EP0655033B1 - Imagerie par transfert thermique - Google Patents

Imagerie par transfert thermique Download PDF

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Publication number
EP0655033B1
EP0655033B1 EP92917131A EP92917131A EP0655033B1 EP 0655033 B1 EP0655033 B1 EP 0655033B1 EP 92917131 A EP92917131 A EP 92917131A EP 92917131 A EP92917131 A EP 92917131A EP 0655033 B1 EP0655033 B1 EP 0655033B1
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EP
European Patent Office
Prior art keywords
layer
receptor
colourant
radiation
donor
Prior art date
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EP92917131A
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German (de)
English (en)
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EP0655033A1 (fr
Inventor
Ranjan Chhaganbhai George Green Cottage Patel
Hsin-Hsin Chou
Keung Kam Kam
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3M Co
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Minnesota Mining and Manufacturing Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • 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
    • B41M5/26—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
    • B41M5/46—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 the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • B41M5/3852—Anthraquinone or naphthoquinone dyes
    • 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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • B41M5/388—Azo dyes
    • 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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • B41M5/39—Dyes containing one or more carbon-to-nitrogen double bonds, e.g. azomethine
    • 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
    • B41M5/46—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 the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
    • B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black

Definitions

  • the present invention relates to a method of thermal transfer imaging, in which a scanning exposure source, such as a laser, is used to effect the thermal transfer of colourant from a donor sheet to a receptor for the thermally transferred colourant.
  • a scanning exposure source such as a laser
  • Thermal transfer imaging involves the imagewise transfer of colourant from a donor sheet to a receptor sheet under the action of heat, the donor and receptor sheets being maintained in intimate, face-to-face contact throughout. This type of imaging is increasingly popular, mainly because it is "dry” (requiring no chemical development) and therefore compatible with the home or office environment.
  • the heat required to effect transfer of the colourant is usually supplied by contacting the assembled (but not bonded) donor and receptor sheets with so called "thermal printheads" comprising arrays of miniature electrically-heated elements, each of which is capable of being activated in a timed sequence to provide the desired imagewise pattern of heating.
  • thermal printheads comprising arrays of miniature electrically-heated elements, each of which is capable of being activated in a timed sequence to provide the desired imagewise pattern of heating.
  • thermal printheads comprising arrays of miniature electrically-heated elements, each of which is capable of being activated in a timed sequence to provide the desired imagewise pattern of heating.
  • thermal transfer media examples include those disclosed in British Patent No. 1385533; British Patent Publication No. 2083726; European Patent Publication Nos. 403932, 403933, 403934, 404042, 405219, 405296, 407744, 408891, 407907 and 408908; US Patent Nos. 3787210, 3946389, 4541830, 4602263, 4788128, 4904572, 4912083, 4942141, 4948776, 4948777, 4948778, 4950639, 4950640, 4952552 and 4973572; International Patent Publication No. PCT WO 88/04237; Japanese Patent Publication Nos. 21-075292 and 30-043294, and Japanese Patent Nos. 51-088016, 56-082293, 63-319191 and 63-319192.
  • the donor sheet comprises a support bearing a donor layer containing the colourant, ordinarily dissolved or dispersed in a binder, with the radiation-absorbing material incorporated in either the same layer as the colourant, e.g., as disclosed in European patent Publication No. 403933, or in a separate underlayer interposed between the support and donor layer, e.g., as disclosed in Japanese Patent No. 63-319191.
  • the donor sheet may be of the diffusion-transfer type (sometimes referred to as "sublimation-transfer” material), whereby colourant is transferred to the receptor in an amount proportional to the intensity of radiation absorbed, or the mass-transfer type, whereby either 0% (zero) or 100% transfer of colourant takes place, depending on whether the absorbed energy reaches a threshold value.
  • diffusion-transfer type sometimes referred to as "sublimation-transfer” material
  • mass-transfer type whereby either 0% (zero) or 100% transfer of colourant takes place, depending on whether the absorbed energy reaches a threshold value.
  • mass-transfer materials both the colourant and binder are transferred to the receptor sheet.
  • the second method involves flood exposure from a momentary source, such as a xenon flash lamp, through a suitable mask held in contact with the assembled donor and receptor sheets.
  • a momentary source such as a xenon flash lamp
  • This method is disclosed in, e.g: Research Disclosure No. 142223 (February 1976); U.S. Patent Nos. 3828359, 4123309, 4123578 and 4157412, and European Patent Publication No. 365222.
  • U.S. Patent Nos. 4123309, 4123578 and 4147412 disclose a composite strip material for use in the preparation of art graphics and the like comprising (a) an accepting tape having a layer of a latent adhesive material and (b) a transfer tape having a donor web carrying a lightly adhered layer of microgranules in face-to-face contact with the adhesive layer. At least one of the microgranule and adhesive layers bears a radiation-absorbing pigment. Upon momentary exposure to a pattern of radiation, the pigment is selectively heated, momentarily softening the adjacent portions of the adhesive layer which, upon solidification, adhere to the microgranules. The accepting and transfer tapes are then separated, with the transferring microgranules adhering to the accepting tape only in the irradiated areas.
  • the pigment is preferably incorporated into the microgranule-containing layer of the transfer tape, thereby providing a direct conductive path to the surface of the adhesive layer.
  • the pigment also serves as a colouring material for the microgranules, with dark coloured microgranules giving dark graphics. Where graphics of a light colour are desired, microgranules of that light color may be used in combination with an accepting tape which comprises a receiving web, a coating of pigment on the receiving web, and a thin layer of adhesive material adhered to the pigment coating. No advantage is taught for placing the pigment in the receptor sheet (other than the visibility of light coloured graphics) and indeed this is said to cause a drop in sensitivity.
