EP0739748A1 - Moyens de formation d'images en écriture directe par laser - Google Patents

Moyens de formation d'images en écriture directe par laser Download PDF

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Publication number
EP0739748A1
EP0739748A1 EP96302794A EP96302794A EP0739748A1 EP 0739748 A1 EP0739748 A1 EP 0739748A1 EP 96302794 A EP96302794 A EP 96302794A EP 96302794 A EP96302794 A EP 96302794A EP 0739748 A1 EP0739748 A1 EP 0739748A1
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EP
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Prior art keywords
dye
laser
medium according
direct write
leuco
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Granted
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EP96302794A
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German (de)
English (en)
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EP0739748B1 (fr
Inventor
Ranjan C. Patel
Tran Van Thien
Andrew W. Mott
John H.A. Stibbard
Robert J.D. Nairne
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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
    • B41M5/40—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—Infra-red radiation-absorbing materials, e.g. dyes, metals, silicates, C black
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco 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

Definitions

  • the invention relates to imaging media addressable by laser irradiation.
  • the media comprise an IR-absorbing dye and a leuco dye, laser exposure at a wavelength absorbed by the IR dye resulting in conversion of the leuco dye to the corresponding dye.
  • thermographic reduction of silver behenate disclosed in EP-A-0582144, EP-A-0599369 and WO95/07822, thermally-stimulated colour-forming reactions between microencapsulated agents described in Japanese publications JP-A-05 124337, JP-A-05 124338, JP-A-05 124339 and JP-A-05 124340, and the thermal decomposition of certain protected leuco dyes disclosed in US-A-4602263, 4720449, 4720450, 4745046, 4818742, 4826976, 4839335, 4904572 and 4960901.
  • an IR absorbing substance converts incident laser radiation to heat which triggers the image-forming process.
  • identity of the IR absorber so long as it acts as an effective photo
  • the present invention provides an alternative direct-write negative acting media based on the photochemical interaction of an IR dye with a leuco dye.
  • a laser-imageable direct-write medium comprising an infrared dye in photoreactive association with a leuco dye, in which irradiation at a wavelength absorbed by said infrared dye converts said leuco dye to the corresponding dye, characterised in that the said infrared dye comprises a chromophore which is formally the product of a one-electron or two-electron oxidation of a p-phenylenediamine or 4,4'-biphenylenediamine.
  • the media of the present invention have a simple construction and do not require additional oxidising agents or the presence of silver salts (light sensitive or otherwise), although they may optionally be used in combination with thermographic media involving reducible silver salts, as will be described in detail hereinafter.
  • a dye image is produced in direct response to laser irradiation.
  • the image media is capable of high sensitivity and good stability before and after imaging.
  • Preferred infrared dyes suitable for use in the invention have a nucleus represented by formula I(a) or I(b):- in which n is 1 or 2;
  • the rings and substitutents R 1 -R 6 may optionally bear one or more additional substitutents, such as alkyl groups, aryl groups (including fused aryl rings), hydroxy, alkoxy, thioether, mercapto, nitrile, nitro, halide, ketone, ester, amide and carboxylic acid groups.
  • n 1 and X is an anion such as Cl0 4 , CF 3 S0 3 , BF 4 , PF 6 , AsF 6 .
  • each amino group has associated with it a lone pair of electrons which are in conjugated with the delocalised pi-system of the adjacent aromatic ring. Removal of one electron from the system (i.e., one-electron oxidation) gives compounds which may be represented as the amine cation radicals I(a), and removal of a second electron (two-electron oxidation) gives compounds which may be represented as the quinoneimmonium di-cations I(b). It will be appreciated that each of formulae I(a) and I(b) represents only one of many possible resonance structures, and these formulae must be interpreted as being inclusive of said resonance structures.
  • compounds of formula I(b) could equally well be depicted as bis(amine cation radicals), and compounds of formula I(a) as quinoneimmonium monocations.
