EP0809144B1 - Thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton - Google Patents

Thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton Download PDF

Info

Publication number
EP0809144B1
EP0809144B1 EP19970201458 EP97201458A EP0809144B1 EP 0809144 B1 EP0809144 B1 EP 0809144B1 EP 19970201458 EP19970201458 EP 19970201458 EP 97201458 A EP97201458 A EP 97201458A EP 0809144 B1 EP0809144 B1 EP 0809144B1
Authority
EP
European Patent Office
Prior art keywords
recording material
image
thermal
materials
substantially non
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19970201458
Other languages
English (en)
French (fr)
Other versions
EP0809144A1 (de
Inventor
Bartholomeus Horsten
Johan Loccufier
Geert Defieuw
Luc Leenders
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
Agfa Gevaert AG
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, Agfa Gevaert AG filed Critical Agfa Gevaert NV
Priority to EP19970201458 priority Critical patent/EP0809144B1/de
Publication of EP0809144A1 publication Critical patent/EP0809144A1/de
Application granted granted Critical
Publication of EP0809144B1 publication Critical patent/EP0809144B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • 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
    • B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron

Definitions

  • the present invention relates to a substantially non-photosensitive thermographic material suitable for thermal development. In particular, it concerns improvements in stabilization thereof.
  • Thermal imaging or thermography is a recording process wherein images are generated by the use of imagewise modulated thermal energy.
  • Direct thermal 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.
  • a typical heat-sensitive (thermographic) copy paper includes in the heat-sensitive layer a thermoplastic binder, e.g ethyl cellulose, a water-insoluble silver salt, e.g. silver stearate and an appropriate organic reducing agent, of which 4-methoxy-1-hydroxy-dihydronaphthalene is a representative. Localized heating of the sheet in the thermographic reproduction process causes a visible change to occur in the heat-sensitive layer.
  • Thermosensitive copying paper is used in "front-printing” or “back-printing” using infra-red radiation absorbed and transformed into heat in contacting infra-red light absorbing image areas of an original as illustrated in Figures 1 and 2 of US-P 3,074,809.
  • DOS 2127 169 discloses a light- and heat-sensitive recording material, comprising a support and at least one light- and/or heat-sensitive layer thereon, which contains a binder and an oxidation-reduction image-forming combination comprising (i) a heavy metal salt oxidizing agent, (ii) a reducing agent and (iii) a stabilizer precursor together with a photosensitive silver halide or another photosensitive metal salt, a sensitizing dye and/or an activator-toning agent, characterized in that it contains as stabilizer precursor an azole thioether or a blocked azole thione.
  • azoles are unsaturated heterocyclic five-membered rings with at least one nitrogen atom.
  • DOS 2740324 discloses a thermally developable light-sensitive material, comprising a support, having therein or in at least one layer thereon containing (a) an organic silver salt, (b) a photocatalyst and (c) a reducing agent, and (d) at least one 1,2,4-triazole compound.
  • WO 94/03833 discloses a heat-processed color image-recording material comprising (a) a support carrying in one or more layers a dye-providing material capable of releasing a diffusible dye upon cleavage in the presence of silver ions and/or a soluble silver complex, a thermal solvent, a silver salt oxidizing material, and a binder and, (b) on the same or a second support and image-receiving layer capable of receiving the diffusible dye released from said dye-providing material, said image-recording material additionally includes an auxiliary ligand capable of complexing with the silver ions of said silver salt oxidizing material, said ligand dissolving sufficient silver salt oxidizing material to provide a total concentration of silver species greater than or equal to twice the concentration obtained in the absence of the auxiliary ligand.
  • Stabilization to light of direct thermal recording materials utilizing oxidation-reduction image-forming processes based on substantially light-insensitive organic silver salts and reducing agents therefor is important for images for medical applications requiring long term stability for legal reasons, which may be viewed using a viewbox. Furthermore improved stabilization to light must not be achieved at the expense of other image characteristics in particular colour neutrality of both the background and the maximum density.
  • the colour neutrality of black monochrome images can be quantified by spectrophotometric measurements according to ASTM Norm E179-90 in a R(45/0) geometry with evaluation according to ASTM Norm E308-90 to produce the CIELAB a* and b* coordinates and the colour neutrality of the maximum density can be quantified using the numerical colour value (NCV).
  • NCV D 1 x D 2 (D 3 ) 2 where D 1 , D 2 and D 3 are lowest, next highest and highest respectively of the optical densities measured with a MacBethTM TR924 densitometer through blue, green and red filters.