  • a xenon flash lamp which produces broad spectrum bluish-white light in a flash is the preferred exposure source, with the desired imagewise pattern of radiation provided by exposing the composite strip material through a mask bearing image information.
  • Xenon flash lamps tend to be bulky, have high power consumption and pose heat dissipation problems, but more importantly, it is very difficult in practice, to obtain large area images of high quality by this method without damaging the mask bearing the image information. This is because, under normal circumstances, the opaque areas of the mask are themselves absorbing and, since the entire area of the mask is illuminated, a large amount of energy is absorbed by the mask with no means by which it can be dissipated quickly. Consequently, high temperatures are generated within the mask, leading to melting or distortion. As the energy absorbed is proportional to the area exposed, the problem becomes more acute with larger-sized images.
  • a xenon lamp is a broad band emitter
  • the use of a xenon flash exposure generally necessitates the use of carbon black and other materials having a similarly broad absorption as the radiation-absorber, in order to make effective use of the available energy.
  • the current trend is to substitute infrared-absorbing dyes for carbon black in pursuit of higher resolution, and also in order to reduce the likelihood of image contamination by the radiation-absorber, e.g., as disclosed in European Patent Publication Nos. 312923, 403930, 403931, 403932, 403933, 403934, 404042, 405219, 405296, 407744, 408891, 408907 and 408908.
  • dyes have a relatively narrow absorption band, higher intensity xenon flashes are required, which compounds the heat-distortion problem described earlier.
  • Japanese Patent No. 3-043294 discloses the use of an infrared-absorbing material in a separate sheet which is held in face-to-face contact with a heat-sensitive medium, but there is no disclosure of thermal transfer as described herein.
  • JP-A-4153087 discloses image receiving materials for use in sublimation thermal transfer or melting thermal transfer in which a light/heat conversion layer and a thermal image receiving layer are positioned on an image receiving support.
  • Thermal transfer donor sheets comprising a layer of an organic or inorganic colourant vapor-deposited on a controlled-release layer are disclosed, respectively, in U.S. Patent Application Serial Nos. 07/775782 (US-A-5139598) and 07/776602, filed October 11th, 1991. Only thermal printhead imaging is taught in connection with these materials.
  • U.S. Patent Nos. 4599298 and 4657840 disclose radiation sensitive imaging materials comprising (sequentially): (i) a support, (ii) a vapor-deposited colourant layer, and (iii) a vapor-deposited layer of a metal, metal oxide or metal sulphide.
  • Layer (iii) may be ablated imagewise using a laser, and the exposed areas of layer (ii) may be transferred to a receptor by application of heat, e.g., by direct contact with a heated platen or roller.
  • European Patent Publication No. 125086 discloses photoresistive elements comprising (sequentially): (i) a support, (ii) a vapor-deposited colourant layer, and (iii) a photoresist overlayer.
  • the imagewise exposed elements are subjected to a development step to remove the resist layer in either the exposed or unexposed regions of the element, depending on whether the resist material is positive or negative-acting, and uniformly heated, e.g., by direct contact with a heated platen, to effect the selective transfer of the colourant.
  • a receptor may receive the transferred colourant or the element with the dye selectively removed can be used as the final image.
  • the colourant can also be transferred without development where the permeability of the resist layer to the colourant is changed on exposure.
  • the present invention seeks to provide alternative thermal transfer methods and thermal transfer materials.
  • thermo transfer imaging which comprises the following steps:
  • the method of the invention utilises a scanning exposure source, such as a laser, to effect the thermal transfer of colourant from a donor sheet to a receptor sheet.
  • a scanning exposure source such as a laser
  • Colourant is used herein in its broadest sense, as covering any material capable of modifying the surface of the receptor and regardless of whether the modification is visible to the naked eye.
  • the radiation-absorbing material is incorporated in the receptor sheet.
  • the inclusion of the radiation-absorbing material in the receptor sheet offers significant advantages over conventional thermal transfer materials, in which the radiation-absorbing material is present in the donor sheet, both in terms of higher resolution and greater sensitivity, since the heating effect is induced directly in the receptor.
  • the receptor sheet includes a receptor layer for thermally transferred colourant, with the radiation-absorbing material containing in the receptor layer or, more preferably, in an ordinarily adjacent underlayer thereto.
  • the donor sheets may be of the diffusion-transfer (sublimation-transfer) type, whereby colourant is transferred to the receptor sheet in an amount proportional to the intensity of the energy absorbed (giving a continuous tone image), but are preferably of the mass-transfer type, whereby essentially 0 (zero) or 100% transfer of colourant takes place depending on whether the absorbed energy exceeds a threshold value.
  • Mass-transfer donor sheets have several advantages, such as the provision of matched positive and negative images (on the donor and receptor sheet respectively), saturated colours, and the ability to image large areas with a uniform optical density, and are well-suited to half-tone imaging.
  • poor resolution and high energy requirements have hampered their use in conventional thermal transfer imaging systems.
  • the method of the invention is capable of producing mass-transfer images of unexpectedly high resolution and low energy requirement.
  • the mass-transfer materials comprise a support bearing a vapor-deposited colourant layer, preferably separated by a controlled release layer, as disclosed in U.S. Patent Applications Serial Nos. 07/775782 (US-A-5139598) and 07/776602, filed October 11th, 1991. These donor sheets are found to give high resolution images with good colour saturation, high transparency and uniform optical density.
  • a thermal transfer medium comprising a donor sheet having a donor layer comprising a vapor-deposited thermally transferable colourant and a receptor sheet comprising a radiation-absorbing material.
  • the donor support may optionally have a controlled release layer (described hereinafter) onto which the colourant is vapor-deposited.
  • the radiation-absorbing material may be contained in a separate, dedicated layer (referred to herein as a "radiation-absorbing layer"), e.g., in an underlayer to the vapor-deposited colourant layer in the donor sheet or any receptor layer(s) in the receptor sheet.
  • the radiation-absorbing material may be included in one of the other component layers of the donor or receptor sheets, e.g., the receptor layer of the receptor sheet. Where the colourant is itself radiation-absorbing such that it is to be regarded as the radiation-absorbing material, then no other radiation-absorbing material is required.
