EP0692733B1 - Procédé directe pour l'enregistrement thermique - Google Patents

Procédé directe pour l'enregistrement thermique Download PDF

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Publication number
EP0692733B1
EP0692733B1 EP95201273A EP95201273A EP0692733B1 EP 0692733 B1 EP0692733 B1 EP 0692733B1 EP 95201273 A EP95201273 A EP 95201273A EP 95201273 A EP95201273 A EP 95201273A EP 0692733 B1 EP0692733 B1 EP 0692733B1
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EP
European Patent Office
Prior art keywords
recording process
process according
reducing agent
silver
silver salt
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EP95201273A
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German (de)
English (en)
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EP0692733A3 (fr
EP0692733A2 (fr
Inventor
Carlo Uyttendaele
Herman Uytterhoeven
Bartholomeus Horsten
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/4989—Photothermographic 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49827—Reducing agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49872—Aspects relating to non-photosensitive layers, e.g. intermediate protective layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
    • G03C2001/7488—Sliding layers or means

Definitions

  • the present invention relates to a direct thermal imaging process with improved neutral 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 infrared light absorbing substances converting infrared 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
  • thermography A wide variety of chemical systems has been suggested for use in thermography as described e.g. on page 138 of the above mentioned book of Kurt I. Jacobson et al.
  • Thermal recording materials are known for the production of black-and-white images as well as for the production of color images.
  • a thermal recording sheet suited for thermographic formation of organic dyes contains a leuco dye type chromogenic component consisting of a leuco dye, an organic color developer and a metal chelate type chromogenic component consisting of an electron acceptor and an electron donor, wherein the electron acceptor is a metal double salt of a fatty acid having 16 to 35 carbon atoms, and the electron donor is a polyhydric hydroxy aromatic compound, e.g. a 3,4-dihydroxy benzoic acid amide [see compound (2)].
  • thermographic materials the image forming layers of which contain a substantially light-insensitive organic silver salt that at elevated temperature is reduced to silver by a selected organic reducing agent such as hydroquinone, substituted hydroquinones, hindered phenols, pyrogallol, methyl gallate, leuco dyes and the like (ref. US-P 5,275,932).
  • Preferred reducing agents for use in combination with said silver salt yield silver images of high optical density, and maintain there reducing property on storage without giving rise to substantial fog.
  • the obtaining of good colour neutrality is particularly problematic when using in thermal recording a thermal print head of which the heat supplied by each micro-resistor is very intensive during a very short heating time so that locally relatively high temperatures are reached that have a "browning" influence on the colour of the silver formed in the reduction process.
  • a direct thermal recording process wherein a direct thermal recording material is heated dot-wise and said direct thermal recording material comprises on a substrate an imaging layer containing uniformly distributed in a film-forming polymeric binder (i) one or more substantially light-insensitive organic silver salts being no double salts, said silver salt(s) being in thermal working relationship with (ii) an organic reducing agent therefor, characterized in that said reducing agent is a benzene compound the benzene nucleus of which is substituted by no more than two hydroxy groups which are present in 3,4-position on said nucleus and have in the 1-position of said nucleus a substituent linked to said nucleus by means of a carbonyl group.
  • thermo working relationship is meant here that said substantially light-insensitive silver salt and said organic reducing agent can react by means of heat, i.e. at elevated temperature, 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 in molten state.
  • Preferred "carbonyl" substituted 3,4-dihydroxy-benzene reducing agents for use according to the present invention are less volatile than catechol and are selected from the group consisting of 3,4-dihydroxy-benzoic acid, an alkyl or aryl ester thereof, 3,4-dihydroxy-benzaldehyde, 3,4-dihydroxy-benzamide and aryl or alkyl (3,4-dihydroxyphenyl) ketones.
  • the alkyl esters of 3,4-dihydroxybenzoic acid comprise e.g. from 1 to 18 carbon atoms, but are preferably C1-C4 alkyl esters.
  • Substantially light-insensitive organic silver salts particularly suited for use in a direct thermal recording process according to the present invention are silver salts (no double 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”.
  • silver benzoate and silver phthalazinone may be used likewise to produce a thermally developable silver image.
  • the silver image density depends on the coverage of said substantially light-insensitive silver salts in combination with the above mentioned reducing agent(s) and has to be preferably such that, on heating above 100 °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(s) are present in different layers wherefrom by heat they can come into reactive contact with each other.
  • the film-forming polymeric binder of the imaging layer of the direct thermal recording material used according to the present invention is preferably a water-insoluble thermoplastic resin or mixture of such resins, wherein the silver salt can be dispersed homogeneously.
  • a water-insoluble 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 ⁇ , ⁇ -ethylenically 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 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.
  • 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 oprating with reducible silver salts.
  • Suitable toning agents are 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 succinimides and the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type within the scope of following general formula : in which : X represents O or N-alkyl; each of R 1 , R 2 , R 3 and R 4 (same or different) represents hydrogen, alkyl, e.g.
  • C1-C20 alkyl preferably C1-C4 alkyl, cycloalkyl. e.g. cyclopentyl or cyclohexyl, alkoxy, preferably methoxy or ethoxy, alkylthio with preferably up to 2 carbon atoms, hydroxy, dialkylamino of which the alkyl groups have preferably up to 2 carbon atoms or halogen, preferably chlorine or bromine; or R 1 and R 2 or R 2 and R 3 represent the ring members required to complete a fused aromatic ring, preferably a benzene ring, or R 3 and R 4 represent the ring members required to complete a fused aromatic or cyclohexane ring. Toners within the scope of said general formula are described in GB-P 1,439,478 and US-P 3,951,660.
  • a toner compound particularly suited for use in combination with the above mentioned 3,4-dihydroxy 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 F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H.
  • antistatic agents e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H.
  • ultraviolet light absorbing compounds white light reflecting and/or ultraviolet radiation reflecting pigments, and/or optical brightening agents.
  • the substrate also called support for the heat-sensitive imaging layer of the thermosensitive recording material used 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.
  • 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 thin resin sheet or web wherefrom during said heating no transfer of imaging material can take place.
  • 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 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 and fluoroalkyl C 2 -C 20 aliphatic acids.
  • Examples of 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 layers acting as so-called 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 : silver behenate 5.13 g/m 2 polyvinyl butyral (BUTVAR B79-tradename) 5.13 g/m 2 3,4-dihydro-2,4-dioxo-1,3,2H-benzoxazine 0.39 g/m 2 BAYSILON ⁇ l (tradename of Bayer AG - Germany) 12 mg/m 2 reducing agent A to I as in Table 1 applied in chemical equivalent weight (g/m 2 ) coverage Material Reducing agent Coverage g/m 2 A Indane I 0.98 B 3,4-Dihydroxybenzoic acid 0.88 C Ethyl ester of 3,4-dihydroxybenzoic acid 1.03 D n-Butyl ester of
  • the materials B, C, D, E and F are invention materials, the other ones are comparative test materials.
  • thermosensitive recording materials A to I are used in a thermal head printer.
  • the printer was equipped with a thin film thermal head with a resolution of 300 dpi and was operated with a line time of 18 msec (the line time being the time needed for printing one line). During said line time the print head received constant power.
  • the average printing power being the total amount of electrical input energy during one line time divided by the line time and by the surface area of the heat-generating resistors was 9.8 W/mm 2 being sufficient to obtain maximum optical density in each of said recording materials.
  • 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
  • NCV D ortho A 0.16 3.4 B 0.68 3.7 C 0.57 3.4 D 0.62 3.5 E 0.72 3.4 F 0.63 3.9 G 0.39 4.1 H 0.12 2.6 I 0.33 3.6

