[go: up one dir, main page]

EP0539001B1 - Rubans donneurs de colorants fluorescents pour l'enregistrement par le transfert thermique - Google Patents

Rubans donneurs de colorants fluorescents pour l'enregistrement par le transfert thermique Download PDF

Info

Publication number
EP0539001B1
EP0539001B1 EP92307718A EP92307718A EP0539001B1 EP 0539001 B1 EP0539001 B1 EP 0539001B1 EP 92307718 A EP92307718 A EP 92307718A EP 92307718 A EP92307718 A EP 92307718A EP 0539001 B1 EP0539001 B1 EP 0539001B1
Authority
EP
European Patent Office
Prior art keywords
fluorescent
white
image
layer
colorant
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
EP92307718A
Other languages
German (de)
English (en)
Other versions
EP0539001A1 (fr
Inventor
Hsin-Hsin C/O Minnesota Mining And Chou
Christopher E. C/O Minnesota Mining And Kunze
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.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0539001A1 publication Critical patent/EP0539001A1/fr
Application granted granted Critical
Publication of EP0539001B1 publication Critical patent/EP0539001B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/14—Multicolour printing
    • 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

Definitions

  • Fluorescent colorants have been used in printing both as a deterrent to counterfeiting and to provide visually attractive images.
  • colorants that are fluorescent in the visible region of the electromagnetic spectrum are used, there is difficulty in obtaining good, detailed fluorescent color images when the colorant is printed over a colored background. Under these conditions, fluorescent colorants tend to appear muddy or washed out.
  • Japanese Published patent application (Kokai) 1-258,990 discloses a thermal transfer donor ribbon coated with heat meltable ink layer regions of 3 primary colors or 4 primary colors plus black and a region containing a fluorescent dye. Overprinting of the respective regions with fluorescent dye is disclosed.
  • Japanese Published patent application (Kokai) 63-281,890 discloses a recording material having a thermo-fusible ink layer containing a fluorescent compound and a thermo-fusible ink layer containing colorant and a thermo-fusible ink layer containing an extender with hiding power.
  • U.S. Patent Nos. 4,627,997; 4,866,025; 4,871,714; 4,876,237; and 4,891,352 describe thermal transfer of various fluorescent materials.
  • the fluorescent materials are patch coated on a donor ribbon along with magenta, cyan and yellow ink patches. These patents are directed at colorless fluorescent inks that emit in the visible spectrum upon exposure to ultraviolet radiation.
  • U.S. Patent 3,647,503 describes a multicolored heat transfer sheet in which colored layers are sequentially coated on a substrate. That patent is directed at multicolored transfer imaging and requires good porosity of the uppermost layer to provide good transfer of dye from lower layers. This is the opposite effect desired in the present invention.
  • WIPO published patent application number 10268 (1989) discloses a thermal transfer ribbon having a transfer coating including a fluorescent coloring material of a reddish-orange hue in a wax material.
  • the transfer coating contains 50-90% wax, including 20-45% hydrocarbon wax, 35-65% paraffin wax, 2-30% carnauba wax and 2-25% acetate copolymer; 5-20% fluorescent pigment, and 5-20% color toning pigment. No mention is made of using an opaque white background layer to improve image clarity.
  • U.S. Patent No. 4,472,479 describes a impact ribbon having a layer of fluorescent dye over-coated with a layer of reflective barrier pigment, and an alternate construction wherein the barrier pigment is included within the fluorescent pigment layer.
  • Barrier pigments disclosed in the patent include finely divided reflective materials such as powdered gold and bronze pigments, and powdered aluminum.
  • Opaque dyes and pigments such as titanium dioxide, silica, and alumina are specifically excluded (column 3, lines 33-44) as having a tendency to blend with the fluorescent materials on impact transfer.
  • the use of reflecting barrier pigments is also described in German Patent 3,042,526.
  • U.S. Patent No. 4,816,344 discloses thermal mass transfer of fluorescent pigments, but makes no mention of using an opaque white pigment layer to provide color clarity.
  • EP-A-208385 discloses a thermal mass transfer system and any reference to white materials in relation to erasing an image of a colour dye image. There is no indication of a white layer deposited as an underlayer to a fluorescent dye.
  • EP-A-313355 which relates to thermal transfer layers does not disclose white thermal transfer layers nor particularly the possibility of depositing a white underlayer in relation to a fluorescent dye.
  • the present invention overcomes deficiencies of the prior art in providing good quality fluorescent images that are generated by thermal transfer onto colored backgrounds.
  • the clarity of fluorescent images produced by this method is improved by transferring an opaque white pigment layer simultaneous or prior to transfer of the fluorescent pigment layer of the donor ribbon.
  • This invention relates to thermal mass transfer imaging. More particularly, this invention relates to transfer of "false color” images using fluorescent pigments.
  • This invention relates to thermal mass transfer printing, particularly thermal mass transfer printing using fluorescent materials.