  • the radiation-absorbing material ordinarily absorbing radiation in the wavelength region 600 to 1070 nm, more usually 750 to 980 nm, may comprise any suitable material able to absorb the radiant energy of the exposing source, convert it to heat energy and transfer that energy to the colourant in its immediate vicinity.
  • suitable radiation-absorbing materials include pigments, such as carbon black, e.g., as disclosed in British Patent No. 2083726, and dyes, including: (but not limited to): phthalocyanine dyes, e.g., as disclosed in U.S. Patent No. 4942141; ferrous complexes, e.g., as disclosed in U.S. Patent No.
  • squarylium dyes e.g., as disclosed in U.S. Patent No. 4942141
  • chalcogenopyrylo-arylidene dyes e.g., as disclosed in U.S. Patent No. 4948776
  • bis(chalcogenopyrylo)polymethine dyes e.g., as disclosed in U.S. Patent No. 4948777
  • oxyindolizine dyes e.g., as disclosed in U.S. Patent No. 4948778
  • bis(aminoaryl)polymethine dyes e.g., as disclosed in U.S. Patent No.
  • merocyanine dyes e.g., as disclosed in U.S. Patent No. 4950640
  • tetraarylpolymethine dyes dyes derived from anthraquinones and naphthaquinones, e.g., as disclosed in U.S. Patent No. 4952552
  • cyanine dyes e.g., as disclosed in U.S. Patent No. 4973572
  • trinuclear cyanine dyes e.g., as disclosed in European Patent Publication No. 403933
  • oxonol dyes e.g., as disclosed in European Patent Publication No.
  • indene-bridged polymethine dyes e.g., as disclosed in European Patent Publication No. 407744
  • nickel-dithiolene dye complexes e.g., as disclosed in European Patent Publication No. 408908
  • croconium dyes e.g., as disclosed in EP-A-568267.
  • the radiation-absorbing material is preferably present in an amount and distribution sufficient so that absorption of the exposing radiation by the material will locally generate sufficient heat to enable transfer of the colourant from the donor sheet to the receptor sheet.
  • the amount of radiation-absorbing material required for efficient colourant transfer will vary widely depending on the nature of the material used etc., but it is preferably present in an amount sufficient to provide a transmission optical density of at least 1.0 absorbance units, more preferably at least 1.5 absorbance units at the wavelength of the exposing radiation.
  • the radiation-absorbing layer ordinarily comprises a binder layer having dissolved or dispersed therein the radiation-absorbing material.
  • the binder of the radiation-absorbing layer may comprise any of a number of suitable materials including: poly(vinyl acetals), such as poly(vinyl formal) and poly(vinyl butyral); polycarbonates; poly(styrene-acrylonitrile); polysulfones; poly(phenylene oxide); poly(vinylidene chloride-vinyl acetate) copolymers, and mixtures thereof, although binder materials having a glass-transition temperature (T g ) of greater than 100°C are preferred to ensure that the colourant adheres to the receptor sheet/layer and not the radiation-absorbing layer during thermal transfer.
  • T g glass-transition temperature
  • the radiation-absorbing layer comprises a mixture of dye or pigment and a binder
  • a suitable solvent e.g., lower alcohols, ketones, esters, chlorinated hydrocarbons, and mixtures thereof.
  • a suitable solvent e.g., lower alcohols, ketones, esters, chlorinated hydrocarbons, and mixtures thereof.
  • Any of the well-known solvent-coating techniques may be used, such as knife-coating, roller-coating, wire-wound bars etc.
  • the thickness of the radiation-absorbing layer must be sufficient to provide the necessary optical density, and will depend on factors such as the extinction coefficient of the dye or pigment used, and its solubility in the binder. Relatively thin layers (e.g., up to 5 ⁇ m dry thickness) are preferred.
  • the radiation-absorbing layer may comprise a continuous layer of a solid, radiation-absorbing pigment or dye without a binder.
  • a particularly suitable pigment in this context is "black aluminium oxide", which is a graded mixture of aluminium and aluminium oxide.
  • Layers of this materials may be formed by vapour depositing aluminium metal in the presence of controlled amounts of oxygen, as disclosed in U.S. Patent Nos. 4430366 and 4364995.
  • Very thin ( ⁇ 1 ⁇ m) coatings of this material show a high optical density over a wide wavelength range, covering the visible and infrared, which ensures compatibility with a wide range of exposure sources.
  • Receptor sheets for thermally transferred colourant normally comprises a support sheet having coated on at least one major surface thereof a receptor layer, ordinarily comprising a heat-softenable (low T g ), usually thermoplastic, binder, but when the radiation-absorbing material is present in the receptor layer, then the binder may require a higher T g , typically 100°C or greater.
  • the binder should soften during the imaging process to an extent that is sufficient to induce transfer of the colourant, but is not so great as to cause ablation, lateral flow or transfer to the donor sheet. This is more likely to be a problem when the radiation-absorbing material is present in the receptor layer.
  • the choice of binder is governed to a large extent by the nature of the donor sheet being used. For example, where the donor sheet comprises a layer of vapor-deposited dye or pigment, it is found that low T g receptor layers (containing the radiation-absorbing material) are unsuitable for the reasons outlined above, whereas high T g layers give good results.
  • the radiation-absorbing material When the radiation-absorbing material is present in a separate underlayer, that is, a layer interposed between the support and, ordinarily adjacent, the receptor layer, it is preferably coated in a high T g binder, typically having a T g of greater than 90°C, with the receptor (over)layer comprising a lower T g material having, e.g., a T g of from 40 to 90°C.
  • a high T g binder typically having a T g of greater than 90°C
  • the receptor (over)layer comprising a lower T g material having, e.g., a T g of from 40 to 90°C.
  • Preferred high T g binders include polyesters and polycarbonates, e.g., bisphenol-A polycarbonate.
  • the receptor layer may comprise, e.g., a polycarbonate, a polyurethane, a polyester, a poly(vinyl chloride), poly(styrene-acrylonitrile), poly(ethylene-acrylic acid), poly(caprolactone), poly(vinylidene chloride-vinyl acetate) or a mixtures thereof.
  • the receptor layer may be present in any amount which is effective for the intended purpose.
  • the radiation-absorbing material is present in the receptor sheet, it is preferably colourless to the human eye or is photobleachable, so as to avoid "staining" the image.
  • the final image is that remaining on the donor, or when the image on the receptor is subsequently transferred to a second receptor, such considerations are unimportant.
  • radiation-absorbers with reduced staining properties include phthalocyanines (e.g., as disclosed in U.S. Patent No. 4788128): nickel-dithiolene complexes (e.g., as disclosed in European Patent Publication No. 408908), and croconium dyes (e.g., as disclosed in EP-A-568267).
