image receiving layer may also comprise a heat-cured product of poly(vinyl chloride/co-vinyl acetate/co-vinyl alcohol) and polyisocyanate. Suitable dye-image-receiving layers have been described in e.g. EP 133,011, EP 133,012, EP 144,247, EP 227,094, and EP 228,066.
  • singlet oxygen quenchers such as HALS-compounds (Hindered Amine Light Stabilizers) and/or antioxidants can be incorporated into the dye-image-receiving layer.
  • the dye/binder layer of the dye-donor element or the dye-image-receiving layer of the receiver sheet may also contain a releasing agent that aids in separating the dye-donor element from the receiver sheet after transfer.
  • the releasing agents can also be incorporated in a separate layer on at least part of the dye/binder layer and/or of the dye-image-receiving layer.
  • Suitable releasing agents are solid waxes, fluorine- or phosphate-containing surface-active agents and silicone oils. Suitable releasing agents have been described in e.g. EP 133,012, JP 85/19,138, and EP 227,092.
  • the dye-donor elements according to the invention are used to form a dye transfer image, which process comprises placing the dye/binder layer of the dye-donor element in face-to-face relation with the dye-image-receiving layer of the receiver sheet and image-wise heating from the back of the dye-donor element.
  • the transfer of the dye is accomplished by heating for about several milliseconds at a temperature of 400°C.
  • a monochromic dye transfer image is obtained.
  • a multicolour image can be obtained by using a dye-donor element containing three or more primary colour dyes and sequentially performing the process steps described above for each colour.
  • the above sandwich of dye-donor element and receiver sheet is formed on three occasions during the time when heat is applied by the thermal printing head. After the first dye has been transferred, the elements are peeled apart.
  • a second dye-donor element (or another area of the dye-donor element with a different dye area) is then brought in register with the dye-receiving element and the process is repeated.
  • the third colour and optionally further colours are obtained in the same manner.
  • thermal heads In addition to thermal heads, laser light, infrared flash, or heated pens can be used as the heat source for supplying heat energy.
  • Thermal printing heads that can be used to transfer dye from the dye-donor elements of the present invention to a receiver sheet are commercially available.
  • the dye/binder layer or another layer of the dye element has to contain a compound that absorbs the light emitted by the laser and converts it into heat e.g. carbon black.
  • the support of the dye-donor element may be an electrically resistive ribbon consisting of e.g. a multilayer structure of a carbon-loaded polycarbonate coated with a thin aluminium film.
  • Current is injected into the resistive ribbon by electrically addressing a printing head electrode resulting in highly localized heating of the ribbon beneath the relevant electrode.
  • the fact that in this case the heat is generated directly in the resistive ribbon and that it is thus the ribbon that gets hot leads to an inherent advantage in printing speed using the resistive ribbon/electrode head technology as compared to the thermal head technology, according to which the various elements of the thermal head get hot and must cool down before the head can move to the next printing position.
  • a series I of dye-donor elements for use according to thermal dye sublimation transfer were prepared as follows.
  • a polyethylene terephthalate film support having a thickness of 5.7 »m was coated on both sides with a solution of 1% by weight of an aromatic copolyester essentially consisting of terephthalic acid, isophthalic acid, ethylene glycol, adipic acid, neopentyl glycol, and glycerol in ethyl methyl ketone to form on both sides a subbing layer having a wet thickness of 10 »m.
  • a dye composition forming black was prepared by dissolving 2.4 % by weight of dye A, 6 % by weight of dye B, 2 % by weight of dye C, 6.4 % by weight of dye D in ethyl methyl ketone, and 8 % by weight of binder as identified in Table 1 hereinafter, and dispersing therein 1 % by weight of the above-identified amide wax Ceridust 3910.(tradename)