  • thermosensitive element comprising a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith and a binder, on a support
  • thermosensitive element further comprises in reactive association with the substantially light-insensitive organic silver salt and the organic reducing agent a substituted or unsubstituted 1,2,4-triazole compound with at least one of the nitrogen atoms having a hydrogen atom and none of the carbon atoms being part of a thione-group, the compound not being annulated with an aromatic ring system.
  • a thermal image recording process comprising the steps of: (i) providing a substantially non-photosensitive black and white recording material, as described above; (ii) bringing an outermost layer of the recording material into proximity with a heat source; (iii) applying heat from a heat source image-wise to the recording material while maintaining proximity to the heat source to produce an image; and (iv) separating the recording material from the heat source.
  • a thermal image forming process is realized, wherein the heat source is a thermal head.
  • a thermal image forming process is realized, wherein the heat source is a thin film thermal head.
  • a thermal image recording process is realized, wherein the image is a black monochrome image with a background after 3 days exposure of the image-wise heated substantially non-photosensitive recording material on top of a 5mm thick white PVC window of a specially constructed light-box fitted with PlaniluxTM TLD 36W/54 fluorescent lamps placed such that the tops of the fluorescent lamps are 35mm below the undermost side of the image-wise heated substantially non-photosensitive recording material at a temperature of 30°C and a relative humidity of 85%, which has CIELAB a* and b* coordinates as calculated according to ASTM Norm E308-90 from spectrophotometric measurements carried out according to ASTM Norm E179-90 in a R(45/0) geometry in the ranges of 1.5 to +0.4 for the CIELAB a* coordinate and of -5.0 to +4.7 for the CIELAB b* coordinate.
  • thermosensitive element comprises a substituted or unsubstituted 1,2,4-triazole compound with at least one of the nitrogen atoms having a hydrogen atom and none of the carbon atoms being part of a thione-group, the compound not being annulated with an aromatic ring system.
  • the 1,2,4-triazole compound is substituted at a carbon atom with an alkyl, substituted alkyl, alkaryl, substituted alkaryl, aryl or substituted aryl thioether group.
  • Preferred 1,2,4-triazole compounds with superior stabilizing and image-tone improving properties without an annulated aromatic ring system are:
  • thermosensitive element comprises a substantially light-insensitive organic silver salt and an organic reducing agent therefor in thermal working relationship therewith in reactive association with a substituted or unsubstituted 1,2,4-triazole compound with at least one of the nitrogen atoms having a hydrogen atom and none of the carbon atoms being part of a thione-group, the ring not being annulated with an aromatic ring system.
  • the element may comprise a layer system in which the ingredients may be dispersed in different layers, with the proviso that all three ingredients are in reactive association with one another i.e.
  • the reducing agent and the 1,2,4-triazole compound must be present in such a way that they are able to diffuse to said substantially light-insensitive organic silver salt particles so that reduction of the organic silver salt to silver giving the desired image-tone can take place. Furthermore the 1,2,4-triazole compound must be present in such a way that the thermosensitive element can be stabilized against the influence of light.
  • Preferred organic silver salts 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, with silver behenate being particularly preferred.
  • Such silver salts are also called "silver soaps”.
  • Suitable organic reducing agents for the reduction of said substantially light-insensitive organic silver salts are organic compounds containing at least one active hydrogen atom linked to O, N or C, such as is the case with, aromatic di- and tri-hydroxy compounds; aminophenols; METOL (tradename); p-phenylenediamines; alkoxynaphthols, e.g. 4-methoxy-1-naphthol described in US-P 3,094,41; pyrazolidin-3-one type reducing agents, e.g.
  • PHENIDONE (tradename); pyrazolin-5-ones; indan-1,3-dione derivatives; hydroxytetrone acids; hydroxytetronimides; hydroxylamine derivatives such as for example described in US-P 4,082,901; hydrazine derivatives; and reductones e.g. ascorbic acid; see also US-P 3,074,809, 3,080,254, 3,094,417 and 3,887,378.
  • catechol-type reducing agents i.e. reducing agents containing at least one benzene nucleus with two hydroxy groups (-OH) in ortho-position
  • 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.
  • catechol-type reducing agents are benzene compounds in which the benzene nucleus 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.
  • the silver image density depends on the coverage of the above defined reducing agent(s) and organic silver salt(s) and has to be preferably such that, on heating above 100 °C, an optical density of at least 2.5 can be obtained. Preferably at least 0.10 moles of reducing agent per mole of organic silver salt is used.