  • a further complicating factor is the fact that dyes of formula I(a) may disproportionate to a 1:1 mixture of I(b) and I(c).
  • dyes used in the invention will be depicted as quinoneimmonium di-cations as in formula I(b), but this should not be interpreted as excluding monocationic species I(a), nor the presence of significant amounts of the fully-reduced form I(c).
  • Infrared dyes of formula I(a) and/or I(b) are disclosed in numerous publications, notably US-4656121, WO90/12342, JP63319191 and EP-0599369, and are variously known as diamine dication dyes, amine cation radical dyes, bis(amine cation radical) dyes, immonium dyes, di-immonium dyes etc.
  • amine cation radical dye will be used to denote the infrared dyes suitable for use in the invention.
  • amine cation radical dyes of Formula I suitable for use in the invention include:-
  • Compound (1) is available commercially under the trade name Cyasorb IR 165 from Glendale Protective Technologies Inc.
  • Leuco dyes suitable for use in the invention are the essentially colourless reduced forms of visible-absorbing dyes, so that conversion of the leuco to the corresponding dye provides a visible colouration.
  • the leuco dye must be stable to storage at ambient or moderately elevated temperatures in the presence of the IR dye in its ground state. For this reason "protected" leuco dyes, for example, acyl or sulphonyl derivatives are preferred.
  • the leuco dye converts to the corresponding visible dye. It is believed this process involves transfer of an electron from a molecule of the leuco dye to a photoexcited molecule of the IR dye, followed by loss of hydrogen (or the protecting group, if present) to form a molecule of visible dye. The net result is bleaching of the IR dye with concomitant build-up of colour from the visible dye.
  • Leuco dyes suitable for use in the invention are capable of transferring an electron to a photoexcited dye.
  • the HOMO (highest occupied molecular orbital) of the leuco dye has a higher energy than the LUMO (lowest unoccupied molecular orbital) of the photoexcited IR dye.
  • the relationship between the energy of these orbitals is illustrated in Figure 1 of the accompanying drawings.
  • A represents the relevant orbitals of the IR dye in its ground state with the HOMO at energy E and the LUMO at higher energy E*.
  • E the LUMO
  • E leuco energy of the HOMO of the leuco dye
  • the ideal situation occurs when the IR dye and leuco dye are selected so that E ⁇ E leuco ⁇ E* so that electron transfer from the leuco dye to the IR dye tends to occur when the IR dye is in its photoexcited state. If the energy level of the HOMO of the leuco dye is too high, i.e., E leuco is greater than E*, electron transfer will tend to occur in the absence of photoexcitation, being energetically favourable. This leads to spontaneous bleaching of the IR dye on mixing of the IR dye with the leuco dye. This situation may be alleviated to a certain extent by coating the IR dye and the leuco dye in separate layers and/or using sterically hindered leuco dyes to inhibit the ground state reaction.
  • IR dye and leuco dye may be screened empirically by coating roughly equimolar amounts of each on a suitable substrate (in the same or adjacent layers, with or without added binder) and monitoring the absorption spectrum before and after irradiation at or near the absorption maximum of the IR dye.
  • a suitable substrate in the same or adjacent layers, with or without added binder
  • a preferred class of leuco dye suitable for use with dyes such as compound (1), are N-acyl or N-sulphonyl derivatives of leuco-phenazine, -phenoxazine and -phenothiazine dyes. These have a nucleus of formula
  • alkyl, alkoxy and alkylthio groups contain up to 15, preferably up to 5, carbon atoms; and aryl, aryloxy and arylthio groups contain up to 10, preferably up to 6, carbon atoms.
  • the rings and substitutents may optionally bear one or more additional substitutents, such as alkyl groups, aryl groups including fused aryl rings, hydroxy, alkoxy, thioether, mercapto, nitrile, nitro, halide, ketone, ester, amide and carboxylic acid groups.