  • the receptor layer may, subsequent to imaging, be separable from the layer containing the radiation-absorbing material.
  • the support of the receptor can be made of any material to which an image receptive layer can be adhered, includes materials that are smooth or rough, transparent or opaque, flexible or rigid and continuous or sheetlike. The material should be able to withstand the heat required to transfer the colourant without decomposing or distortion. Of course at least one of the donor and receptor sheets must be transparent to the exposing radiation to allow for irradiation of the radiation-absorbing material, with the support material chosen accordingly.
  • Suitable support materials are well known in the art, representative examples of which include (but are not limited to): polyesters, especially poly(ethylene terephthalate) and poly(ethylene naphthalate); polysulfones; polyolefins, such as poly(ethylene), poly(propylene) and poly(styrene); polycarbonates; polyimides; polyamides; cellulose esters, such as cellulose acetate and cellulose butyrate; poly(vinyl chloride), and derivatives thereof.
  • a preferred support material is white-filled or transparent poly(ethylene terephthalate) or opaque paper.
  • the support may also be reflective, such as baryta-coated paper, ivory paper, condenser paper, or synthetic paper.
  • the support generally has a thickness of 0.05 to 5mm, with 0.05mm to 1mm preferred.
  • the receptor (and where appropriate the donor) support may contain fillers, such as carbon black, titania, zinc oxide and dyes, and may be treated or coated with those materials generally used in the formation of films, such as coating aids, lubricants, antioxidants, ultraviolet radiation absorbers, surfactants, and catalysts.
  • the donor sheet comprises a layer of a vapor-deposited colourant and either the colourant itself constitutes the radiation-absorbing material such that it will transfer unaided on irradiation of the assembled donor and receptor sheets, or the donor sheet further comprises a radiation-absorbing material in a separate, ordinarily adjacent, underlayer to the colourant layer, or the receptor comprises a radiation-absorbing material.
  • a vapor-deposited colourant donor layer offers significant advantages over conventional thermal transfer donor materials, in which the colourant is dissolved or dispersed in a binder, both in terms of higher resolution and greater sensitivity (speed).
  • a vapor-deposited colourant is free from contamination by binder materials and produces a pure, more intense image on the receptor sheet. Also the transferred image shows a highly uniform optical density, even when large areas are transferred.
  • Preferred organic colourants include (but are not limited to): copper phthalocyanine and Pigment Yellow PY17 (commercially available from Sun Chemical Corporation) and Pigment violet PV19 (commercially available from Ciba Geigy Corporation).
  • Preferred inorganic colourants include (but are not limited to): metals, such as aluminium, copper, gold, silver etc., and metal oxides, especially "black aluminium oxide", as disclosed in U.S. Patent Nos. 4430366 and 4364995, which gives a neutral black colour.
  • the vapor-deposited colourant layer is preferably coated at a sufficient thickness to provide a transmission optical density of at least 0.5 absorbance units, preferably at least 1.0 absorbance units.
  • the thickness of the colourant layer depends upon the colourant used and the desired minimum optical density, but it can be as thin as a few tens of nanometers or as thick as several micrometers, e.g., 10 to 1000nm thick, preferably 50 to 500nm thick, and more preferably 100 to 400nm thick.
  • the colourant is typically pre-purified by sublimation prior to vapor-deposition.
  • vapour deposition of colourant layers are well known in the art, and include resistive heating methods, radio frequency sputtering, plasma deposition, chemical vapour-deposition, epitaxy deposition and electron beam deposition methods. Specific examples may be found, e.g., in U.S. Patent Nos. 4430366, 4364995, 4587198, 4599298 and 4657840, and U.S. Patent Application Serial Nos. 07/775782 and 07/776602.
  • the colourant layer may be continuous or discontinuous, e.g., it may be deposited in the form of a pattern or in the form of alphanumeric characters by use of suitable masking techniques during the vapour deposition.
  • the colourant layer is continuous.
  • the vapour-deposited colourant layer exhibits anisotropic cohesive forces.
  • it may possess a columnar microstructure (as disclosed in US-A-5139598) in which the cohesive forces operating between the columns are substantially smaller than the cohesive forces acting within individual columns.
  • Factors which are believed to affect the microstructure of the deposited layer include the substrate temperature, the deposition rate (which is a function of the evaporation source temperature, the source-to-substrate distance and the substrate temperature), the deposition angles, and the chamber pressure.
  • the colourant layer itself is suitably radiation-absorbing, and a separate radiation-absorbing material is not required
  • the colourant layer is preferably vapour-deposited onto a controlled release layer present on the support of the donor sheet.
  • a controlled release layer present on the support of the donor sheet.
  • Controlled release layers are particularly useful in the case of inorganic colourants, such as black aluminium oxide, which otherwise adhere too strongly to the most commonly used donor supports, and hence require inconveniently high irradiation intensities to effect transfer.
  • Controlled release layers are described in detail in U.S. Patent Application Serial Nos. 07/775782 (US-A-5139598) and 07/776602, and may comprise, e.g., mixtures of two or more polymers that differ markedly in their affinity towards the donor support, or may comprise inorganic particles, such as boehmite (aluminium monohydrate) particles, hydrophobic silica particles, alumina particles, titania particles etc.
  • controlled release layer is preferred for use with inorganic colourants
  • a particularly preferred controlled release layer for use with black aluminium oxide comprises a coating of boehmite particles, which are available as an aqueous dispersion under the trade name "CATAPAL D” from Vista Chemical Co., Houston, Texas, U.S.A.
  • the former type of controlled release layer is preferred for use with organic colourants.
  • the support of the donor sheet ordinarily comprises a transparent substrate to allow for irradiation of the radiation-absorbing material by the exposure source.
  • suitable support materials include (but are not limited): polyether sulfones; polyimides, such as polyimide-amides and polyether imides; polycarbonates; polyacrylates; polysulfones; cellulose ester, such as ethyl cellulose, cellulose acetate, cellulose acetate hydrogen phthalate, cellulose acetate butyrate, cellulose acetate propionate, cellulose triacetate etc.; a poly (vinyl alcohol-vinyl acetal) copolymers; polyester, such as poly(ethylene terephthalate) which may be biaxially stabilized and poly(ethylene naphthalate); fluorinated polymers, such as poly(vinylidene fluoride) and poly(tetrafluoroethylene-hexafluoropropylene); polyvinyl resins, such as poly(vinyl a