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (10)

  1. Procédé d'enregistrement thermique direct dans lequel on chauffe un matériau d'enregistrement thermique direct sous forme de points et ledit matériau d'enregistrement thermique direct comprend, sur un substrat, une couche formatrice d'image contenant, distribués de manière uniforme dans un liant polymère filmogène, (i) un ou plusieurs sels d'argent organiques essentiellement non photosensibles, qui ne sont pas des sels doubles, ledit ou lesdits sels d'argent se trouvant en relation de travail thermique avec (ii) un agent de réduction organique pour ce ou ces derniers, caractérisé en ce que ledit agent de réduction est un composé de benzène dont le noyau benzénique porte au maximum deux groupes hydroxyle présents en position 3,4 sur ledit noyau et possède, en position 1 dudit noyau, un substituant lié audit noyau au moyen d'un groupe carbonyle.
  2. Procédé d'enregistrement selon la revendication 1, dans lequel ledit agent de réduction du type du 3,4-dihydroxybenzène est un membre choisi parmi le groupe constitué par l'acide 3,4-dihydroxybenzoïque, un ester alkylique ou arylique de ce dernier, le 3,4-dihydroxybenzaldéhyde, le 3,4-dihydroxybenzamide et une alkyl- ou aryl-(3,4-dihydroxyphényl)cétone.
  3. Procédé d'enregistrement selon la revendication 1 ou 2, dans lequel le ou lesdits agents de réduction considérés comme étant le ou les agents de réduction primaires ou principaux est ou sont présents conjointement avec un ou plusieurs agents de réduction auxiliaires.
  4. Procédé d'enregistrement selon l'une quelconque des revendications précédentes, dans lequel ledit sel d'argent organique essentiellement non photosensible est un sel d'argent d'un acide carboxylique aliphatique (acide gras) contenant au moins 12 atomes de carbone.
  5. Procédé d'enregistrement selon la revendication 4, dans lequel ledit sel d'argent organique est le palmitate d'argent, le stéarate d'argent ou le béhénate d'argent ou encore des mélanges de ces derniers.
  6. Procédé d'enregistrement selon l'une quelconque des revendications précédentes, dans lequel le rapport pondéral du liant au sel d'argent dans la couche formatrice d'image se situe dans le domaine de 1/2 à 6/1.
  7. Procédé d'enregistrement selon l'une quelconque des revendications précédentes, dans lequel ledit liant est un polyvinylbutyral.
  8. Procédé d'enregistrement selon l'une quelconque des revendications précédentes, dans lequel ledit sel d'argent organique essentiellement non photosensible et ledit agent de réduction organique sont présents dans des couches différentes à partir desquelles ils peuvent venir se mettre en contact réactif l'un avec l'autre sous l'influence de la chaleur.
  9. Procédé d'enregistrement selon l'une quelconque des revendications précédentes, dans lequel la couche formatrice d'image contient, en mélange avec ledit sel d'argent, au moins un agent influençant le ton d'image, à savoir un phtalimide, une phtalazinone, un succinimide ou un composé hétérocyclique répondant à la formule générale ci-après:
    Figure 00190001
    dans laquelle:
    X représente O ou un groupe N-alkyle;
    chacun des radicaux R1, R2, R3 et R4 (identiques ou différents) représente un atome d'hydrogène, un groupe alkyle, un groupe cycloalkyle, un groupe alcoxy, un groupe alkylthio, un groupe hydroxyle, un groupe dialkylamino ou un atome d'halogène; ou bien R1 et R2 ou R2 et R3 représentent ensemble les éléments cycliques requis pour compléter un noyau aromatique condensé ou bien R3 et R4 représentent ensemble les éléments cycliques requis pour compléter un noyau cyclohexane ou aromatique condensé.
  10. Procédé d'enregistrement selon l'une quelconque des revendications précédentes, dans lequel ledit matériau d'enregistrement est muni d'une couche protectrice située le plus à l'extérieur faisant office de couche de glissement.
EP95201273A 1994-07-07 1995-05-16 Procédé directe pour l'enregistrement thermique Expired - Lifetime EP0692733B1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
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US7282468B2 (en) 2005-07-18 2007-10-16 Carestream Health Inc. Direct thermographic materials with catechol borate reducing agents