  • X represents a carbonyl group and R 11 represents an alkyl or aryl group, most preferably aryl, such as phenyl or alkoxyphenyl.
  • R 11 may represent a polyvalent residue linking together two or more leuco-azine structures.
  • R 9 and R 10 represent alkyl groups, Y represents NR 9 R 10 , and Z represents O, or NR 13 where R 13 is alkyl or aryl.
  • Leuco dyes of Formula II have been disclosed in connection with thermographic media employing nitrate salts as oxidising agents in US-A-4563415, and in photothermographic media of the "dry silver” type employing silver salts as oxidising agents in US-A-4594307 and EP-A-0671393 and EP-A-0681210.
  • Leuco dyes of Formula II may be prepared by reduction of the corresponding azine dyes, for example, with sodium hydrosulphide and in situ reaction with a compound of formula R 11 -X-Cl, where R 11 and X have the same meanings as before, as described, for example, in US-A-4563415 and references therein.
  • Formula II does not include all the leuco dyes suitable for use in the invention. Others include:- L6 (yellow)
  • Compound L6 may be prepared from riboflavin by reduction with Zn/acetic acid followed immediately by acylation with acetyl chloride.
  • Direct write imaging elements in accordance with the invention comprise a substrate bearing, in one or more coated layers, the amine cation radical IR dye as described above in photoreactive association with one or more leuco dyes.
  • the substrate may be any suitable dimensionally-stable material, such as paper or plastic film.
  • a preferred material is polyester film of about 50-200 microns, particularly of about 100 micron thickness.
  • Photoreactive association means that the IR dye and the leuco dye must be capable of reacting with each other during laser irradiation of the former. This is clearly possible if both are coated in the same layer, and is also possible when they are coated in separate layers, provided the separate layers melt or otherwise permit mixing of the reagents at the elevated temperatures generated by laser irradiation. As indicated previously, coating the ingredients in separate layers can inhibit unwanted ground state reactions.
  • the ingredients may be coated with or without binders, suitable binders including polyvinylbutyral, vinyl resins, cellulose esters and the like.
  • the leuco dye is coated as an underlayer in a binder comprising a vinyl resin such as a copolymer of vinyl chloride and vinyl acetate for example, of the type supplied by Union Carbide under the trade name "VYNS", while the IR dye is coated as an upper layer in a binder comprising polyvinylbutyral for example, of the type supplied by Monsanto under the trade name "Butvar".
  • a vinyl resin such as a copolymer of vinyl chloride and vinyl acetate for example, of the type supplied by Union Carbide under the trade name "VYNS”
  • the IR dye is coated as an upper layer in a binder comprising polyvinylbutyral for example, of the type supplied by Monsanto under the trade name "Butvar”.
  • a protective topcoat may be added, which may be any transparent material capable of being coated without disturbing the IR dye/leuco dye layer(s). Since the latter are normally coated from organic solvents such as acetone, MEK and the like, preferred topcoats are water soluble polymers such as polyvinylalcohol or gelatin.
  • the IR dye is generally present in an amount sufficient to provide an optical density of at least 0.5 at the intended imaging wavelength, a thin layer containing a high loading of dye being preferable to a thicker layer with a lower loading of dye.
  • the leuco dye is generally present in an amount corresponding to at least one molar equivalent of the IR dye, preferably to at least two molar equivalents, most preferably three molar equivalents. It is a surprising feature of the invention that one molecule of IR dye can apparently convert two or more molecules of leuco dyes to the corresponding dye when the conversion is, as previously theoretically demonstrated not purely thermal. Depending on the desired colour of the generated image, two or more different leuco dyes may be combined in the same coating, for example, to give a black image.
  • Nitrate salts may be incorporated in the media, especially when the leuco dye is of the type depicted in Formula II.
  • a preferred nitrate salt is nickel nitrate, although any of the nitrate salts disclosed in US-A-4563415 may be used.