  • a thermal transfer donor sheet comprising (sequentially): a support; a radiation-absorbing layer comprising a dye or the combination of a pigment and a binder, and a layer of a vapor-deposited thermally transferable colourant.
  • the thermal transfer donor sheet is combined with a receptor sheet and irradiated by radiation of an appropriate wavelength for the radiation-absorbing layer.
  • the radiation-absorbing layer converts the radiant energy of the exposure source to thermal energy and transfers the heat to the colourant causing the transfer of colourant to the receptor sheet in an imagewise fashion.
  • the receptor sheet usually comprises a support having coated on at least one major surface thereof a receptor layer, ordinarily comprising a heat-softenable (i.e., T g ⁇ 100°C), usually thermoplastic, binder - although any suitable receptor for thermally transferred colourant may be used.
  • a heat-softenable i.e., T g ⁇ 100°C
  • thermoplastic usually thermoplastic, binder - although any suitable receptor for thermally transferred colourant may be used.
  • any suitable scanning exposure source may be used to effect the thermal transfer of the colourant from the donor sheet to the receptor sheet, although the preferred exposure source is a laser, with the exposure source and radiation-absorbing material selected such that the output radiation closely matches the wavelength of maximum absorption of the radiation-absorbing material, in order to make effective use of the available energy.
  • laser diodes which offer substantial advantages in terms of their small size, low cost, stability, reliability, ruggedness and ease of modulation in accordance with digitally stored information, are preferred.
  • gas ion lasers such as argon and krypton lasers
  • metal vapor lasers such as copper, gold and cadmium lasers
  • solid state lasers such as ruby or YAG lasers
  • diode lasers such as gallium arsenide lasers
  • laser diodes which offer substantial advantages in terms of their small size, low cost, stability, reliability, ruggedness and ease of modulation in accordance with digitally stored information, are preferred.
  • exposure sources emitting in the infrared region from 750 to 950nm are preferred, although any source emitting radiation in the region 600 to 1070nm may be usefully employed in the practice of the invention.
  • the laser is scanned directly over the assembled donor and receptor sheets, while its intensity is modulated in accordance with digitally stored image information.
  • This method is disclosed in, for example: Japanese Patent No. 51-088016, U.S. Patent No. 4973572, British Patent Nos. 1433025, and British Patent Publication No. 2083726, and provides a very good resolution.
  • the various parameters such as laser power, spot size, scan rate and focus position, it is possible to effect thermal transfer imaging without damaging the photographic mask. This is due to the fact that only a small area of the mask is irradiated at any one instant, with the remainder available to act as a heat sink.
  • the optimum exposure parameters depend on a number of variables, such as the sensitivity of the thermal transfer media and the thermal conductivity of both the mask and the radiation absorber.
  • the mask preferably has a thermal conductivity of at least 2x10 -3 Wcm -1° K -1 .
  • the assembled donor and receptor sheets preferably constitute a system of sufficient sensitivity to allow the thermal transfer of colourant at energy levels of less than 4J/cm 2 .
  • the colourant layer is present in the donor sheet as a discontinuous layer, e.g., as a pattern or as alphanumeric characters
  • simple illumination with a continuous, scanning laser is sufficient without the need of a mask.
  • the laser preferably has a power of at least 5mW, with the upper power limit depending on the characteristics of the mask (if used) and the thermal transfer media, as well as the scan speed and spot size.
  • the laser is focused on the radiation-absorbing layer to give an illuminated spot of small, but finite dimensions, which is scanned over the entire area to be imaged.
  • Exposure of the assembled donor and receptor sheets may be carried out from either side, i.e., through the support of the donor sheet, or through the support of the receptor sheet, providing of course that all layers through which the radiation must pass before reaching the radiation-absorbing material are suitably transparent.
  • the laser output may be adjusted via a cylindrical lens to a narrow line, the longer dimension of which is perpendicular to the direction of scan, thereby permitting a larger area to be scanned in one pass.
  • Scanning of the laser may be carried out by any of the known methods, but will normally involve raster scanning, with successive scans abutting or overlapping as desired. Two or more lasers may scan different areas of a large image simultaneously.
  • the donor and receptor sheets and the mask (if used) are held in intimate contact with each other during imaging. This is achieved by subjecting the assembly of mask (if used) and donor and receptor sheets to pressure, ordinarily of at least 10g/mm 2 , preferably at least 40g/mm 2 and typically about 100g/mm 2 .
  • Multicolour images may be produced by repeating the above described imaging methods with successive donor sheets of different colours, using the same receptor in each case.
  • the final image may be transferred from the original receptor to another substrate, such as paper or card stock.
  • This transfer may be carried out by conventional thermal lamination techniques, as disclosed in, e.g., European Patent Publication No. 454083. If the receptor support is transparent, then radiation-induced transfer is also possible.
  • BIS A is bisphenol-A-polycarbonate of the formula: having a glass-transition temperature (Tg) of 160°C - commercially available from Polysciences Inc.
  • CAB 381-20 is cellulose acetate butyrate having a Tg of 138°C - commercially available from Eastman Kodak.
  • CAB 500 is cellulose acetate butyrate having a Tg of 96°C - commercially available from Eastman Kodak.
  • VINYLITE VYNS is a poly(vinylidene chloride-vinyl acetate) copolymer having a Tg of 79°C - commercially available from Union Carbide.
  • BUTVAR B-76 is a poly(vinyl butyral) resin having a Tg of 56°C - commercially available from Monsanto.
  • This Example demonstrates how a scanning exposure source, such as a laser, can be used to effect thermal transfer of colourant from a donor sheet to a receptor sheet comprising a support bearing a receptor layer for thermally transferred colourant, the receptor sheet further comprising a radiation-absorbing material in either the receptor layer (Receptor Sheets 1 to 3) or in a separate underlayer interposed between the support and receptor layer (Receptor Sheets 4 to 7).
  • a scanning exposure source such as a laser
  • Receptor sheets 1 to 7 were prepared as follows:-
