EP0687572A1 - Méthode pour l'enregistrement par la chaleur - Google Patents

Méthode pour l'enregistrement par la chaleur Download PDF

Info

Publication number
EP0687572A1
EP0687572A1 EP95201340A EP95201340A EP0687572A1 EP 0687572 A1 EP0687572 A1 EP 0687572A1 EP 95201340 A EP95201340 A EP 95201340A EP 95201340 A EP95201340 A EP 95201340A EP 0687572 A1 EP0687572 A1 EP 0687572A1
Authority
EP
European Patent Office
Prior art keywords
acid
process according
recording process
silver salt
silver
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.)
Granted
Application number
EP95201340A
Other languages
German (de)
English (en)
Other versions
EP0687572B1 (fr
Inventor
Carlo C/O Agfa-Gevaert N.V. Uyttendaele
Herman C/O Agfa-Gevaert N.V. Uytterhoeven
Guy C/O Agfa-Gevaert N.V. Jansen
Bartholomeus C/O Agfa-Gevaert N.V. Horsten
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP95201340A priority Critical patent/EP0687572B1/fr
Publication of EP0687572A1 publication Critical patent/EP0687572A1/fr
Application granted granted Critical
Publication of EP0687572B1 publication Critical patent/EP0687572B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/494Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498Photothermographic systems, e.g. dry silver
    • G03C1/4989Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/494Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498Photothermographic systems, e.g. dry silver
    • G03C1/49827Reducing agents
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/494Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498Photothermographic systems, e.g. dry silver
    • G03C1/49836Additives
    • G03C1/49845Active additives, e.g. toners, stabilisers, sensitisers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00Details
    • G03C2200/26Gamma