  • auxiliary reducing agents are e.g. sterically hindered phenols, such as described in US-P 4,001,026; bisphenols, such as described in US-P 3,547,648; sulfonamidophenols, such as described in Research Disclosure, February 1979, item 17842, in US-P 4,360,581 and 4,782,004, and in EP-A 423 891; or organic reducing metal salts, such as stannous stearate described in US-P 3,460,946 and 3,547,648.
  • the auxiliary reducing agents may be present in the imaging layer or in a polymeric binder layer in thermal working relationship therewith.
  • the thermosensitive element may comprise in addition at least one polycarboxylic acid and/or anhydride thereof in a molar percentage of at least 20 with respect to all said organic silver salt(s) present and in thermal working relationship therewith.
  • the polycarboxylic acid may be aliphatic (saturated as well as unsaturated aliphatic and also cycloaliphatic) or an aromatic polycarboxylic acid, may be substituted and 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. adipic acid, pimelic acid etc.
  • 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.
  • thermosensitive element Film-forming binders of the thermosensitive element
  • the film-forming binder of the thermosensitive element containing the substantially light-insensitive organic silver salt may be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic heavy metal salt can be dispersed homogeneously: e.g. cellulose derivatives such as ethylcellulose, cellulose esters, e.g.
  • cellulose nitrate carboxymethylcellulose, starch ethers, galactomannan
  • 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 alcohol, 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, polystyrene and polyethylene or mixtures thereof.
  • the layer containing the organic silver salt is commonly coated onto a support in sheet- or web-form from an organic solvent containing the binder dissolved therein, but may be applied from an aqueous medium as a latex, i.e. as an aqueous polymer dispersion.
  • a latex the dispersible polymer has preferably some hydrophilic functionality.
  • Polymers with hydrophilic functionality for forming an aqueous polymer dispersion (latex) are described e.g. in US-P 5,006,451, but serve therein for forming a barrier layer preventing unwanted diffusion of vanadium pentoxide present as an antistatic agent.
  • the binder to organic silver salt weight ratio is preferably in the range of 0.2 to 6, and the thickness of the recording layer is preferably in the range of 5 to 50 ⁇ m.
  • binders or mixtures thereof may be used in conjunction 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 heavy metal salt, at a temperature above 60°C.
  • the recording layer contains preferably in admixture with said organic silver salts and reducing agents a so-called toning agent known from thermography or photothermography.
  • 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 are described in GB-P 1,439,478 and US-P 3,951,660, for example 3,4-dihydro-2,4-dioxo-1,3,2H-benzoxazine.
  • the recording layer may contain in addition to the ingredients mentioned above other additives such as free fatty acids, surface-active agents, 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, silicone oil, e.g. BAYSILONETM ⁇ l A (from BAYER AG, GERMANY), 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 F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
  • silicone oil e.g. BAYSILONETM ⁇ l A (from BAYER AG, GERMANY)
  • ultraviolet light absorbing compounds e.g. BAYSILONETM ⁇ l A (from BAYER AG, GERMANY)
  • the support for the thermal imaging material according to the present invention may be transparent, translucent or opaque, e.g. having a white light reflecting aspect and 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.
  • a paper base substrate is present which may contain white reflecting pigments, optionally also applied in an interlayer between the substantially non-photosensitive recording material and said paper base substrate.
  • the support may be in sheet, ribbon or web form and subbed if need be to improve the adherence to the thereon coated thermosensitive recording layer.
  • the support may be made of an opacified resin composition as described in EP's 194 106 and 234 563 and US-P's 3,944,699, 4,187,113, 4,780,402 and 5,059,579. Should a transparent base be used, said base may be colourless or coloured, e.g. having a blue colour.
  • One or more backing layers may be provided to control physical properties such as curl and static.
  • the outermost layer of the substantially non-photosensitive recording material may in different embodiments of the present invention be the outermost layer of the thermosensitive element, a protective layer applied to the thermosensitive element or a layer on the opposite side of the support to the thermosensitive element.
  • the thermosensitive element is coated with a protective layer to avoid local deformation of the thermosensitive element and to improve resistance against abrasion.
  • the protective layer preferably comprises a binder, which may be hydrophobic (solvent soluble) of hydrophilic (water soluble).
  • a binder which may be hydrophobic (solvent soluble) of hydrophilic (water soluble).
  • hydrophobic binders polycarbonates as described in EP-A 614 769 are particularly preferred.
  • hydrophilic binders are preferred for the protective layer, as coating can be performed from an aqueous composition and mixing of the hydrophilic protective layer with the immediate underlayer can be avoided by using a hydrophobic binder in the immediate underlayer.