  • the effect of adding a nitrate salt is to facilitate thermal oxidation of the leuco dye to the corresponding dye, in addition to the photochemical oxidation mediated by the IR dye.
  • the nitrate salt is preferably coated in the same layer as the leuco dye, in an amount corresponding to roughly 50% by weight of the leuco dye.
  • any of the well known coating techniques may be used, such as knife coating, slot coating, roller coating, bar coating or spin coating.
  • Materials in accordance with the invention are imaged by exposure to laser radiation. Any laser emitting in the near IR may be used, but diode lasers and YAG lasers are particularly suitable. In exposed areas, the absorption due to the IR dye disappears, to be replaced by a shorter wavelength absorption corresponding to the oxidised form of the leuco dye(s) originally present in the coating. No thermal or other type of processing is necessary. Furthermore, the density of the image produced is directly proportional to the intensity of the laser exposure, and so continuous tone imaging is possible. Hence the materials are particularly useful in medical imaging applications, for example to record the output of digital X-ray equipment, magnetic resonance scanners, CAT scanners and ultrasound scanners.
  • Best results are obtained from a relatively high intensity laser exposure, for example, of at least 10 17 photons/cm 2 /sec. For a laser diode emitting at 830 nm, this corresponds approximately to an output of 0.1W focused to a 20 micron spot. In the case of YAG laser exposure at 1064nm, a flux of at least 3X10 18 photons/cm 2 /sec is preferred, corresponding roughly to an output of 2W focused to a 20 micron spot.
  • any of the known scanning devices may be used, such as flat-bed scanners, external drum scanners or internal drum scanners.
  • the material to be imaged is secured to the drum or bed for example, by vacuum hold-down and the laser beam is focused to a spot of about 20 microns diameter on the IR-absorbing layer. This spot is scanned over the entire area to be imaged while the laser output is modulated in accordance with electronically stored image information.
  • Two or more lasers may scan different areas of the coating simultaneously, and if necessary, the output of two or more lasers may be combined optically into a single spot of higher intensity.
  • Laser address is normally from the coated side, but alternatively may be through the substrate if the latter is transparent to the laser radiation.
  • the imaging media of the invention may be used in combination with thermographic media comprising a silver salt and a developer capable of reducing said silver salt.
  • thermographic media comprising a silver salt and a developer capable of reducing said silver salt.
  • Thermographic media based on the reduction to silver metal of light-insensitive silver salts (such as silver salts of fatty acids) by reducing agents (such as gallate esters, hindered phenols etc.) are well known, and provide a black image on a colourless background in response to heat.
  • reducing agents such as gallate esters, hindered phenols etc.
  • EP0582144, EP0599369 and WO95/07822 disclose the incorporation of infrared-absorbing dyes in such media, enabling address by a scanning laser, absorption of the laser radiation by the IR dye generating sufficient heat to trigger the redox reaction between the developer and silver salt.
  • Amine cation radical dyes are among the IR dyes disclosed as suitable for this purpose.
  • the media disclosed EP0582144, EP0599369 and WO95/07822 are of the direct-write type in that image density is generated directly by laser exposure, but it is also possible to amplify the directly-formed image by a uniform, post-exposure heat treatment, as disclosed in European Patent Application No. 94115226.6, filed September 27 1994.
  • a problem associated with media of this type is the colour (tone) of the silver image formed. Ideally, this should be a neutral black, but in practice is frequently found to be brown, even when toning agents such as phthalazine or phthalazinone are present.
  • the problem may be solved by additionally incorporating in the media leuco dye capable of photoreducing said amine cation radical dye with concomitant generation of a visible dye, in accordance with the invention described hereinbefore.
  • the colouration provided by the photogenerated dye augments the thermographic silver image and serves to modify its tone.
  • cyan-forming leuco dyes are particularly preferred in this embodiment of the invention, as they can convert a yellowish-brown image tone to a pleasing blue-black.