Definitions

  • the present invention relates to a direct thermal imaging process for continuous tone reproduction.
  • Thermal imaging or thermography is a recording process wherein images are generated by the use of imagewise modulated thermal energy.
  • thermography two approaches are known :
  • Thermal dye transfer printing is a recording method wherein a dye-donor element is used that is provided with a dye layer wherefrom dyed portions or incorporated dyes are transferred onto a contacting receiver element by the application of heat in a pattern normally controlled by electronic information signals.
  • Thermography is concerned with materials which are substantially not photosensitive, but are sensitive to heat or thermosensitive. Imagewise applied heat is sufficient to bring about a visible change in a thermosensitive imaging material.
  • thermographic recording materials are of the chemical type. On heating to a certain conversion temperature, an irreversible chemical reaction takes place and a coloured image is produced.
  • thermal printing image signals are converted into electric pulses and then through a driver circuit selectively transferred to a thermal printhead.
  • the thermal printhead consists of microscopic heat resistor elements, which convert the electrical energy into heat via Joule effect.
  • the electric pulses thus converted into thermal signals manifest themselves as heat transferred to the surface of the thermal paper wherein the chemical reaction resulting in colour development takes place.
  • a heat-sensitive recording material is used in the form of an electrically resistive ribbon having a multilayered structure in which a carbon-loaded polycarbonate is coated with a thin aluminium film (ref. Progress in Basic Principles of Imaging Systems - Proceedings of the International Congress of Photographic Science GmbH (Cologne), 1986 ed. by Friedrich Granzer and Erik Moisar - Friedr. Vieweg & Sohn - Braunschweig/Wiesbaden Figure 6. p. 622).
  • Current is injected into the resistive ribbon by electrically addressing a printhead electrode contacting the carbon-loaded substrate, thus resulting in highly localized heating of the ribbon beneath the energized electrode.
  • the recording material is image-wise or pattern-wise heated by means of a modulated laser beam.
  • image-wise modulated infra-red laser light is absorbed in the recording layer in infra-red light absorbing substances converting infra-red radiation into the necessary heat for the imaging reaction.
  • the imagewise applied laser light has not necessarily to be infrared light since the power of a laser in the visible light range and even in the ultraviolet region can be thus high that sufficient heat is generated on absorption of the laser light in the recording material.
  • laser which may be a gas laser, gas ion laser, e.g. argon ion laser, solid state laser, e.g. Nd:YAG laser, dye laser or semi-conductor laser.
  • the image signals for modulating the laser beam or current in the micro-resistors of a thermal printhead are obtained directly e.g. from opto-electronic scanning devices or from an intermediary storage means, e.g. magnetic disc or tape or optical disc storage medium, optionally linked to a digital image work station wherein the image information can be processed to satisfy particular needs.
  • an intermediary storage means e.g. magnetic disc or tape or optical disc storage medium
  • thermographic recording material contains a polymeric binder, di- or triarylmethane thiolactone dye precursor in combination with silver behenate and 3,5-dihydroxybenzoic acid as an organic acidic reagent.
  • Said reagent acts as a weak reducing agent and provides a stable one-pot coating composition.
  • Other organic acidic reagents such as phthalic acid are described in column 6 of said US-P.
  • Banding is a phenomenon characterized by the presence in the thermographic image of parallel stripes of different optical density in the print direction and is typical for the use of thermal printheads containing an array of geometrically juxtaposed heating resistors that may show a spread in resistance value and/or contact-pressure with the recording material.
  • a direct thermal imaging process operating with a thermal printhead in conjunction with a heat-sensitive recording material capable of yielding images with maximum density higher than 2.5 and gradation sufficiently low for continuous tone reproduction as is needed e.g. in portrait reproduction for identification documents and in the medical diagnostic field based on images produced by e.g. radiography ultrasound or nuclear magnetic resonance (NMR) signals.
  • NMR nuclear magnetic resonance
  • a direct thermal imaging process wherein a non-photosensitive direct thermal recording material is heated dot-wise, and said direct thermal recording material comprises an imaging layer containing uniformly distributed in a film-forming polymeric binder (i) one or more substantially light-insensitive organic silver salts, said silver salt(s) being uniformly in thermal working relationship with (ii) one or more organic reducing agents therefor, however neither including 3,5-dihydroxybenzoic acid as acidic reagent nor di-tert-butyl-p-cresol as a sole reducing agent, characterized in that said imaging layer contains at least one polycarboxylic acid and/or anhydride thereof in a molar percentage of at least 20 with respect to said silver salt(s).
  • Said mole percentage is preferably in the range of 20 to 30.
  • thermo working relationship is meant here that said substantially light-insensitive silver salt and said organic reducing agent can react by means of heat to form metallic silver.
  • said ingredients (i) and (ii) may be present in the same binder-containing layer or in different layers wherefrom by heat they can come into reactive contact with each other, e.g. by diffusion or sublimation.
  • NSV numerical gradation value
  • E 2 . 5 is the minimal energy in Joule applied in a dot area of 87 /1 .m x 87 /1 .m of the recording material that obtains by said energy an optical density value of 2.5
  • E o . is the maximal energy in Joule applied in a dot area of the recording material that obtains by said energy an optical density value of 0.1.