  • the resulting composition was coated on one side of the subbed support to form a dye/binder layer thereon having a wet thickness of 10 »m.
  • the resulting dye/binder layer was dried by evaporation of the solvent.
  • a top layer having a wet thickness of 10 »m was coated from a 0.5% by weight solution of polyether-modified polydimethylsiloxane (Tegoglide 410 tradename of Goldschmidt) in isopropanol on the resulting heat-resistant polycarbonate layer.
  • polyether-modified polydimethylsiloxane (Tegoglide 410 tradename of Goldschmidt) in isopropanol
  • the different binders were tested to evaluate their behaviour with respect to causing unwanted dye crystallization.
  • the evaluation was made after 7 days of storage of each dye-donor element in rolled-up state at 45°C and a relative humidity of 70%.
  • the evaluation was made by visual and microscopic inspection of each dye-donor element.
  • Four evaluation levels of dye crystallization could be attributed :
  • a series of dye-donor elements comprising a dye/binder layer for forming black were prepared as described in Example 1, with the proviso that the binder (8% by weight of the coating composition for forming the dye/binder layer) was SAN 4 (which is the above-mentioned Luran 388S (trade name) marketed by BASF and which comprises 35% by weight of acrylonitrile units) and that different solid particles as specified in Table 2 hereinafter are used instead of the amide wax Ceridust 3910 (tradename).
  • the amounts of the solid particles used are also indicated in Table 2 (in % by weight of the coating composition for forming the dye/binder layer).
  • the average particle size of the solid particles is given in »m in Table 2.
  • the different solid particles were tested to evaluate their behaviour with respect to causing unwanted sticking of the side showing the dye/binder layer to the contacting rear side of the dye-donor element in rolled-up state.
  • the sticking behaviour was assessed after 7 days of storage of each dye-donor element in rolled-up state at 45°C and a relative humidity of 70%. The evaluation was made by visual inspection of each dye-donor element after unwinding. Four evaluation levels of sticking behaviour could be attributed :
  • Receiver sheets were prepared by coating a subbed polyethylene terephthalate film support having a thickness of 175 »m with a dye-image-receiving layer from a solution in ethyl methyl ketone of 3,6 g/m2 of poly(vinyl chloride/co-vinyl acetate/co-vinyl alcohol) (Vinylite VAGD tradename of Union Carbide), 0,336 g/m2 of diisocyanate (Desmodur N3300 tradename Bayer AG), and 0,2 g/m2 of hydroxy-modified polydimethylsiloxane (Tegomer H SI 2111 tradename of Goldschmidt).
  • Each dye-donor element which as shown in Example 2, demonstrated no sticking in rolled-up state, was then used for printing in combination with a receiver sheet in a Mitsubishi colour video printer CP100E.
  • a pinhole is an area that is part of an image area onto which transfer of dye should have occurred but in which said transfer of dye was substantially inhibited.
  • the loss of density was determined by measuring the density values on the transferred images obtained from the above dye-donor elements and comparing these density values with those obtained from identical dye-donor elements having no particles in the dye/binder layer.
  • the loss of density was also evaluated with the levels bad (standing for a loss higher than 0.20), good (loss less than 0.20), and excellent (no loss).
  • the amounts of solid particles used are also indicated in Table 3 (in % by weight of the coating composition for forming the dye/binder layer).
  • Table 3 Particles according to the invention Size % Pinholes Density loss Micronized polyethylene wax 620XF (tradename) 2.5 1 E E Micronized amide wax Ceridust 3910 (tradename) 4.5 1 E E Micronized amide wax Ceridust 3910 (tradename) 4.5 0.5 E E E Polyethylene wax Lancowax PE1500F (tradename) 3.0 1 E E Polyethylene wax Ceridust 9610 (tradename) ⁇ 22 1 E E Micronized amide wax Lancowax A1601 (tradename) - 1 E E Cerafak 143 (tradename) - 1 E E Polyethylene wax Ceracol 99 (tradename) - 1 E E E Calcium carbonate Socal N6 (tradename) 0.5 E E Needle length :1-3 »m; width: 0.2-0.8 »m Calcium carbonate Socal N2 (tradename) 0.5 E E Needle length :1-3 »m; width: 0.2-0.8 »m Mixture of