  • Receptor Layer a solution of VINYLITE VYNS (1.5g) and IR-Dye I(0.05g) dissolved in a mixture (10g) of methylethylketone and toluene (1:1) was coated onto the support at a wet thickness of 37.5 ⁇ m.
  • Receptor layer a solution of CAB 500 (1g) and IR-Dye I (0.05g) dissolved in a mixture (10g) of methylethylketone and toluene (1:1).
  • Receptor layer a solution of BIS A (3g) and IR-Dye I (0.1g) dissolved in a mixture (30g) of cyclohexanone and dichloromethane (3:2).
  • IR-absorbing layer a mixture of BIS A (6.7g) and IR-Dye 1 (0.05g) in dichloromethane (53.2g) and cyclohexanone (6.7g) was coated onto the support at a wet thickness of 25 ⁇ m.
  • Receptor layer a solution of BUTVAR B-76 (1g) in a mixture (10g) of methyl ethyl ketone and methanol (1:1) was coated at Kbar 1 onto the dried IR-absorbing layer.
  • Kbars are wire wound coating rods, commercially available from R.K. Print Coat Instruments Ltd.
  • IR-absorbing layer as per Receptor Element 4.
  • Receptor layer a solution of VINYLITE VYNS (1.5g) dissolved in a mixture (10g) of methylethylketone and toluene (1:1) was coated at Kbar 1 onto the dried IR-absorbing layer.
  • IR-absorbing layer as per Receptor Element 4.
  • Receptor layer a solution of CAB 500(1g) dissolved in a mixture (10g) of methylethylketone and methanol (1:1) was coated at Kbar 1 onto the dried IR-absorbing layer.
  • IR-absorbing layer as per Receptor Element 4.
  • Receptor layer a solution of CAB 381-20 (1g) dissolved in a mixture (10g) of methylethylketone and methanol (1:1) was coated at Kbar 1 onto the dried IR-absorbing layer.
  • a sample of each of Receptor Sheets 1 to 7 was placed in face-to-face contact with the following donor sheet, with the donor layer of the donor sheet in intimate contact with the receptor layer of the receptor sheet.
  • Donor layer a copper phthalocyanine pigment commercially available from Sun chemicals Inc., was purified by vacuum sublimation at 500°C and 200Nm -2 (1.5 Torr) (argon) pressure.
  • the purified pigment was loaded in a heater made from stainless steel sheet material and the heater positioned in a custom built 30cm bell jar vacuum coater equipped with a diffusion pump and a 15cm web drive, about 4cm below the web.
  • the support was fed onto the web drive before pumping the vacuum chamber down to 6.7x10 -3 Nm -2 (5x10 -5 Torr) pressure.
  • the heater was heated to 410°C using an applied a.c. power supply to vaporise and deposit the pigment onto the support, the web drive moving at a speed of 0.25cm per second.
  • Each of the contacted donor and receptor sheets was overlaid with a UGRA line dot scale mask and addressed with a laser diode emitting at 830 nm using the imaging assembly described hereinafter with reference to Figure 1.
  • the assembled donor and receptor sheets (with mask) are sandwiched between a transparent pressure plate (2) and a support roller (4) biased against the plate (2) by a suitable weight (6) acting through pivot (8).
  • a mirror (10) and focusing lens (12) mounted on a support (14) are provided to focus the beam (16) from the laser diode (18) onto the IR-absorbing layer of the receptor sheet at the point of maximum pressure provided by the support roller (4).
  • a linear stepped motor drive (20) advances the support (14) along slides (22). The assembly of donor and receptor sheets was imaged at a power level sufficient to produce maximum effect on the donor sheet, but with minimum IR-induced heating in the UGRA half-tone mask.
  • Assemblies 1 to 3 demonstrate that, where the donor sheet comprises a vapor-deposited colourant layer and the radiation-absorbing material is present in the receptor layer of the receptor sheet, then the binder for the latter should desirably have a high glass-transition temperature (Tg) typically greater than 100°C.
  • Tg glass-transition temperature
  • VINYLITE VYNS and CAB 500 results in much binder flow and possible ablation, such that mass transfer from the donor sheet is prevented.
  • Assemblies 4 to 7 demonstrate that the provision of the radiation-absorbing material in an underlayer to the receptor layer permits mass transfer from the donor sheet to the receptor sheet in a clean (100% transfer) manner.
  • the best results were obtained from binders having a Tg of from 40 to 90°C, as materials, such as CAB 381-20 and CAB 500, having a Tg greater than 90°C do not melt/soften sufficiently to allow mass transfer.
  • This Example demonstrates how a scanning exposure source can be used to effect thermal transfer from a donor sheet comprising a layer of a vapor-deposited colourant wherein either the colourant is capable of absorbing the exposing radiation (Donor Sheet D) or a separate radiation-absorbing material is present in an underlayer adjacent the colourant layer (Donor Sheets B, C and E).
  • IR-absorbing layer IR-Dye I (0.05g) was added to BIS-A (3.3g) in dichloromethane (26g) and cyclohexanone (3.3g) and the resulting mixture tumble-stirred for 24 hours. The mixture was coated at 37.5 ⁇ m wet thickness onto the support and dried at room temperature. Care was taken to ensure that dust particles did not deposit on the coating. The transmission optical density of the IR-absorbing layer was measured as 1.2 absorbance units at 830nm.
  • IR-absorbing layer as per Donor Sheet B.
  • Colourant layer violet pigment PV19 - commercially available from Ciba Geigy, was purified by vacuum sublimation at 475°C and 2.7Nm -2 (20 mTorr) pressure as detailed above. The purified pigment was vapor-deposited onto the coated support under virtually identical deposition conditions but using a heater temperature of 400°C.
  • IR-absorbing/Colourant layer a boehmite (Al0.0H) subbing layer (0.4% by weight CATAPAL D, commercially available from Vista Chemical Co.; 10 ⁇ m wet thickness) was coated onto the support, dried at 80°C and overcoated with a vapor-deposited layer of "black aluminium oxide" (approximately 0.15 ⁇ m thick), following the procedure described in U.S. Patent Nos. 4364995 and 4430366. The transmission optical density of the layer was determined to be at least 4.6 absorbance units.
  • IR-absorbing layer as per Donor Sheet D.
  • a sample of each of Donor Sheets B to E was placed in face-to-face contact with Receptor Sheets 8 and 9 (see below), with the donor layer of the donor sheet in intimate contact with the receptor layer of the receptor sheet.
  • Support paper base.
  • Each of the contacted donor and receptor sheets was overlaid with a UGRA line dot scale mask and imaged as described in Example 1, but using the following operating conditions: laser energy 10mW, spot size 10 ⁇ m, scan rate 1.5cm per second and a contact pressure (between support roller and pressure plate) of 50gmm -2 . After exposure, the donor and receptor sheets were separated and the percentage (%) dot transfer and the resolved dot range estimated at a resolution of 60 lines per cm. The results are shown in TABLE 2.
  • the degree of dot transfer was, in the majority of cases, excellent (100% transfer) with good resolution, yielding matched positive and negative images on the donor and receptor sheet, respectively.
  • the images were also characterised by a high uniformity of optical density over large areas.
  • VYNS Union Carbide
  • CAPAL D Vander Chemical Co.