  • Said optical density values are values above the inherent optical density of the "unheated" recording material having always already some optical density by the inherent optical density of the imaging layer and its support.
  • thermo head printer developed for thermosensitometric measurement purposes and having distinct groups of micro-resistors being arranged in succession along the width of the printhead array. From group to group said resistors receive a linearly increasing amount of electrical energy within the line time of the printer. The input of electrical energy per group of resistors is controlled by linearly increasing the period of time from group to group wherein a constant current at constant voltage is applied, said current and voltage being kept constant over the whole printing period.
  • the line time is the time needed for printing one single line with the thermal head.
  • the line time is a period of time of 32 ms wherein the imaging material with respect to the print array travels a distance of one pixel length, viz. 87 ⁇ m.
  • the continuous tone reproduction capability of a heat-sensitive imaging material used according to the present invention is favoured by a relatively high binder to silver salt weight ratio in the imaging layer.
  • a relatively high binder to silver salt weight ratio in the imaging layer Preferably said ratio is in the range of 1/2 to 6/1, and more preferably from 1/1 to 4/1.
  • Substantially light-insensitive organic silver salts particularly suited for use in a direct thermal recording material according to the present invention are silver salts of aliphatic carboxylic acids known as fatty acids, wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, which silver salts are also called "silver soaps”.
  • Modified aliphatic carboxylic acids with thioether group as described e.g. in GB-P 1,111,492 and other organic silver salts as described in GB-P 1,439,478, e.g.
  • silver benzoate and silver phthalazinone may be used likewise to produce a thermally developable silver image.
  • Organic reducing agents suitable for use according to the present invention are aromatic di- and tri-hydroxy compounds having at least two hydroxy groups in ortho- or para-position on the same aromatic nucleus, e.g. benzene nucleus, more particularly e.g. hydroquinone and substituted hydroquinones, catechol, pyrogallol, gallic acid and gallic acid esters.
  • aromatic di- and tri-hydroxy compounds having at least two hydroxy groups in ortho- or para-position on the same aromatic nucleus, e.g. benzene nucleus, more particularly e.g. hydroquinone and substituted hydroquinones, catechol, pyrogallol, gallic acid and gallic acid esters.
  • Particularly useful are polyhydroxy spiro-bis-indane compounds, especially these corresponding to the following general formula: wherein :
  • catechol-type reducing agents by which is meant reducing agents containing at least one benzene nucleus with two hydroxy groups (-OH) in ortho-position e.g. catechol, 3- (3,4-dihydroxyphenyl) propionic acid, 1,2-dihydroxybenzoic acid, gallic acid and esters e.g. methyl gallate, ethyl gallate, propyl gallate, tannic acid, and 3,4-dihydroxy-benzoic acid esters.
  • auxiliary reducing agents are e.g. sterically hindered phenols, that on heating become reactive partners in the reduction of the substantially light-insensitive silver salt such as silver behenate, or are bisphenols, e.g. of the type described in US-P 3,547,648.
  • the auxiliary reducing agents may be present in the imaging layer or in a polymeric binder layer adjacent thereto.
  • polycarboxylic acid(s) and/or anhydrides thereof in thermal working relationship with the substantially light-insensitive silver salt has an image gradation-lowering effect as can be learned from the Examples.
  • the polycarboxylic acid may be aliphatic (saturated as well as unsaturated aliphatic and likewise cycloaliphatic) as well as an aromatic polycarboxylic acid. These acids may be substituted e.g. with alkyl, hydroxyl, nitro or halogen. They may be used in anhydride form or partially esterified on the condition that at least two free carboxylic acids remain or are available in the heat recording step.
  • saturated aliphatic dicarboxylic acids containing at least 4 carbon atoms e.g. : succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane-dicarboxylic acid, decane-dicarboxylic acid, undecane-dicarboxylic acid.
  • Suitable unsaturated dicarboxylic acids are : maleic acid, citraconic acid, itaconic acid and aconitic acid.
  • a particularly effectively gradation lowering substituted polycarboxylic acid is citric acid, and derivative thereof acetonedicarboxylic acid and further iso-citric acid and a-ketoglutaric acid.
  • Preferred aromatic polycarboxylic acids are ortho-phthalic acid and 3-nitro-phthalic acid, tetrachlorophthalic acid, mellitic acid, pyromellitic acid and trimellitic acid and the anhydrides thereof.
  • the silver image density depends on the coverage of said substantially light-insensitive silver salts in combination with said polycarboxylic acids and reducing agent(s) and has to be preferably such that, on heating above 120 °C, an optical density of at least 2.5 can be obtained.
  • the thickness of the imaging layer is preferably in the range of 5 to 50 ⁇ m.
  • said substantially light-insensitive organic silver salt and said organic reducing agent are present in different layers wherefrom by heat they can come into reactive contact with each other.
  • the film-forming water-insoluble polymeric binder of the imaging layer of the present direct thermal recording material is preferably a thermoplastic resin or mixture of such resins, wherein the silver salt can be dispersed homogeneously.
  • a thermoplastic resin or mixture of such resins wherein the silver salt can be dispersed homogeneously.
  • all kinds of natural, modified natural or synthetic water-insoluble resins may be used, e.g. cellulose derivatives such as ethylcellulose. cellulose esters, e.g.