  • thermal mass transfer donor ribbons of the invention are suitable for imaging applications in desktop publishing, direct digital non-critical color proofing, and short-run sign manufacture, for example and is especially useful for fluorescent color generation.
  • the invention discloses a fluorescent thermal mass transfer donor ribbon comprising a substrate coated on at least a portion thereof with a fluorescent colorant containing ink layer and another portion or the same portion is coated thereon with a opaque white background ink layer.
  • the invention discloses a process for transfer imaging wherein two layers of material, an opaque white background ink layer and a fluorescent colorant containing ink layer, are thermally transferred in a single step to a receptor film, wherein the resulting thermally transferred fluorescent image is exposed.
  • the invention discloses a fluorescent thermal mass transfer donor ribbon comprising interspersed patches of a fluorescent colorant containing transfer layer and an opaque white background ink layer.
  • the invention discloses a process for transfer imaging comprising the steps of thermally transferring a opaque white background ink layer from a donor ribbon to a receptor sheet of film thereby creating a white background image, and thermally transferring a fluorescent colorant containing ink layer from said donor ribbon onto said white background image.
  • thermoly transferable layer containing fluorescent colorant is coated onto a substrate, and another thermally transferable layer containing opaque white pigment is over-coated onto the first thermally transferable layer.
  • thermally transferable layers containing opaque white and fluorescent colorants, respectively are coated in an alternating or parallel patch-type manner.
  • fluorescent thermal mass transfer donor ribbons of the present invention comprise a substrate having coated on at least a portion thereof a fluorescent colorant containing ink layer, wherein said fluorescent colorant containing ink layer is coated thereon with an opaque white background ink layer.
  • fluorescent colorant thermal transfer ribbons are prepared by coating a fluorescent colorant containing ink onto at least a portion of one side of a suitable substrate and coating an opaque white background ink layer onto the exposed fluorescent colorant containing layer. In this embodiment, it is desirable to reduce the thickness of the opaque white background ink layer to facilitate good thermal mass transfer imaging of both the white and fluorescent ink layers.
  • a high pigment to binder ratio is obtained improving the light scattering ability of the opaque white background layer and permitting the use of thin opaque white background ink layers.
  • Fluorescent colorant containing ink layers of the present invention comprise a fluorescent colorant and a binder. Preferably, they are prepared by dispersing colorant in a binder.
  • Opaque white background ink layers comprise a white pigment in a binder.
  • the binder for either of the two embodiments of thermally transferable layers comprises at least one of a wax-like substance and a polymeric resin.
  • Fluorescent colorants suitable for use in the present invention include organic and inorganic fluorescent dyes and pigments.
  • fluorescent inorganic pigments include zinc sulfide-copper mixtures, zinc sulfide-copper plus cadmium sulfide-copper mixtures, zinc oxide-zinc mixtures and the like.
  • fluorescent organic pigments include Lumogen L yellow, Lumogen L Brilliant Yellow, Lumogen L Red Orange; A, AX, D, and GT series Day-GloTM pigments (Day-Glo Corp., Cleveland, OH), and the like.
  • fluorescent dyes include thioflavine (Colour Index (CI) 49005); Basic Yellow BG (CI 46040); Fluorescein (CI 45350); Rhodamine B (CI 45170); Rhodamine 6G (CI 45160); Eosin (CI 45380); and conventional white fluorescent brighteners such as, for instance, as CI fluorescent Brightening Agent 85, 166 and 174, fluorescent colorants may be those obtained by rendering the above mentioned fluorescent dyes oil soluble (and simultaneously water insoluble) with organic acids such, for instance, as Oil Pink #312 obtained by rendering Rhodamine B oil soluble and Barifast Red 1308 obtained by rendering Rhodamine 6G oil soluble (produced by Orient Chemical Co.).
  • Fluorescent colorants may also be obtained by lake formation of the above fluorescent dyes with metal salts and other precipitants such as, Fast Rose and Fast Rose Conc obtained by lake formation of Rhodamine 6G (produced by Dainichi Seika Kogyo K.K.), and so forth.
  • the present invention may be employed with ultraviolet or infrared fluorescing colorants, it is preferred that the fluorescent colorants of the present invention should have fluorescence emission in the wavelength range of 350 to 700 nm, more preferably in the range of 400 to 650 nm.
  • Suitable white pigments include, but are not limited to, white metal oxides such as titanium dioxide, zinc oxide, aluminum oxide and hydroxide, magnesium oxide, etc.; white metal sulfates such as barium sulfate, zinc sulfate, calcium sulfate, etc., and white metal carbonates such as calcium carbonate, etc.
  • white metal oxides such as titanium dioxide, zinc oxide, aluminum oxide and hydroxide, magnesium oxide, etc.
  • white metal sulfates such as barium sulfate, zinc sulfate, calcium sulfate, etc.
  • white metal carbonates such as calcium carbonate, etc.
  • the white pigments may be optionally treated with surface modifying agents to improve their dispersibility in the binder.