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

Abstract

Un procédé d'imagerie par transfert thermique dans lequel une source d'exposition à balayage, par exemple un laser, est utilisée pour effectuer un transfert thermique de colorant d'une feuille émettrice vers une feuille réceptrice pour le colorant transféré thermiquement. Selon un aspect, un matériau absorbant les rayonnements est incorporé dans la feuille réceptrice, de telle sorte qu'une exposition en forme d'image des feuilles émettrice et réceptrice en contact provoque l'échauffement des zones exposées de la feuille réceptrice et donc le transfert thermique du colorant. Selon un autre aspect, la feuille émettrice comprend une couche de colorant déposée par vapeur, et soit le colorant lui-même est capable d'absorber le rayonnement d'exposition, soit la feuille émettrice comprend en plus un matériau absorbant les rayonnements dans une sous-couche séparée de la couche de colorant. De nouveaux types de feuilles émettrices et réceptrices pour un transfert thermique sont également décrits.

Claims (22)

  1. Procédé de formation d'image par transfert thermique qui comprend les étapes suivantes :
    (a) la mise en contact d'une feuille réceptrice et d'une feuille donneuse comportant une couche de donneur comprenant un colorant thermiquement transférable de telle sorte que la couche de donneur soit en contact intime avec la feuille réceptrice, une des feuilles donneuse et réceptrice comprenant une matière absorbante de rayonnement pouvant absorber un rayonnement d'une source d'exposition de telle sorte qu'une exposition selon un mode de formation d'une image des feuilles mises en contact provoque un chauffage dans les régions exposées, ce chauffage provoquant un transfert thermique de colorant de la feuille donneuse à la feuille réceptrice en vue de former une image, et
    (b) l'exposition selon un mode de formation d'une image des feuilles mises en contact en utilisant une source d'exposition à balayage, caractérisé en ce que la couche de donneur comprend une couche d'un colorant déposé en phase vapeur.
  2. Procédé suivant la revendication 1, dans lequel le récepteur comprend un support sur lequel est appliquée une couche de récepteur pour le colorant et la matière absorbante de rayonnement est présente soit dans la couche de récepteur soit dans une couche sous-jacente séparée à celle-ci.
  3. Procédé suivant la revendication 2, dans lequel la couche de récepteur comprend une couche d'un liant contenant la matière absorbante de rayonnement dissoute ou dispersée.
  4. Procédé suivant la revendication 2, dans lequel la feuille réceptrice comprend un support sur lequel sont successivement appliquées une couche absorbante de rayonnement comprenant la matière absorbante de rayonnement et, comme couche supérieure à celle-ci, la couche de récepteur.
  5. Procédé suivant la revendication 1, dans lequel le colorant transférable thermiquement déposé en Phase vapeur peut absorber le rayonnement d'exposition de telle sorte qu'il se transférera sans aide lors de l'exposition de la feuille mise en contact.
  6. Procédé suivant l'une quelconque des revendications précédentes, dans lequel la feuille donneuse comprend un support comportant une couche de séparation contrôlée sur laquelle le colorant est déposé en phase vapeur.
  7. Procédé suivant la revendication 1, dans lequel la feuille donneuse comprend un support sur lequel sont appliquées successivement une couche absorbante de rayonnement comprenant la matière absorbante de rayonnement suivie d'une couche de colorant transférable thermiquement déposée en phase vapeur.
  8. Procédé suivant l'une quelconque des revendications précédentes, dans lequel la couche de colorant est déposée en phase vapeur sous la forme d'un film de topographie anisotrope.
  9. Procédé suivant l'une quelconque des revendications 1 à 4, 6 et 7, dans lequel la matière absorbante de rayonnement est choisie parmi le noir de carbone et d'autres pigments, les complexes de colorants de nickel-dithiolène, les complexes ferreux, les colorants de cyanine, les colorants de mérocyanine, les colorants d'oxyindolizine, les colorants de polyméthine à pont d'indène, les colorants de cyanine trinucléaire, les colorants de bis(aminoaryl)polyméthine, les colorants de tétraarylpolyméthine, les colorants de chalcogénopyrylo-arylidène, les colorants de bis(chalcogénopyrylo)polyméthine, les colorants de phtalocyanine, les colorants de squarylium, les colorants provenant d'anthraquinones et de naphtaquinones et les colorants de croconium.
  10. Procédé suivant l'une quelconque des revendications précédentes, dans lequel la matière colorante transférable thermiquement est un colorant ou pigment.