  • cellulose nitrate polymers derived from a,;8-ethy!enica!!y unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl acetals that are made from polyvinyl alcohol as starting material in which only a part of the repeating vinyl alcohol units may have reacted with an aldehyde, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters and polyethylene or mixtures thereof.
  • aldehyde preferably polyvinyl butyral
  • copolymers of acrylonitrile and acrylamide polyacrylic acid esters, polymethacrylic acid esters and polyethylene or mixtures thereof.
  • a particularly suitable polyvinyl butyral containing a minor amount of vinyl alcohol units is marketed under the tradename BUTVAR B79 of Monsanto USA and provides a good adherence to paper and properly subbed polyester supports.
  • the layer containing the organic silver salt is commonly coated from an organic solvent containing the binder in dissolved form.
  • the binder of the imaging layer may be combined with waxes or "heat solvents” also called “thermal solvents” or “thermosolvents” improving the reaction speed of the redox-reaction at elevated temperature.
  • heat solvent in this invention is meant a non-hydrolyzable organic material which is in solid state in the recording layer at temperatures below 50 ° C but becomes a plasticizer for the recording layer in the heated region and/or liquid solvent for at least one of the redox-reactants, e.g. the reducing agent for the organic silver salt, at a temperature above 60 ° C.
  • redox-reactants e.g. the reducing agent for the organic silver salt
  • the recording layer contains in admixture with said organic silver salt and reducing agents a so-called toning agent known from thermography or photo-thermography.
  • Suitable toning agents are the phthalimides and phthalazinones within the scope of the general formulae described in US-P 4,082,901. Further reference is made to the toning agents described in US-P 3,074,809, 3,446,648 and 3,844,797.
  • Other particularly useful toning agents are the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type within the scope of following general formula : in which :
  • a toner compound particularly suited for use in combination with polyhydroxy benzene reducing agents is 3,4-dihydro-2,4-dioxo-1,3,2H-benzoxazine described in US-P 3,951,660.
  • the imaging layer may contain other additives such as free fatty acids, antistatic agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in FaC(CF 2 )sCONH-(CH 2 CH 2 0)-H, ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, and/or optical brightening agents.
  • antistatic agents e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in FaC(CF 2 )sCONH-(CH 2 CH 2 0)-H
  • ultraviolet light absorbing compounds e.g. in FaC(CF 2 )sCONH-(CH 2 CH 2 0)-H
  • white light reflecting and/or ultraviolet radiation reflecting pigments e.g. in FaC(CF 2 )sCONH-(CH 2 CH 2 0)-H
  • ultraviolet light absorbing compounds e.g. in FaC(CF 2 )sCONH-(CH 2 CH 2 0)
  • the support for the heat-sensitive recording material according to the present invention is preferably a thin flexible carrier made e.g. from paper, polyethylene coated paper or transparent resin film, e.g. made of a cellulose ester, e.g. cellulose triacetate, polypropylene polycarbonate or polyester, e.g. polyethylene terephthalate.
  • the support may be in sheet, ribbon or web form and subbed if need be to improve the adherence to the thereon coated heat-sensitive imaging layer.
  • the coating of the imaging layer may proceed by any coating technique e.g. as described in Modern Coating and Drying Technology, edited by Edward D. Cohen and Edgar B. Gutoff, (1992) VCH Publishers Inc. 220 East 23rd Street, Suite 909 New York, NY 10010, U.S.A.
  • Direct thermal imaging can be used for both the production of transparencies and reflection type prints.
  • the support may be transparent or opaque, e.g. the support has a white light reflecting aspect.
  • a paper base is used which may contain white light reflecting pigments, optionally also applied in an interlayer between the recording layer and said base.
  • said base may be colourless or coloured, e.g. has a blue colour.
  • the recording materials of the present invention are particularly suited for use in thermographic recording techniques operating with thermal print-heads.
  • Suitable thermal printing heads are e.g. a Fujitsu Thermal Head (FTP-040 MCS001), a TDK Thermal Head F415 HH7-1089, and a Rohm Thermal Head KE 2008-F3.
  • the imagewise heating of the recording material with said printheads proceeds through a contacting but removable resin sheet or web wherefrom during said heating no transfer of imaging material can take place.
  • the imaging layer when being the outermost layer may contain hydrophilic finely divided (colloidal) optically transparent inert inorganic pigments such as transparent colloidal silica not masking the lateron formed silver image.
  • the imaging layer is coated with a protective coating and/or contains substances having anti-sticking properties e.g. (a) lubricating agent(s).
  • the outermost layer of the heat-sensitive recording material according to the present invention may comprise a dissolved lubricating material and/or a dispersed particulate lubricating material, e.g. talc particles, optionally protruding from the outermost layer.
  • suitable lubricating materials are a surface active agent, a liquid lubricant, a solid lubricant or mixtures thereof.
  • the surface active agents may be any agents known in the art such as carboxylates, sulfonates, phosphates, aliphatic amine salts, aliphatic quaternary ammonium salts, polyoxyethylene alkyl ethers. polyethylene glycol fatty acid esters, fluoroalkyl C 2 -C 2o aliphatic acids.
  • liquid lubricants include silicone oils, synthetic oils, saturated hydrocarbons and glycols.
  • solid organic lubricants include various higher alcohols such as stearyl alcohol, fatty acids and fatty acid esters.
  • outermost slipping layers are mentioned layers made from a styrene-acrylonitrile copolymer or a styrene-acrylonitrile-butadiene copolymer or binder mixture hereof containing as lubricant in an amount of 0.1 to 10 % by weight with respect to said binder(s) a polysiloxane-polyether copolymer or polytetrafluoroethylene or a mixture hereof.