  • a protective layer according to the present invention may further comprise a thermomeltable particle optionally with a lubricant present on top of the protective layer as described in WO 94/11199.
  • the lubricant which may be a surface active agent, a solid lubricant or a liquid lubricant, may be applied with or without a polymeric binder.
  • the surface active agents may be any agents known in the art such as carboxylates, sulfonates, aliphatic amine salts, aliphatic quaternary ammonium salts, polyoxyethylene alkyl ethers, polyethylene glycol fatty acid esters, fluoroalkyl C 2 -C 20 aliphatic acids.
  • liquid lubricants include silicone oils, synthetic oils, saturated hydrocarbons, glycols and phosphoric acid derivatives.
  • solid lubricants include various higher alcohols such as stearyl alcohol, fatty acids and phosphoric acid derivatives.
  • Such protective layers may also comprise particulate material, e.g. talc particles, optionally protruding from the protective outermost layer as described in WO 94/11198.
  • Other additives can also be incorporated in the protective layer e.g. colloidal particles such as colloidal silica.
  • the outermost layer of the substantially non-photosensitive recording material may comprise a hydrophilic binder.
  • Suitable hydrophilic binders for the outermost layer are, for example, gelatin, polyvinylalcohol, cellulose derivatives or other polysaccharides, hydroxyethylcellulose, hydroxypropylcellulose etc., with hardenable binders being preferred and polyvinylalcohol being particularly preferred.
  • the outermost layer according to the present invention may be crosslinked.
  • Crosslinking can be achieved by using crosslinking agents such as described in WO 95/12495 for protective layers, e.g. tetraalkoxysilanes, polyisocyanates, zirconates, titanates, melamine resins etc., with tetraalkoxysilanes such as tetramethylorthosilicate and tetraethylorthosilicate being preferred.
  • the outermost layer of the substantially non-photosensitive recording material according to the present invention may comprise a matting agent.
  • Suitable matting agents are described in WO 94/11198 and include e.g. talc particles and optionally protrude from the outermost layer.
  • Solid or liquid lubricants or combinations thereof such as described above for use in protective layers are also suitable for incorporation in the outermost layer to improve the slip characteristics of the substantially non-photosensitive recording materials according to the present invention.
  • an antistatic layer is the outermost layer on the other side of the support to the thermosensitive element.
  • any layer of the substantially non-photosensitive recording material of the present invention may proceed by any coating technique e.g. such 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.
  • Thermographic imaging is carried by the image-wise application of heat either in analogue fashion by direct exposure through an image or by reflection from an image or in digital fashion pixel by pixel either by using an infra-red heat souce, for example with a Nd-YAG laser or other infra-red laser, or direct thermal imaging with a thermal head.
  • an infra-red heat souce for example with a Nd-YAG laser or other infra-red laser, or direct thermal imaging with a thermal head.
  • 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.
  • the operating temperature of common thermal printheads is in the range of 300 to 400°C and the heating time per picture element (pixel) may be 50ms or less, the pressure contact of the thermal printhead with the substantially non-photosensitive recording material being e.g. 100-500g/cm 2 to ensure a good transfer of heat.
  • the imagewise heating of the substantially non-photosensitive recording material with the thermal printing heads may proceed through a contacting but removable resin sheet or web wherefrom during said heating no transfer of substantially non-photosensitive recording material can take place.
  • the direct thermal image-wise heating of the substantially non-photosensitive recording material proceeds by Joule effect heating in that selectively energized electrical resistors of a thermal head array are used in contact or close proximity with said recording layer.
  • 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. Activation of the heating elements can be power-modulated or pulse-length modulated at constant power.
  • EP-A 622 217 discloses a method for making an image using a direct thermal imaging element in which improvements in continuous tone reproduction are obtained by heating the thermal recording element by means of a thermal head having a plurality of heating elements in a specific manner.
  • Direct thermal imaging can be used for both the production of transparencies and reflection type prints.
  • Application of the present invention is envisaged in the fields of both graphics images requiring high contrast images with a very steep print density applied dot energy dependence and continuous tone images requiring a weaker print density applied dot energy dependence, such as required in the medical diagnostic field.
  • substantially non-photosensitive recording materials on a white opaque base are used, whereas in the medical diagnostic field black-imaged transparencies are widely used in inspection techniques operating with a light box.
  • a subbed polyethylene terephthalate support having a thickness of 175 ⁇ m was doctor blade-coated from a coating composition containing butanone as a solvent and the following ingredients so as to obtain thereon, after drying for 1 hour at 50°C, layers with the compositions given in table 1 for comparative examples 1 to 5 and invention examples 1 and 2.