  • Suitable wax-like substances have a melting point or softening point of from about 50° to 140° C , and include but are not limited to higher fatty acid ethanolamines such as stearic acid monoethanolamide, lauric acid monoethanolamide, coconut oil monoethanolamide; higher fatty acid esters such as sorbitan behenic acid ester; glycerine higher fatty acid esters such as glycerine monostearic acid ester, acylated sorbitols such as acetylsorbitol and benzoylsorbitol, acylated mannitols such as acetylmannitol; and waxes such as beeswax, paraffin wax, carnauba wax, ChlorezTM waxes, etc.; and mixtures thereof.
  • higher fatty acid ethanolamines such as stearic acid monoethanolamide, lauric acid monoethanolamide, coconut oil monoethanolamide
  • higher fatty acid esters such as sorbitan behe
  • Preferred wax-like materials include stearic acid monoethanolamide (mp 91°-95° C), lauric acid monoethanolamide (mp 80°-84° C), coconut oil fatty acid monoethanolamide (mp 67°-71° C), sorbitan behenic acid ester (mp 68.5° C), sorbitan stearic acid ester (mp 51° C), glycerine monostearic acid ester (mp 63° - 68° C), acetyl sorbitol (mp 99.5° C.), benzoyl sorbitol (mp 129° C), and acetyl mannitol (mp 119°-120° C).
  • Suitable polymeric resins have melting or softening points in the range of about 20° to 180° C, preferably in the range of 40° to 140° C, more preferably in the range of 55° to 120° C, and most preferably in the range of 60° to 100° C and include, but are not limited to, polycaprolactone, polyethylene glycols, aromatic sulfonamide resins, acrylic resins, polyamide resins, polyvinyl chloride and chlorinated polyvinyl chloride resins, vinyl chloride-vinyl acetate copolymers, alkyd resins, urea resins, melamine resins, polyolefins, benzoguanamine resins and copolycondensates or copolymers of the above resin materials.
  • Preferred polymeric resins are polycaprolactones having an average molecular weight of 10,000 g/mol (mp 60°-65° C) polyethylene glycols having an average molecular weight of 6000 g/mol (mp ⁇ 62° C), low condensation polymerized melamine toluenesulfonamide resins (sp ⁇ 105° C), low condensation polymerized benzyltoluene sulfonamide resins (sp ⁇ 68° C), acrylic resins (sp ⁇ 85° C), and linear polyamide resins (sp ⁇ 60° C).
  • mp and “sp” refer to "melting point” and "softening point,” respectively.
  • the fluorescent colorant containing ink layer and opaque white background ink layer have a melting point (mp) or softening point (sp) of 50°-140° C to enhance the thermal transferring property.
  • mp melting point
  • sp softening point
  • Suitable substrate materials for the thermal mass transfer donor element may be any flexible material to which a fluorescent colorant containing ink layer may be adhered.
  • Suitable substrates may be smooth or rough, transparent, opaque, and continuous or sheet-like. They may be essentially non-porous.
  • Preferred backings are white-filled or transparent polyethylene terephthalate or opaque paper.
  • Non-limiting examples of materials that are suitable for use as a substrate include polyesters, especially polyethylene terephthalate, polyethylene naphthalate, polysulfones, polystyrenes, polycarbonates, polyimides, polyamides, cellulose esters, such as cellulose acetate and cellulose butyrate, polyvinyl chlorides and derivatives, etc.
  • the substrate generally has a thickness of 1 to 500 »m, preferably 2 to 100 »m, more preferably 3 to 10 »m.
  • non-porous in the description of the invention it is meant that ink, paints and other liquid coloring media will not readily flow through the substrate (e.g., less than 0.05 ml per second at 7 torr applied vacuum, preferably less than 0.02 ml per second at 7 torr applied vacuum).
  • the lack of significant porosity prevents absorption of the heated receptor layer into the substrate.
  • fluorescent thermal mass transfer ribbons are prepared by coating a fluorescent colorant containing ink layer and an opaque white background ink layer onto one side of a suitable substrate in a pattern such that the two ink layers are interspersed in a manner so that the area of the substrate covered by each ink layer is substantially equal.
  • the white and the fluorescent image may be identical (coextensive in all directions), substantially overlap, completely overlap, outline one another, or border each other.
  • the fluorescent thermal mass transfer ribbons of the present invention are generally employed in combination with a receptor sheet in a process for transfer imaging wherein two layers of material, an opaque white background ink layer and a fluorescent colorant-containing ink layer, are transferred in a single step or sequential steps.
  • the fluorescent thermal transfer donor ribbons of the invention are suitable for image production in desktop publishing, direct digital non-critical color proofing, short run sign manufacture, and so forth, especially for graphics desiring fluorescent color generation.
  • Coating of the thermally transferable layers on the donor sheets may be accomplished by many standard web coating techniques such as imprint gravure, single or double slot extrusion coating, and the like. Imprint gravure is particularly useful for patch-type coatings in which there are interspersed regions of opaque white and fluorescent colorants on a ribbon or sheet. Layer coating thicknesses useful in the present invention are 0.1 to 50 »m, preferably 0.5 to 10 »m, most preferably 1 to 6 »m.