  • Another suitable outermost slipping layer may be obtained by coating a solution of at least one silicon compound and a substance capable of forming during the coating procedure a polymer having an inorganic backbone which is an oxide of a group IVa or IVb element as described in published European patent application 0554576.
  • a subbed polyethylene terephthalate support having a thickness of 100 ⁇ m was doctor blade-coated from a coating composition containing methyl ethyl ketone as a solvent and the following ingredients so as to obtain thereon after drying for 1 h at 50 ° C an imaging layer containing :
  • thermo head printer developed for thermosensitometric measurement purposes and having distinct groups of micro-resistors being arranged in succession along the width of the printhead array. From group to group said resistors receive a linearly increasing amount of electrical energy within the line time of the printer.
  • the input of electrical energy per group of resistors is controlled by linearly increasing the period of time from group to group wherein a constant current at constant voltage is applied, said current and voltage being kept constant over the whole printing period.
  • the line time is a period of time of 32 ms wherein the imaging material with respect to the print array travels a distance of a pixel length of 87 ⁇ m.
  • the print head was separated from the imaging layer by a thin intermediate material and made contact with the slipping layer of a separatable intermediate 5 ⁇ m thick polyethylene terephthalate ribbon being coated in consecutive order with a subbing layer, heat-resistant layer and said slipping layer (anti-friction layer) giving the ribbon a total thickness of 6 ⁇ m.
  • Said subbing layer also called primer layer, is a layer of a copolyester being a polycondensation product of ethylene glycol, adipic acid, neopentyl glycol, terephthalic acid, isophthalic acid and glycerol.
  • TEGOGLIDE 410 polyether modified polydimethylsiloxane
  • the numerical gradation value (NGV) corresponding with the quotient of the fraction (2.5 - 0.1 )/(E 2 . 5 -E o . i ) was determined; herein E 2 . 5 is the energy in Joule applied in a dot area of 87 ⁇ m x 87 ⁇ m of the imaging layer that obtains by said energy an optical density value of 2.5, and E o ., is the energy in Joule applied in a dot area of the imaging layer material that obtains by said energy an optical density value of 0.1.
  • the applied energy in Joule is actually the electrical input energy measured for each resistor of the thermal head.
  • the recording materials A5 and A6 are invention materials, the other ones are comparative test materials.
  • a subbed polyethylene terephthalate support having a thickness of 100 ⁇ m was doctor blade-coated from a coating composition containing methyl ethyl ketone as a solvent and the following ingredients so as to obtain thereon after drying for 1 h at 50 ° C an imaging layer containing :
  • the recording materials B4 and B5 are invention materials whereas the recording materials B1 to B3 5 are "non-invention" comparative test materials.
  • a subbed polyethylene terephthalate support having a thickness of 100 ⁇ m was doctor blade-coated from a coating composition containing methyl ethyl ketone as a solvent and the following ingredients so as to obtain thereon after drying for 1 h at 50 ° C an imaging layer containing :
  • Material CO is the "blanco" material free from polyacid.
  • the recording material C3 is an invention material whereas the recording materials C1 and C2 are "non-invention" comparative test materials.
  • a subbed polyethylene terephthalate support having a thickness of 100 ⁇ m was doctor blade-coated from a coating composition containing methyl ethyl ketone as a solvent and the following ingredients so as to obtain thereon after drying for 1 h at 50 ° C an imaging layer containing :
  • Material CO is the "blanco" material free from polyacid.
  • the recording material D3 is an invention material whereas the recording materials D1 and D2 are "non-invention" comparative test materials.
  • a subbed polyethylene terephthalate support having a thickness of 100 ⁇ m was doctor blade-coated from a coating composition containing methyl ethyl ketone as a solvent and the following ingredients so as to obtain thereon after drying for 1 h at 50 ° C an imaging layer containing :
  • the recording material E4 is an invention materials, the other ones are “non-invention" comparative test materials.
  • a subbed polyethylene terephthalate support having a thickness of 100 ⁇ m was doctor blade-coated from a coating composition containing methyl ethyl ketone as a solvent and the following ingredients so as to obtain thereon after drying for 1 h at 50 ° C an imaging layer containing :
  • Material EO is a blanco material free from polyacid.
  • the recording material E1 and E2 are invention materials.
  • a subbed polyethylene terephthalate support having a thickness of 100 ⁇ m was doctor blade-coated from a coating composition containing methyl ethyl ketone as a solvent and the following ingredients so as to obtain thereon after drying for 1 h at 50 ° C an imaging layer containing :
  • the recording materials G1 to G3 are invention materials.
  • a subbed polyethylene terephthalate support having a thickness of 100 ⁇ m was doctor blade-coated from a coating composition containing methyl ethyl ketone as a solvent and the following ingredients so as to obtain thereon after drying for 1 h at 50 ° C an imaging layer containing per m 2 :
  • the maximum optical density (Dmax) obtainable with di-tert-butyl-p-cresol or 3,5-dihydroxy benzoic acid as sole reducing agents is too low for defining the numerical gradation value NGV (see non-invention recording materials X2, X3, X5 and X6).
  • the optical background density, also called minimum density (Dmin) is practically the same for all of the recording materials X1-X6.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP95201340A 1994-06-15 1995-05-23 Méthode pour l'enregistrement par la chaleur Expired - Lifetime EP0687572B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP95201340A EP0687572B1 (fr) 1994-06-15 1995-05-23 Méthode pour l'enregistrement par la chaleur