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* Cited by examiner, † Cited by third party
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EP0775595B1 (fr) 1995-11-27 1999-09-15 Agfa-Gevaert N.V. Matériaux pour l'enregistrement par la chaleur avec un dérivé de l'acide phosphorique comme lubrifiant
EP0779539B1 (fr) 1995-11-27 2002-07-17 Agfa-Gevaert Matériau thermographique avec une couche organique antistatique à l'extérieure
EP0775592B1 (fr) 1995-11-27 2002-09-11 Agfa-Gevaert Procédé thermique pour former des images
EP0782043B1 (fr) 1995-12-27 2003-01-15 Agfa-Gevaert Matériel thermographique pour l'enregistrement avec reproduction améliorée du ton
EP0978760B1 (fr) * 1998-08-07 2003-07-02 Agfa-Gevaert Matériaux d'enregistrements thermographiques
US6211115B1 (en) 1998-08-07 2001-04-03 Agfa-Gevaert Reducing agents for use in thermographic recording materials
US6759367B2 (en) 2001-03-29 2004-07-06 Agfa-Gevaert Thermographic recording material with improved print archivability without loss in printability
EP1245404A1 (fr) * 2001-03-29 2002-10-02 Agfa-Gevaert Matériau thermographique d'enregistrement produisant des imprimés avec une bonne densité et un bon ton d'image et ayant une archivabilité améliorée
EP1270255A1 (fr) * 2001-06-29 2003-01-02 Agfa-Gevaert Produit thermographique d' enregistrement avec ton de l'image amélioré
US6693062B2 (en) 2001-06-29 2004-02-17 Agfa-Gevaert Thermographic recording material with improved image tone
EP1300251B1 (fr) 2001-10-02 2006-12-27 Agfa-Gevaert Enregistrement thermique au moyen d'un spot mobile
US7175977B2 (en) 2003-12-18 2007-02-13 Agfa-Gevaert Stabilizers for use in thermographic recording materials
US7097961B2 (en) 2004-05-17 2006-08-29 Agfa Gevaert Stabilizers for use in substantially light-insensitive thermographic recording materials
EP1637338B1 (fr) 2004-09-17 2007-04-04 Agfa-Gevaert Matériau d'enregistrement thermographique pratiquement insensible à la lumière
US7179768B2 (en) 2004-11-05 2007-02-20 Agfa-Gevaert Toning agents for use in thermographic recording materials
EP2199100A1 (fr) 2008-12-22 2010-06-23 Agfa-Gevaert N.V. Laminés de sécurité pour documents de sécurité

Family Cites Families (4)

* 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
US3080254A (en) * 1959-10-26 1963-03-05 Minnesota Mining & Mfg Heat-sensitive copying-paper
EP0582144B1 (fr) * 1992-08-03 1997-04-23 Minnesota Mining And Manufacturing Company Matériau d'enregistrement thermosensible adressé par laser
JP2681907B2 (ja) * 1992-11-20 1997-11-26 日本製紙株式会社 感熱記録体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7282468B2 (en) 2005-07-18 2007-10-16 Carestream Health Inc. Direct thermographic materials with catechol borate reducing agents

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Publication number Publication date
EP0692733A3 (fr) 1996-03-20
EP0692733A2 (fr) 1996-01-17

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