  • the donor ribbons of the present invention are generally used in thermal printing by contacting the transferable layer of the donor ribbon with a receptor sheet or film such that at least one thermally transferable donor layer is in contact with the receptor sheet.
  • Heat is applied, either from a thermal stylus or an infrared heat source such as an infrared laser or a heat lamp and the donor layer is transferred to the receptor.
  • the heat may be applied to the back of either the donor ribbon or receptor sheet or may be directly introduced to a transferable donor layer.
  • Preferred receptor sheet materials are Dai Nippon Type I and Type V receptor films (Dai Nippon Insatsu K.K.,Tokyo, Japan), Dupont 4-CastTM receptor film (E.I. Dupont de Nemours Co., Wilmington, DE), Scotchcal film (3M Co., St. Paul, MN), and polyethylene terephthalate.
  • the receptor sheets may be colored, that is they may have an optical density of at least 0.2 in the visible region of the electromagnetic spectrum.
  • a release coating is applied to the back side of the donor ribbon (i.e., the side opposite the thermally transferable donor layer(s)) to improve handling characteristics of the ribbon and reduce friction.
  • Suitable release materials include, but are not limited to, silicone materials including poly(lower alkyl)siloxanes such as polydimethylsiloxane and silicone-urea copolymers, and perfluorinated compounds such as perfluoropolyethers.
  • This comparative example demonstrates the preparation of a fluorescent colorant donor ribbon and formation of fluorescent images on various receptor films by thermal transfer.
  • GT series Aurora Pink pigment Day-Glo Corp., Cleveland, OH
  • ChlorowaxTM 70 a chlorinated paraffin wax, mp 102° C, obtained from Occidental Petroleum Co.,
  • the resultant transferred image had slightly uneven edges on the dots at 7.9 dpm (200 dpi resolution); (b) 76 »m PET film (at approximately 1.6 J/cm2 using the same thermal printer as in (a), a resolution of 7.9 dpm (200 dpi) for the transferred image although dots at 7.9 dpm (200 dpi) were slightly uneven; (c) Type 1 and Type V Dai Nippon dye transfer receptors (Dai Nippon Insatsu K.K.,Tokyo, Japan) at approximately 1.6J/cm2 using the same thermal printer as in (a) transferred dot images at 7.9 dpm (200 dpi) were slightly uneven.
  • This example demonstrates the preparation of a fluorescent pigment donor ribbon construction consisting of a substrate coated sequentially with fluorescent pigment containing layer and an opaque white layer.
  • This film was printed onto the Dai Nippon dye Type I transfer receptor sheet at approximately 1.6 J/cm2 using the thermal printer of the Comparative Example at a resolution of 7.9 dpm (200 dpi).
  • the resultant transferred fluorescent image was visually determined to have improved color clarity compared to the images in the Comparative Example.
  • This example demonstrates an alternate printing method in which an opaque white layer is printed and then overprinted with fluorescent material.
  • a solution of fluorescent pigment was mixed as in the Comparative Example. This solution was coated out at approximately 5 »m onto 6 »m PET film. This film was dried 3 minutes at 70° C.
  • This example demonstrates a two layer construction wherein an opaque white background ink layer is coated on a fluorescent colorant containing ink layer supported by a substrate.
  • EHEC low an ethyl hydroxyethyl cellulose with extra low viscosity, flow temperature > 175° C, obtained from Dow Chemical Co., Midland, MI.
  • Each dispersion was independently mixed in a ball mill for 6 to 10 hr.
  • the fluorescent layer was coated onto 6 »m polyethylene terephthalate film at 8.33 »m wet thickness using a number 5 Meyer bar (R&D Specialties, Webster, NY). The coating was air dried for 2 minutes then the opaque white layer was coated on top of the fluorescent layer at a 5 »m wet thickness using a number 3 Meyer bar. The coated film was oven dried for about 2 min at 70° C.
  • Image transfer was accomplished using the thermal printer of the Comparative Example wherein the opaque white and fluorescent layer were transferred simultaneously using a thermal energy of 3.8 J/cm2.
  • the fluorescent image had good color clarity as judged by eye and a resolution of at least 7.9 dpm (200 dpi).
  • Fluorescent dispersions in toluene were prepared according to the method of the Comparative Example in amounts described in Table 1, and alternately coated with an opaque white dispersion according the method of Example 5 in amounts described in Table 1 onto 6 »m thick, 22.9 cm (9 inch) wide polyethylene terephthalate film in 33.0 cm (13 inch) long patches and oven dried two to 3 minutes at 60 to 80° C.
  • the thermally transferable fluorescent films thus prepared were imaged onto Dai Nippon Type V receptor film using the thermal printer of the Comparative Example 1.
  • the fluorescent layer was coated onto 6»m PET film at 8.33 »m wet thickness using a number 5 Meyer Bar (R&D Specialties, Webster, NY). The coating was air dried for 3 minutes, then the opaque layer was coated on top of the florescent layer at a 5 »m wet thickness using a number 3 Meyer bar. The film was oven-dried for about 5 minutes at 70°C.
  • Image-transfer was accomplished using the thermal printer of the Comparative Example wherein the opaque white and fluorescent layer were transferred simultaneously using a thermal energy of 3.8 J/cm2.
  • the fluorescent image had good color clarity as judged by eye and a resolution of at least 7.9 dpm (200 dpi).