Landscapes

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

Claims (10)

  1. Élément donneur de colorant pour les procédés de transfert thermique de colorant comprenant un support présentant sur l'une de ces faces une couche de colorant dans un liant, cette couche contenant au moins un colorant supporté par un liant contenant un copolymère aux unités de styrène et d'acrylonitrile, et des particules solides réparties uniformément, caractérisé en ce que le copolymère contient au moins 15 % en poids d'unités d'acrylonitrile et les particules solides sont choisies parmi les cires solides, le carbonate de calcium et le polyméthylsilylsesquioxane.
  2. Un élément donneur de colorant suivant la revendication 1, caractérisé en ce que les particules solides présentent une grandeur de particule moyenne comprise entre 0,3 et 40 »m.
  3. Un élément donneur de colorant suivant la revendication 1, caractérisé en ce que les particules solides présentent une grandeur de particule moyenne comprise entre 1,5 et 8 »m.
  4. Un élément donneur de colorant suivant l'une quelconque des revendications précédentes, caractérisé en ce que les cires solides sont choisies parmi les cires polyoléfiniques, les cires d'ester et les cires d'amide.
  5. Un élément donneur de colorant suivant la revendication 4, caractérisé en ce que la cire d'amide est une cire d'éthylènebis(stéaramide).
  6. Un élément donneur de colorant suivant l'une quelconque des revendications précédentes, caractérisé en ce que le copolymère contient au moins 60 % en poids d'unités de styrène et au moins 25 % en poids d'unités d'acrylonitrile,
  7. Un élément donneur de colorant suivant l'une quelconque des revendications précédentes, caractérisé en ce que le rapport pondéral du colorant au liant est compris entre 3:1 et 1:2.
  8. Un élément donneur de colorant suivant l'une quelconque des revendications précédentes, caractérisé en ce que son revers a été enduit d'une couche thermostable contenant un polycarbonate dérivant d'un bis(hydroxyphényl)cycloalcane (diphénol).
  9. Élément donneur de colorant pour les procédés de transfert thermique de colorant comprenant un support présentant sur l'une de ces faces une couche de colorant dans un liant, cette couche contenant au moins un colorant supporté par un liant et des particules de polyméthylsilylsesquioxane.
  10. Procédé de formation d'une image moyennant les opérations suivantes :
    - le chauffage sous forme d'image d'un élément donneur de colorant comprenant un support portant une couche de colorant dans un liant, cette couche contenant au moins un colorant, un liant contenant un copolymère aux unités de styrène et d'acrylonitrile, et des particules solides réparties uniformément, caractérisé en ce que le copolymère contient au moins 15 % en poids d'unités d'acrylonitrile et les particules solides sont choisies parmi les cires solides, le carbonate de calcium et le polyméthylsilylsesquioxane, et
    - le transfert du colorant chauffé sous forme d'image sur une feuille réceptrice.
EP19920203496 1992-01-28 1992-11-16 Eléments donneurs de colorant pour le transfert thermique de colorants Expired - Lifetime EP0554583B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19920203496 EP0554583B1 (fr) 1992-01-28 1992-11-16 Eléments donneurs de colorant pour le transfert thermique de colorants

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP19920200229 EP0554576B1 (fr) 1992-01-28 1992-01-28 Elément donneur de colorant pour utilisation dans le transfert thermique de colorant par sublimation
EP92200229 1992-01-28
EP19920203496 EP0554583B1 (fr) 1992-01-28 1992-11-16 Eléments donneurs de colorant pour le transfert thermique de colorants

Publications (2)

Publication Number Publication Date
EP0554583A1 EP0554583A1 (fr) 1993-08-11
EP0554583B1 true EP0554583B1 (fr) 1995-05-24

Family

ID=26131254

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920203496 Expired - Lifetime EP0554583B1 (fr) 1992-01-28 1992-11-16 Eléments donneurs de colorant pour le transfert thermique de colorants

Country Status (1)