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP94201717 1994-06-15
EP94201717 1994-06-15
EP95201340A EP0687572B1 (fr) 1994-06-15 1995-05-23 Méthode pour l'enregistrement par la chaleur

Publications (2)

Publication Number Publication Date
EP0687572A1 true EP0687572A1 (fr) 1995-12-20
EP0687572B1 EP0687572B1 (fr) 1997-08-20

Family

ID=26136341

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95201340A Expired - Lifetime EP0687572B1 (fr) 1994-06-15 1995-05-23 Méthode pour l'enregistrement par la chaleur

Country Status (1)

Country Link
EP (1) EP0687572B1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0782043A1 (fr) 1995-12-27 1997-07-02 Agfa-Gevaert N.V. Matériel thermographique pour l'enregistrement avec reproduction améliorée du ton
WO1998052100A1 (fr) * 1997-05-13 1998-11-19 Imation Corp. Acide gallique en tant que revelateur thermique direct laser
EP0901040A1 (fr) * 1997-09-03 1999-03-10 Agfa-Gevaert N.V. Matériau d'enregistrement thermographique pratiquement insensible à la lumière ayant une meilleure stabilité et un ton de l'image amélioré
US5922528A (en) * 1998-03-20 1999-07-13 Eastman Kodak Company Thermographic imaging element
US5928856A (en) * 1998-03-20 1999-07-27 Eastman Kodak Company Thermographic imaging element
US5928855A (en) * 1998-03-20 1999-07-27 Eastman Kodak Company Thermographic imaging element
US5994052A (en) * 1998-03-20 1999-11-30 Eastman Kodak Company Thermographic imaging element
US6066445A (en) * 1996-12-19 2000-05-23 Eastman Kodak Company Thermographic imaging composition and element comprising said composition
EP1006000A1 (fr) * 1998-11-30 2000-06-07 Agfa-Gevaert N.V. Procédé d'impression d'étiquette pour materiaux d'imagerie thermique directe comprenant un sel d'argent organique
EP1059560A1 (fr) * 1999-06-04 2000-12-13 Agfa-Gevaert N.V. Matériau thermographique d'enregistrement avec ton de l'image amélioré
US6244766B1 (en) 1998-11-30 2001-06-12 Agfa-Gevaert Label-printing process for substantially light-insensitive elongated materials including an organic silver salt
EP1158355A1 (fr) * 2000-05-25 2001-11-28 Agfa-Gevaert N.V. Matériau thermographique d' enregistrement avec ton de l' image amélioré

Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3074809A (en) 1959-10-26 1963-01-22 Minnesota Mining & Mfg Heat-sensitive copying-paper
US3347675A (en) 1965-06-18 1967-10-17 Eastman Kodak Co Solid homogeneous compositions containing silver halide processing agents
GB1111492A (en) 1964-08-14 1968-04-24 Agfa Gevaert Ag Photographic material
US3438776A (en) 1964-12-28 1969-04-15 Eastman Kodak Co Non-aqueous silver halide photographic process
US3440049A (en) 1966-06-03 1969-04-22 Du Pont Polyhydroxy-spiro-bis-indane photographic tanning agent
US3446648A (en) 1965-09-27 1969-05-27 Minnesota Mining & Mfg Reactive copying sheet and method of using
GB1161777A (en) * 1966-02-21 1969-08-20 Fuji Photo Film Co Ltd Thermally Developable Light-sensitive Elements
GB1163187A (en) * 1966-06-06 1969-09-04 Fuji Photo Film Co Ltd Improvements in or relating to Light-Sensitive, Heat Developable, Photographic Material
US3547648A (en) 1968-01-26 1970-12-15 Minnesota Mining & Mfg Copy-sheet
US3667959A (en) 1970-05-01 1972-06-06 Eastman Kodak Co Photosensitive and thermosensitive element,compositions and process
US3844797A (en) 1972-04-27 1974-10-29 Agfa Gevaert Photosensitive recording material
US3951660A (en) 1972-12-16 1976-04-20 Agfa-Gevaert, A.G. Dry copying material
GB1439478A (en) 1972-12-16 1976-06-16 Agfa Gevaert Ag Dry copying material
US4082901A (en) 1973-04-04 1978-04-04 Agfa-Gevaert N.V. Thermographic material
US4260677A (en) 1976-03-12 1981-04-07 Minnesota Mining And Manufacturing Company Thermographic and photothermographic materials having silver salt complexes therein
DE3339810A1 (de) 1982-11-05 1984-05-10 Fuji Photo Film Co., Ltd., Minami Ashigara, Kanagawa Waermeentwickelbares farbphotographisches material
EP0119615A2 (fr) 1983-03-16 1984-09-26 Fuji Photo Film Co., Ltd. Procédé de formation d'images à sec
EP0122512A2 (fr) 1983-03-25 1984-10-24 Fuji Photo Film Co., Ltd. Procédé de formation d'images à sec et matériau à cet effet
US4740446A (en) 1985-11-12 1988-04-26 Agfa Gevaert Aktiengesellschaft Heat development process and color photographic recording material suitable for this process
US4904572A (en) 1988-04-18 1990-02-27 Polaroid Corporation Thermographic recording materials and coating composition therefor
US4912083A (en) 1989-06-20 1990-03-27 Eastman Kodak Company Infrared absorbing ferrous complexes for dye-donor element used in laser-induced thermal dye transfer
US4948777A (en) 1989-06-16 1990-08-14 Eastman Kodak Company Infrared absorbing bis(chalcogenopyrylo)polymethine dyes for dye-donor element used in laser-induced thermal dye transfer
EP0486246A1 (fr) * 1990-11-14 1992-05-20 Canon Kabushiki Kaisha Matériel photosensible développable à chaud
EP0492411A1 (fr) 1990-12-21 1992-07-01 Diafoil Hoechst Co., Ltd Matériau pour l'impression par transfert thermique d'encre
EP0501072A1 (fr) 1991-02-25 1992-09-02 Minnesota Mining And Manufacturing Company Feuille de transfert thermique de colorant avec un revêtement anti-collage
EP0554576A1 (fr) 1992-01-28 1993-08-11 Agfa-Gevaert N.V. Elément donneur de colorant pour utilisation dans le transfert thermique de colorant par sublimation
EP0622217A1 (fr) 1993-04-27 1994-11-02 Agfa-Gevaert N.V. Méthode pour la production d'une image avec des éléments thermosensibles pour emploi direct