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Impression-Transfer Materials And Handling Thereof (AREA)

Claims (9)

  1. Elément donneur de transfert thermique de masse comprenant un substrat sur lequel sont appliqués un colorant fluorescent transférable thermiquement et une matière blanche opaque transférable thermiquement, ledit élément donneur pouvant transférer un fond blanc sur une surface réceptrice avec une couche de colorant fluorescent sur le fond blanc.
  2. Elément donneur suivant la revendication 1, dans lequel le colorant fluorescent comprend une couche sur le substrat et la matière blanche opaque comprend une couche appliquée sur le colorant fluorescent.
  3. Elément donneur suivant la revendication 1, dans lequel le colorant fluorescent comprend des plaques de colorant sur le substrat et la matière blanche opaque comprend des plaques de colorants sur des aires du substrat où le colorant fluorescent n'est pas présent.
  4. Elément donneur suivant l'une quelconque des revendications 1, 2 et 3, dans lequel la matière blanche opaque comprend des oxydes métalliques blancs, des sulfates métalliques blancs ou des carbonates métalliques blancs.
  5. Elément donneur suivant l'une quelconque des revendications précédentes, dans lequel la matière blanche opaque est mélangée à une cire ou résine polymérique.
  6. Procédé de formation d'une image fluorescente sur une surface réceptrice, comprenant un transfert thermique de masse d'une image blanche sur une surface réceptrice et un transfert thermique de masse au-dessus d'au moins une partie de l'image blanche d'une image fluorescente.
  7. Procédé suivant la revendication 6, dans lequel les transferts de l'image blanche et de l'image fluorescente sont réalisés en même temps.
  8. Procédé suivant la revendication 6, dans lequel les transferts de l'image blanche et de l'image fluorescente sont réalisés à la suite l'un de l'autre.
  9. Procédé suivant la revendication 6, dans lequel l'image blanche et l'image fluorescente se recouvrent sensiblement et l'image blanche et l'image fluorescente sont sensiblement les mêmes.
EP92307718A 1991-10-25 1992-08-24 Rubans donneurs de colorants fluorescents pour l'enregistrement par le transfert thermique Expired - Lifetime EP0539001B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US78446991A 1991-10-25 1991-10-25
US784469 1991-10-25