  • Imaging elements in accordance with this aspect of the invention typically comprise a substrate bearing, in one or more coated layers, a laser-imageable direct-write medium as defined previously, which medium additionally comprising a binder, a silver salt and a developer which is a reducing agent for said silver salt.
  • the substrate may be any suitable dimensionally-stable material, as described previously, but is preferably a polyester film with a thickness of about 50 to 100 ⁇ m.
  • the binder, silver salt and developer may be selected from the relevant materials disclosed in the prior art e.g., as disclosed in EP0582144, EP0599369 and WO95/07822 (which are hereby incorporated by reference).
  • Preferred binders are polyvinylbutyral, vinyl resins, acrylic resins, cellulose esters and the like.
  • Preferred silver salts are light-insensitive silver salts of organic acids, notably silver behenate.
  • Preferred developers are hindered phenols or alkyl esters of hydroxybenzoic acids such as methyl gallate, propyl gallate etc.
  • Other ingredients may also be present, such as toners, surfactants, coating aids etc. as described in the prior art. The relative proportions of the various ingredients are also as described in the prior art.
  • the leuco dye and amine cation radical dye constituting the direct-write media of the invention may be coated separately from the thermographic silver salt media (e.g., as a topcoat), or may be added to the layer(s) comprising the thermographic media.
  • a preferred construction comprises (in sequence) a transparent polyester film substrate, a first layer comprising silver behenate, developer and leuco dye dispersed in a binder, and a second layer comprising IR-absorbing amine cation radical dye in binder.
  • a protective topcoat e.g., of gelatin, polyvinylacohol etc. may be added, but is not essential.
  • Imaging may be carried out using the methods and apparatus detailed earlier.
  • the imaged element may be subjected to uniform thermal processing (e.g., at about 70 to 130°C for about 5 to 30 seconds) to intensify the silver image.
  • IR165 refers to "Cyasorb IR165" which is a bis(amine cation radical) dye as shown in structure (1) above, and was obtained from Glendale Protective Technologies Inc.
  • Leuco dyes L1-L6 had the structure shown above, and were prepared from the corresponding dyes by reduction followed by acylation in situ, according to known methods as disclosed in US-A-4563415, and British patent application nos. 9404805.5 and 9404806.3.
  • This example compares the ability of various IR dyes to oxidise leuco-phenoxazines to the corresponding dyes as a result of laser irradiation.
  • Two-layer constructions were prepared by coating unsubbed polyester base with an underlayer comprising a binder and leuco dye, air drying, then applying a topcoat of IR165 in a binder. Both coatings were made by wire-wound bar at 12 microns wet thickness.
  • the layer compositions were as follows:-
  • This example shows the effect of varying the ratio of IR dye to leuco dye.
  • a first series of coatings were made, similar to Element 4 of Example 2 except that the quantity of IR165 in the top layer was varied from 0.01g to 0.20g.
  • a second series was also prepared, identical to the first except that the underlayer additionally comprised 0.1g nickel nitrate.
  • Sensitivity is seen to increase with increasing amounts of IR dye until the molar ratio of IR dye to leuco dye reaches approximately 1:3, at which point it levels off.
  • This example demonstrates the continuous tone properties of media in accordance with the invention.
  • Element 4 was imaged via the 830nm laser diode with the laser power modulated during scans between 1mW and 116mW in 256 steps in accordance with image information at 1200 dpi in order to simulate continuous tone exposure.
  • the scan speed was 150 cm/sec. This produced a blue-green image of excellent tonal graduation and resolution, with Dmax of 2.4.
  • Element 8 which was prepared in identical fashion to Element 4 - 7 except that instead of a single leuco dye, the underlayer comprised 0.1g each of L1 and L5. In this case a dark blue-grey image was obtained, with Dmax 1.2.