Patent Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3074809A (en) 1959-10-26 1963-01-22 Minnesota Mining & Mfg Heat-sensitive copying-paper
GB1111492A (en) 1964-08-14 1968-04-24 Agfa Gevaert Ag Photographic material
US3438776A (en) 1964-12-28 1969-04-15 Eastman Kodak Co Non-aqueous silver halide photographic process
US3347675A (en) 1965-06-18 1967-10-17 Eastman Kodak Co Solid homogeneous compositions containing silver halide processing agents
US3446648A (en) 1965-09-27 1969-05-27 Minnesota Mining & Mfg Reactive copying sheet and method of using
GB1161777A (en) * 1966-02-21 1969-08-20 Fuji Photo Film Co Ltd Thermally Developable Light-sensitive Elements
US3440049A (en) 1966-06-03 1969-04-22 Du Pont Polyhydroxy-spiro-bis-indane photographic tanning agent
GB1163187A (en) * 1966-06-06 1969-09-04 Fuji Photo Film Co Ltd Improvements in or relating to Light-Sensitive, Heat Developable, Photographic Material
US3547648A (en) 1968-01-26 1970-12-15 Minnesota Mining & Mfg Copy-sheet
US3667959A (en) 1970-05-01 1972-06-06 Eastman Kodak Co Photosensitive and thermosensitive element,compositions and process
US3844797A (en) 1972-04-27 1974-10-29 Agfa Gevaert Photosensitive recording material
GB1439478A (en) 1972-12-16 1976-06-16 Agfa Gevaert Ag Dry copying material
US3951660A (en) 1972-12-16 1976-04-20 Agfa-Gevaert, A.G. Dry copying material
US4082901A (en) 1973-04-04 1978-04-04 Agfa-Gevaert N.V. Thermographic material
US4260677A (en) 1976-03-12 1981-04-07 Minnesota Mining And Manufacturing Company Thermographic and photothermographic materials having silver salt complexes therein
DE3339810A1 (de) 1982-11-05 1984-05-10 Fuji Photo Film Co., Ltd., Minami Ashigara, Kanagawa Waermeentwickelbares farbphotographisches material
EP0119615A2 (fr) 1983-03-16 1984-09-26 Fuji Photo Film Co., Ltd. Procédé de formation d'images à sec
EP0122512A2 (fr) 1983-03-25 1984-10-24 Fuji Photo Film Co., Ltd. Procédé de formation d'images à sec et matériau à cet effet
US4740446A (en) 1985-11-12 1988-04-26 Agfa Gevaert Aktiengesellschaft Heat development process and color photographic recording material suitable for this process
US4904572A (en) 1988-04-18 1990-02-27 Polaroid Corporation Thermographic recording materials and coating composition therefor
US4948777A (en) 1989-06-16 1990-08-14 Eastman Kodak Company Infrared absorbing bis(chalcogenopyrylo)polymethine dyes for dye-donor element used in laser-induced thermal dye transfer
US4912083A (en) 1989-06-20 1990-03-27 Eastman Kodak Company Infrared absorbing ferrous complexes for dye-donor element used in laser-induced thermal dye transfer
EP0486246A1 (fr) * 1990-11-14 1992-05-20 Canon Kabushiki Kaisha Matériel photosensible développable à chaud
EP0492411A1 (fr) 1990-12-21 1992-07-01 Diafoil Hoechst Co., Ltd Matériau pour l'impression par transfert thermique d'encre
EP0501072A1 (fr) 1991-02-25 1992-09-02 Minnesota Mining And Manufacturing Company Feuille de transfert thermique de colorant avec un revêtement anti-collage
EP0554576A1 (fr) 1992-01-28 1993-08-11 Agfa-Gevaert N.V. Elément donneur de colorant pour utilisation dans le transfert thermique de colorant par sublimation
EP0622217A1 (fr) 1993-04-27 1994-11-02 Agfa-Gevaert N.V. Méthode pour la production d'une image avec des éléments thermosensibles pour emploi direct

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
A.S.DIAMOND: "Handbook of Imaging Materials", 1991, M. DEKKER INC., NEW YORK, pages: 498 - 499
CHEMICAL ABSTRACTS, vol. 91, no. 18, 29 October 1979, Columbus, Ohio, US; abstract no. 149477x, A.KORCZYNSKI ET AL.: "HEAT-SENSITIVE PAPER FOR OBTAINING BLACK-AND-WHITE REPRODUCTIONS." page 587; *
E.D.COHEN, E.B.GUTOFF: "Modern Coating and Drying Technology", 1992, VCH PUBLISHERS INC., NEW YORK
F. GRANZER, E. MOISAR: "Proceedings of the International Congress of Photographic Science Koeln", 1986, article "Progress in Basic Principles of Imaging Systems", pages: 622
K.I. JACOBSON, R.E. JACOBSON: "Imaging Systems", 1976, THE FOCAL PRESS, LONDON & NEW YORK