Publications (2)

Publication Number Publication Date
EP0539001A1 EP0539001A1 (fr) 1993-04-28
EP0539001B1 true EP0539001B1 (fr) 1995-06-21

Family

ID=25132532

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92307718A Expired - Lifetime EP0539001B1 (fr) 1991-10-25 1992-08-24 Rubans donneurs de colorants fluorescents pour l'enregistrement par le transfert thermique

Country Status (6)

Country Link
EP (1) EP0539001B1 (fr)
JP (1) JPH05212973A (fr)
KR (1) KR930007680A (fr)
CA (1) CA2076186A1 (fr)
DE (1) DE69203073T2 (fr)
TW (1) TW211545B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7063264B2 (en) 2001-12-24 2006-06-20 Digimarc Corporation Covert variable information on identification documents and methods of making same
US7661600B2 (en) 2001-12-24 2010-02-16 L-1 Identify Solutions Laser etched security features for identification documents and methods of making same
US7789311B2 (en) 2003-04-16 2010-09-07 L-1 Secure Credentialing, Inc. Three dimensional data storage
US7793846B2 (en) 2001-12-24 2010-09-14 L-1 Secure Credentialing, Inc. Systems, compositions, and methods for full color laser engraving of ID documents
US7804982B2 (en) 2002-11-26 2010-09-28 L-1 Secure Credentialing, Inc. Systems and methods for managing and detecting fraud in image databases used with identification documents
US7815124B2 (en) 2002-04-09 2010-10-19 L-1 Secure Credentialing, Inc. Image processing techniques for printing identification cards and documents
US7824029B2 (en) 2002-05-10 2010-11-02 L-1 Secure Credentialing, Inc. Identification card printer-assembler for over the counter card issuing

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9217321D0 (en) * 1992-08-14 1992-09-30 Columbia Ribbon & Manufacturin Thermal transfer printing ribbon and method of printing
JPH06328862A (ja) * 1993-05-07 1994-11-29 Minnesota Mining & Mfg Co <3M> 熱染料転写画像形成に使用する質量転写可能なドナーリボン
JPH0752552A (ja) * 1993-07-12 1995-02-28 Minnesota Mining & Mfg Co <3M> 熱染料転写画像用質量転写ドナーリボン
US5830824A (en) * 1997-02-28 1998-11-03 Eastman Kodak Company Plasticizers for dye-donor element used in thermal dye transfer
US7153561B2 (en) 2003-07-11 2006-12-26 Kimberly-Clark Wordwide, Inc. Absorbent article with graphic design thereon
US7364085B2 (en) 2003-09-30 2008-04-29 Digimarc Corporation Identification document with printing that creates moving and three dimensional image effects with pulsed illumination

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4880324A (en) * 1985-06-24 1989-11-14 Canon Kabushiki Kaisha Transfer method for heat-sensitive transfer recording
JPH01108089A (ja) * 1987-10-21 1989-04-25 Canon Inc 感熱転写材
WO1989010268A1 (fr) * 1988-04-28 1989-11-02 Ncr Corporation Ruban de transfert thermique
GB8826456D0 (en) * 1988-11-11 1988-12-14 Ici Plc Dyesheet