Country Link
EP (1) EP0554583B1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE154547T1 (de) * 1993-12-17 1997-07-15 Agfa Gevaert Nv Thermisches farbstoffdiffusionsübertragungsverfahren und farbstoffdonorelement dafür
DE69419307T2 (de) * 1994-03-25 2000-02-24 Agfa-Gevaert N.V., Mortsel Thermotransferbildaufzeichnungsverfahren und Donorelement

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3635141C1 (de) * 1986-10-15 1988-03-03 Pelikan Ag Thermocarbonband mit einer kunststoffgebundenen Aufschmelzfarbe sowie ein Verfahren zur Herstellung dieses Bandes
JP2584457B2 (ja) * 1987-09-18 1997-02-26 花王株式会社 感熱転写用インク及びインクフィルム
US4753921A (en) * 1987-10-13 1988-06-28 Eastman Kodak Company Polymeric subbing layer for slipping layer of dye-donor element used in thermal dye transfer
US4853367A (en) * 1988-03-25 1989-08-01 Eastman Kodak Company Particulate polypropylene waxes for dye-donor element used in thermal dye transfer

Also Published As

Publication number Publication date
EP0554583A1 (fr) 1993-08-11

Similar Documents

Publication Publication Date Title
US5330962A (en) Thermal dye transfer printing method for obtaining a hard copy of a medical diagnostic image
US5374602A (en) Dye-donor elements for thermal dye transfer
EP0554583B1 (fr) Eléments donneurs de colorant pour le transfert thermique de colorants
US5436217A (en) Thermal dye diffusion transfer method and dye donor element for use therein
EP0573080B1 (fr) Elément donneur de colorant pour utilisation dans le transfert thermique de colorant par sublimation
US5674804A (en) Dye donor element for use in thermal dye transfer printing
EP0433496B1 (fr) Couche adhésive pour éléments donateurs de colorant utilisés dans le transfert thermique de colorants
EP0481130B1 (fr) Elément récepteur pour le transfert de colorant par thermosublimation
EP0634291B1 (fr) Elément donneur de colorant pour utilisation selon le procédé de transfert thermique de colorant
USRE36519E (en) Plasticizers for dye-donor element used in thermal dye transfer
US5324706A (en) Dye-donor element for thermal dye sublimation transfer
US5585323A (en) Heat-resistant layer for a dye-donor element
US5376149A (en) Dye-receiving element for thermal dye sublimation
JPH0641673B2 (ja) 熱転写シート
US6337304B1 (en) Thermal transfer recording material
EP0531580B1 (fr) Elément donneur de colorant pour le transfert thermique de colorant par sublimation
EP0594239B1 (fr) Elément donneur de colorant comprenant des colorants magenta de type tricyanovinylaniline
US5342820A (en) Dye-donor element for use according to thermal dye sublimation transfer
EP0574055B1 (fr) Elément recepteur de colorant pour le transfert thermique par sublimation de colorant
EP0598437B1 (fr) Elément donneur de colorant contenant des colorants de type dicyanovinylaniline
EP0671996B1 (fr) Element copulant renfermant des colorants de jaune de dicyanovinylaniline
EP0481129A1 (fr) Elément récepteur pour le transfert de colorant par thermosublimation
EP0593817A1 (fr) Elément donneur de colorant comprenant des colorants de type tricyanovinylaniline

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB NL

17P Request for examination filed

Effective date: 19931216

17Q First examination report despatched

Effective date: 19940111

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB NL

REF Corresponds to:

Ref document number: 69202693

Country of ref document: DE

Date of ref document: 19950629

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19951023

Year of fee payment: 4

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19961130

REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

Effective date: 19961118

REG Reference to a national code

Ref country code: FR

Ref legal event code: D6

BERE Be: lapsed

Owner name: AGFA-GEVAERT N.V.

Effective date: 19961130

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19971029

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19971030

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981116

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19981218

Year of fee payment: 7

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19981116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990730

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000601

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20000601

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20001027

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020702