  • binder solution 4.5g silver behenate (10%w/w dispersion in 2-butanone) 3.0g phthalazinone 0.05g leuco dye L1 0.15g methyl gallate 0.075g
  • binder solution 0.5g IR165 0.2g 2-butanone 5.5g
  • binder solution refers to a 20%w/w solution in 2-butanone of poly(tetrahydrophyranyl methacrylate), prepared as described in WO92/09934.
  • Imaging was carried out as described in Example 4 using the 987 nm laser diode source, and the imaged element placed in an oven at 85°C for 20 seconds. A dense blue-black image was obtained for scan speeds of 600 cm/sec or less.
  • a similar element was prepared without the leuco dye, and was subjected to the same imaging and processing routine. Although a silver image of similar density was obtained, it was noticeably browner in appearance.
EP19960302794 1995-04-20 1996-04-19 Moyens de formation d'images en écriture directe par laser Expired - Lifetime EP0739748B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9508028 1995-04-20
GBGB9508028.9A GB9508028D0 (en) 1995-04-20 1995-04-20 Laser addressable direct-write media

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EP0739748A1 true EP0739748A1 (fr) 1996-10-30
EP0739748B1 EP0739748B1 (fr) 1999-03-31

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JP (1) JPH08297346A (fr)
DE (1) DE69601891T2 (fr)
GB (1) GB9508028D0 (fr)

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EP0181085A1 (fr) * 1984-10-01 1986-05-14 Minnesota Mining And Manufacturing Company Précurseurs de colorants phénazine stabilisés et leur emploi dans un système pour la formation d'images
EP0331890A2 (fr) * 1988-03-07 1989-09-13 Seiko Instruments Inc. Matériau pour l'impression multicolore par transfert
EP0366461A2 (fr) * 1988-10-28 1990-05-02 Nippon Paper Industries Co., Ltd. Milieu d'enregistrement optique
EP0384665A2 (fr) * 1989-02-20 1990-08-29 Nippon Paper Industries Co., Ltd. Matériau d'enregistrement optique
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WO1998007576A1 (fr) * 1996-08-20 1998-02-26 Minnesota Mining And Manufacturing Company Compositions photoblanchissables absorbables par laser
EP0841189A1 (fr) * 1996-11-08 1998-05-13 Eastman Kodak Company Elément contenant un colorant stabilisant qui absorbe dans l'infrarouge pour la formation d'une image par laser
WO2003056507A1 (fr) 2001-12-24 2003-07-10 Digimarc Id Systems, Llc Systemes, compositions et procedes de gravure au laser en couleur de documents d'identification
EP1459246A1 (fr) * 2001-12-24 2004-09-22 Digimarc ID Systems, LLC Systemes, compositions et procedes de gravure au laser en couleur de documents d identification
EP1459246A4 (fr) * 2001-12-24 2006-09-06 Digimarc Id Systems Llc Systemes, compositions et procedes de gravure au laser en couleur de documents d identification
US6958181B1 (en) 2003-09-05 2005-10-25 Hewlett-Packard Development Company, L.P. Protected activators for use in leuco dye compositions
US7364841B2 (en) 2003-09-12 2008-04-29 Konica Minolta & Medical Graphic, Inc. Silver salt photothermographic dry imaging material
EP1519223A1 (fr) * 2003-09-12 2005-03-30 Konica Minolta Medical & Graphic Inc. Matériau photothermographique à base de sel d'argent pour le développement à sec
US7138225B2 (en) 2003-09-12 2006-11-21 Konica Minolta Medical & Graphic, Inc. Silver salt photothermographic dry imaging material