  11. Procédé suivant la revendication 10, dans lequel la matière colorante est un colorant organique ou un pigment inorganique choisi parmi les métaux, les oxydes métalliques et leurs mélanges.
  12. Procédé suivant l'une quelconque des revendications précédentes, dans lequel l'étape (b) comprend de plus l'assemblage d'un masque photographique en contact intime avec les feuilles donneuse et réceptrice mises en contact et l'exposition de l'assemblage à travers le masque photographique, le rayonnement d'exposition effectuant le transfert thermique de colorant de la feuille donneuse à la feuille réceptrice dans des Zones définies par les régions transparentes du masque.
  13. Procédé suivant la revendication 12, dans lequel une pression d'au moins 10g/mm2 est appliquée à l'assemblage constitué du masque photographique et des feuilles donneuse et réceptrice.
  14. Procédé suivant l'une ou l'autre des revendications 12 et 13, dans lequel les feuilles donneuse et réceptrice mises en contact constituent un système qui est suffisamment sensible pour effectuer le transfert de colorant à des niveaux d'énergie inférieurs à 4J/cm2.
  15. Procédé suivant l'une quelconque des revendications précédentes, dans lequel la source d'exposition à balayage est un laser ou une diode laser.
  16. Procédé suivant la revendication 15, dans lequel le laser a une puissance d'au moins 5mW.
  17. Feuille donneuse de transfert thermique comprenant successivement un support, une couche absorbante de rayonnement comprenant un colorant ou la combinaison d'un pigment et d'un liant et une couche d'un colorant transférable thermiquement déposé en phase vapeur.
  18. Feuille donneuse de transfert thermique suivant la revendication 17, dans laquelle la matière absorbante de rayonnement absorbe le rayonnement ayant une longueur d'onde de 600 à 1070 nm.
  19. Feuille donneuse de transfert thermique suivant l'une ou l'autre des revendications 17 et 18, dans laquelle la couche absorbante de rayonnement comprend une couche d'un liant contenant la matière absorbante de rayonnement dissoute ou dispersée.
  20. Feuille donneuse de transfert thermique suivant la revendication 19, dans laquelle le liant de la couche absorbante de rayonnement a une température de transition vitreuse (Tg) d'au moins 100°C.
  21. Combinaison d'une feuille donneuse de transfert thermique suivant l'une quelconque des revendications 17 à 20 et d'un récepteur pour le colorant transférable thermiquement précité.
  22. Milieu de transfert thermique comprenant une feuille donneuse comportant une couche de donneur comprenant une couche d'un colorant transférable thermiquement déposé en phase vapeur et une feuille réceptrice pour le colorant transféré thermiquement comprenant une matière absorbante de rayonnement.
EP92917131A 1992-08-12 1992-08-12 Imagerie par transfert thermique Expired - Lifetime EP0655033B1 (fr)

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DE69601432T2 (de) * 1995-03-16 1999-10-07 Minnesota Mining & Mfg Schwarz-Metall wärmebildbare Transparenz-Elemente
GB9617416D0 (en) * 1996-08-20 1996-10-02 Minnesota Mining & Mfg Thermal bleaching of infrared dyes
GB9607637D0 (en) * 1996-04-12 1996-06-12 Ici Plc Method receiver medium and apparatus for dye sublimation transfer printing
DE69825909T2 (de) * 1997-09-02 2005-09-08 Kodak Polychrome Graphics Llc, Norwalk Laseradressierbare schwarze thermische übertragungsdonorelemente
WO2000041894A1 (fr) * 1999-01-15 2000-07-20 3M Innovative Properties Company Element de transfert thermique a nouvelle couche de conversion de lumiere en chaleur
EP1670645B1 (fr) 2003-09-26 2012-05-02 Eastman Kodak Company Agent de blanchiment biguanidique pour l'imagerie par transfert thermique
US8142987B2 (en) 2004-04-10 2012-03-27 Eastman Kodak Company Method of producing a relief image for printing
US7317577B2 (en) 2004-05-14 2008-01-08 Eastman Kodak Company Methods for producing a black matrix on a lenticular lens
KR101736043B1 (ko) * 2015-05-28 2017-05-16 김승수 전사 인쇄 방법

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JPH04153087A (ja) * 1990-10-17 1992-05-26 Konica Corp 熱転写用受像材料、転写方法及び印刷校正版の作成方法

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US4587198A (en) * 1984-07-16 1986-05-06 Minnesota Mining And Manufacturing Company Dye transfer image process
US5139598A (en) * 1991-10-11 1992-08-18 Minnesota Mining And Manufacturing Company Vapor deposited multi-layered films--a method of preparation and use in imaging

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JPH04153087A (ja) * 1990-10-17 1992-05-26 Konica Corp 熱転写用受像材料、転写方法及び印刷校正版の作成方法

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DE69215904D1 (de) 1997-01-23
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JPH08503425A (ja) 1996-04-16
EP0655033A1 (fr) 1995-05-31
DE69215904T2 (de) 1997-07-10

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