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0782043A1 (fr) 1995-12-27 1997-07-02 Agfa-Gevaert N.V. Matériel thermographique pour l'enregistrement avec reproduction améliorée du ton
US6066445A (en) * 1996-12-19 2000-05-23 Eastman Kodak Company Thermographic imaging composition and element comprising said composition
WO1998052100A1 (fr) * 1997-05-13 1998-11-19 Imation Corp. Acide gallique en tant que revelateur thermique direct laser
EP0901040A1 (fr) * 1997-09-03 1999-03-10 Agfa-Gevaert N.V. Matériau d'enregistrement thermographique pratiquement insensible à la lumière ayant une meilleure stabilité et un ton de l'image amélioré
US5994052A (en) * 1998-03-20 1999-11-30 Eastman Kodak Company Thermographic imaging element
US5928855A (en) * 1998-03-20 1999-07-27 Eastman Kodak Company Thermographic imaging element
US5928856A (en) * 1998-03-20 1999-07-27 Eastman Kodak Company Thermographic imaging element
US5922528A (en) * 1998-03-20 1999-07-13 Eastman Kodak Company Thermographic imaging element
EP1006000A1 (fr) * 1998-11-30 2000-06-07 Agfa-Gevaert N.V. Procédé d'impression d'étiquette pour materiaux d'imagerie thermique directe comprenant un sel d'argent organique
WO2000032403A1 (fr) * 1998-11-30 2000-06-08 Agfa-Gevaert Procede d'impression d'etiquettes utilisant des materiaux d'imagerie allonges sensiblement insensibles a la lumiere, notamment un sel organique d'argent
US6244766B1 (en) 1998-11-30 2001-06-12 Agfa-Gevaert Label-printing process for substantially light-insensitive elongated materials including an organic silver salt
EP1059560A1 (fr) * 1999-06-04 2000-12-13 Agfa-Gevaert N.V. Matériau thermographique d'enregistrement avec ton de l'image amélioré
EP1158355A1 (fr) * 2000-05-25 2001-11-28 Agfa-Gevaert N.V. Matériau thermographique d' enregistrement avec ton de l' image amélioré

Also Published As

Publication number Publication date
EP0687572B1 (fr) 1997-08-20

Similar Documents

Publication Publication Date Title
US5527758A (en) Direct thermal imaging process with improved tone reproduction
US5599647A (en) New toning agents for thermographic and photothermographic materials and process
EP0692733B1 (fr) Procédé directe pour l'enregistrement thermique
EP0687572B1 (fr) Méthode pour l'enregistrement par la chaleur
US5682194A (en) Direct thermal imaging
US5863859A (en) Heat-sensitive material suited for use in direct thermal recording
US5559075A (en) Recording material for direct thermal imaging
EP0903625B1 (fr) Matériaux d'enregistrements thermographiques
US5582953A (en) Direct thermal recording process
EP0752616B1 (fr) Nouveaux agents d'amélioration du ton pour des matériaux et procédés thermographiques et photothermographiques
EP0599369B1 (fr) Matériau d'enregistrement thermosensible
US5817598A (en) Thermal image forming process with improved slip performance therein
US5527757A (en) Recording material for direct thermal imaging
US5885765A (en) Thermographic recording material with improved tone reproduction
US5637550A (en) Heat-sensitive recording material having image-stabilization properties
EP0782043B1 (fr) Matériel thermographique pour l'enregistrement avec reproduction améliorée du ton
EP0809144A1 (fr) Matériau d'enregistrement thermographique à stabilité augmentée et ton d'image amélioré
EP0730196B1 (fr) Matériau d'enregistrement thermosensible à propriétés stabilisatrices de l'image
EP0775592B1 (fr) Procédé thermique pour former des images
US5759953A (en) Thermographic recording material with improved slip properties
EP0685760B1 (fr) Matériau pour l'enregistrement thermosensible
US6306573B1 (en) Production process for a benzotriazole-containing thermographic recording material with improved stability and image-tone
US5854174A (en) Substantially non-photosensitive thermographic recording material with improved stability and image-tone
EP0663301B1 (fr) Matériau d'enregistrement pour un procédé direct de formation d'images thermiques
EP1006406B1 (fr) Matériau d'enregistrement thermographique noir et blanc ayant une stabilité à la lumière solaire améliorée

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB NL

17P Request for examination filed

Effective date: 19960620

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

17Q First examination report despatched

Effective date: 19970129

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB NL

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19970820

Ref country code: BE

Effective date: 19970820

REF Corresponds to:

Ref document number: 69500570

Country of ref document: DE

Date of ref document: 19970925

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
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
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

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

Ref country code: GB

Payment date: 20140408

Year of fee payment: 20

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

Ref country code: DE

Payment date: 20140408

Year of fee payment: 20

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

Ref country code: FR

Payment date: 20140513

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69500570

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20150522

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 EXPIRATION OF PROTECTION

Effective date: 20150522