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7063264B2 (en) 2001-12-24 2006-06-20 Digimarc Corporation Covert variable information on identification documents and methods of making same
US7661600B2 (en) 2001-12-24 2010-02-16 L-1 Identify Solutions Laser etched security features for identification documents and methods of making same
US7793846B2 (en) 2001-12-24 2010-09-14 L-1 Secure Credentialing, Inc. Systems, compositions, and methods for full color laser engraving of ID documents
US7815124B2 (en) 2002-04-09 2010-10-19 L-1 Secure Credentialing, Inc. Image processing techniques for printing identification cards and documents
US8833663B2 (en) 2002-04-09 2014-09-16 L-1 Secure Credentialing, Inc. Image processing techniques for printing identification cards and documents
US7824029B2 (en) 2002-05-10 2010-11-02 L-1 Secure Credentialing, Inc. Identification card printer-assembler for over the counter card issuing
US7804982B2 (en) 2002-11-26 2010-09-28 L-1 Secure Credentialing, Inc. Systems and methods for managing and detecting fraud in image databases used with identification documents
US7789311B2 (en) 2003-04-16 2010-09-07 L-1 Secure Credentialing, Inc. Three dimensional data storage

Also Published As

Publication number Publication date
DE69203073D1 (de) 1995-07-27
TW211545B (fr) 1993-08-21
JPH05212973A (ja) 1993-08-24
KR930007680A (ko) 1993-05-20
CA2076186A1 (fr) 1993-04-26
DE69203073T2 (de) 1996-01-25
EP0539001A1 (fr) 1993-04-28

Similar Documents

Publication Publication Date Title
US5397763A (en) Method for heat transfer recording
EP0539001B1 (fr) Rubans donneurs de colorants fluorescents pour l&#39;enregistrement par le transfert thermique
EP1270246B1 (fr) Méthode pour former des images fluorescentes, impression, et feuille pour transfert thermique
JP3656772B2 (ja) 熱転写シート、印字物及び記録方法
US4866025A (en) Thermally-transferable fluorescent diphenylpyrazolines
CA2005942A1 (fr) 7-aminocarbostyryles fluorescents transferables par voie thermique
CA2004697A1 (fr) Composes fluorescents transferables thermiquement
EP0623479B1 (fr) Rubans donneurs de colorants pour l&#39;enregistrement par transfert thermique
EP1088675B1 (fr) Matériau d&#39;enregistrement par transfer thermique, procédé de formation d&#39;image et support d&#39;image
JP2003011588A (ja) 印画物及びその印画で使用する熱転写リボン
EP1193081B1 (fr) Composition d&#39;encre et feuille pour l&#39;impression par transfert thermique l&#39;utilisant
JP5062267B2 (ja) 印画物
GB2351158A (en) Process for controlling the gloss of a thermal dye transfer image using expandable microspheres
US5506189A (en) Mass transferable donor ribbons for use in thermal dye transfer imaging
EP0365392B1 (fr) Elément donneur de colorant magenta utilisé pour le transfert thermique et feuille de transfert thermique l&#39;utilisant
US5593803A (en) Process for applying images to non-adhesive surfaces in thermal dye transfer imaging
JP2003025736A (ja) 熱転写シートおよび印画物
JPH0740668A (ja) 熱転写シート
JP2004066828A (ja) 感熱色素転写プリント及びその上にオーバーレイヤーを形成するための方法
JPH06219060A (ja) 熱転写受像シート
EP1216840B1 (fr) Elément donneur de colorant contenant une couche protectrice transférable
JP2919505B2 (ja) 透明型ｏｈｐ用熱転写受像シート
JPH021387A (ja) サーマルダイトランスファーに用いられる色素供与素子におけるダイトランスファー効率の向上
JP2020199686A (ja) 積層体、積層体と熱転写シートとの組合せ、積層体と熱転写シートと中間転写媒体との組合せ、及び印画物
JPH09136490A (ja) 熱転写用被転写体及び熱転写画像形成方法

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 IT NL

17P Request for examination filed

Effective date: 19931025

17Q First examination report despatched

Effective date: 19931116

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

ITF It: translation for a ep patent filed
AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL

REF Corresponds to:

Ref document number: 69203073

Country of ref document: DE

Date of ref document: 19950727

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

Ref country code: FR

Payment date: 19970721

Year of fee payment: 6

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

Ref country code: NL

Payment date: 19970722

Year of fee payment: 6

Ref country code: DE

Payment date: 19970722

Year of fee payment: 6

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

Ref country code: BE

Payment date: 19970725

Year of fee payment: 6

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

Ref country code: GB

Payment date: 19970728

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: 19980824

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

Ref country code: BE

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

Effective date: 19980831

BERE Be: lapsed

Owner name: MINNESOTA MINING AND MFG CY

Effective date: 19980831

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: 19990301

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

Effective date: 19980824

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: 19990430

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

Effective date: 19990301

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: 19990601

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: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050824