US7172992B2 (en) 2003-09-26 2007-02-06 Eastman Kodak Company Biguanide bleaching agent for a thermal-imaging receptor element
US8409790B2 (en) 2004-04-10 2013-04-02 Eastman Kodak Company Method of producing a relief image for printing
US8142987B2 (en) 2004-04-10 2012-03-27 Eastman Kodak Company Method of producing a relief image for printing
US8530117B2 (en) 2004-04-10 2013-09-10 Eastman Kodak Company Method of producing a relief image for printing
WO2005108102A1 (fr) * 2004-04-27 2005-11-17 Hewlett-Packard Development Company, L.P. Compositions de formation de couleur multicouches et methode d'imagerie associee
US7317577B2 (en) 2004-05-14 2008-01-08 Eastman Kodak Company Methods for producing a black matrix on a lenticular lens
US8796583B2 (en) 2004-09-17 2014-08-05 Eastman Kodak Company Method of forming a structured surface using ablatable radiation sensitive material
CN103228455A (zh) * 2010-12-07 2013-07-31 爱克发-格法特公司 防伪文件前体的彩色激光标记方法
CN103228445B (zh) * 2010-12-07 2015-10-21 爱克发-格法特公司 防伪文件和使其安全的彩色激光标记方法
WO2012076493A1 (fr) 2010-12-07 2012-06-14 Agfa-Gevaert Marquage laser couleur d'articles et précurseurs de documents de sécurité
US8921265B2 (en) 2010-12-07 2014-12-30 Agfa-Gevaert N.V. Colour laser marking methods of security documents
CN103228445A (zh) * 2010-12-07 2013-07-31 爱克发-格法特公司 防伪文件和使其安全的彩色激光标记方法
CN103260888A (zh) * 2010-12-07 2013-08-21 爱克发-格法特公司 彩色激光标记制品的安全文档前体
WO2012076406A1 (fr) * 2010-12-07 2012-06-14 Agfa-Gevaert Documents de sécurité et procédés de marquage couleur au laser pour garantir leur sécurité
CN103260888B (zh) * 2010-12-07 2015-05-06 爱克发-格法特公司 彩色激光标记具有聚合物箔的制品的方法和包含聚合物箔和无色层的制品
US8786651B2 (en) 2010-12-07 2014-07-22 Agfa-Gevaert N.V. Colour laser marking methods of security document precursors
EP2463096A1 (fr) * 2010-12-07 2012-06-13 Agfa-Gevaert Documents de sécurité et procédés de marquage laser en couleur permettant de les sécuriser
CN103228455B (zh) * 2010-12-07 2015-04-01 爱克发-格法特公司 防伪文件前体的彩色激光标记方法
US8912118B2 (en) 2010-12-07 2014-12-16 Agfa-Gevaert N.V. Colour laser marking of articles and security document precursors
US8975211B2 (en) 2010-12-07 2015-03-10 Agfa-Gevaert N.V. Security documents and colour laser marking methods for securing them
WO2012171728A1 (fr) * 2011-06-17 2012-12-20 Agfa-Gevaert Marquage laser couleur d'objets et de documents de sécurité
US8921266B2 (en) 2011-06-17 2014-12-30 Agfa-Gevaert N.V. Colour laser marking of articles and security documents
CN103608184A (zh) * 2011-06-17 2014-02-26 爱克发-格法特公司 彩色激光标记制品和安全文件
EP2535201A1 (fr) * 2011-06-17 2012-12-19 Agfa-Gevaert Marquage laser en couleur d'articles et documents de sécurité
CN103608184B (zh) * 2011-06-17 2015-11-25 爱克发-格法特公司 彩色激光标记制品和安全文件
US9067450B2 (en) 2011-09-12 2015-06-30 Agfa-Gevaert N.V. Colour laser marking methods of security document precursors
CN104169099A (zh) * 2012-03-16 2014-11-26 爱克发-格法特公司 彩色可激光标记的层压材料和文件
CN104169099B (zh) * 2012-03-16 2017-03-22 爱克发-格法特公司 彩色可激光标记的层压材料、文件及制备彩色可激光标记文件的方法

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EP0739748B1 (fr) 1999-03-31
GB9508028D0 (en) 1995-06-07
DE69601891D1 (de) 1999-05-06
DE69601891T2 (de) 1999-08-19
JPH08297346A (ja) 1996-11-12

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