  • the printer was equipped with a thin film thermal head with a resolution of 300 dpi and was operated with a line time of 19ms (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 1.5mJ/dot being sufficient to obtain maximum optical density in each of said substantially non-photosensitive recording materials.
  • the print head was separated from the imaging layer by a thin intermediate material contacted with a slipping layer of a separable 5 ⁇ m thick polyethylene terephthalate ribbon coated successively with a subbing layer, heat-resistant layer and said slipping layer (anti-friction layer) giving the ribbon with a total thickness of 6 ⁇ m.
  • the optical maximum and minimum densities of the prints given in table 2 were measured through a visual filter with a MacbethTM TR924 densitometer in the grey scale step corresponding to data levels of 255 and 0 respectively.
  • NCV values were determined at optical densities (D) with a visual filter of 1, 2 and 3 for the fresh materials and for the same materials after being heated at 57°C in a relative humidity of 34% for 3 days for the materials of comparative examples 1 to 5 and invention examples 1 and 2 and the NCV-values obtained summarized in table 2.
  • the NCV-values in table 2 enable materials with different stabilizing compounds at different concentrations to be compared on the basis of their colour neutrality, the dependence of their colour neutrality upon image optical density and the pre-exposure evolution in colour neutrality.
  • the stability of the image background of the materials of comparative examples 1 to 5 and invention examples 1 and 2 to post-image development exposure was evaluated by first thermally treating the materials for 3 days at 57°C and 34% relative humidity, next producing images in the materials by image-wise thermal development and finally exposing the images formed in the materials for 3 days on top of the white PVC window of a specially constructed light-box placed in a Votsch conditioning cupboard set at 30°C and a relative humidity of 85%. Only a central area of the window 550mm long by 500mm wide was used for mounting the test materials to ensure uniform exposure.
  • the stainless steel light-box used was 650mm long, 600mm wide and 120mm high with an opening 610mm long and 560mm wide with a rim 10mm wide and 5mm deep round the opening, thereby forming a platform for a 5mm thick plate of white PVC 630mm long and 580mm wide, making the white PVC-plate flush with the top of the light-box and preventing light loss from the light-box other than through the white PVC-plate.
  • This light-box was fitted with 9 PlaniluxTM TLD 36W/54 fluorescent lamps 27mm in diameter mounted length-wise equidistantly from the two sides, with the lamps positioned equidistantly to one another and the sides over the whole width of the light-box and with the tops of the fluorescent tubes 30mm below the bottom of the white PVC plate and 35mm below the materials being tested.
  • the suitability of a material was assessed on the basis of the initial background density determined through a blue filter using a MacBethTM TR924 densitometer, the background density through a blue filter after exposure on the lightbox for 3 days at 30°C and 85% relative humidity and the L*, a* and b* CIELAB-values of the background after 3 days and 6 days exposure in the lightbox at 30°C and 85% relative humidity.
  • the L*, a* and b* CIELAB-values of the background were determined by spectrophotometric measurements according to ASTM Norm E179-90 in a R(45/0) geometry with evaluation according to ASTM Norm E308-90.
  • Colour neutrality on the basis of CIELAB-values corresponds to a* and b* values of zero, with a negative a*-value indicating a greenish image-tone becoming greener as a* becomes more negative, a positive a*-value indicating a reddish image-tone becoming redder as a* becomes more positive, a negative b*-value indicating a bluish image-tone becoming bluer as b* becomes more negative and a positive b*-value indicating a yellowish image-tone becoming yellower as b* becomes more positive.
  • Visually acceptable colour neutrality corresponds to an a*-value between -1.5 and +0.4 together with b*-value between -5.0 and +4.4.
  • Comparative examples 1 to 5 show by comparison with invention examples 1 and 2 that substantially non-photosensitive recording materials comprising a thermosensitive element comprising a substituted or unsubstituted 1,2,4-triazole compound with at least one of the nitrogen atoms having a hydrogen atom and none of the carbon atoms being part of a thione-group, the compound not being annulated with an aromatic ring system, exhibit images with superior stability and images and background with superior colour neutrality compared with materials without such compounds (comparative example 1), materials with tribromomethyl benzenesulfinate, C01, a classical stabilizer for photothermographic materials (as disclosed in US-P 3,874,946) C01 (comparative examples 2 and 3) and materials with the classical silver halide photographic emulsion stabilizer C02, an unsaturated annulated 5-membered heterocyclic ring consisting of nitrogen and carbon atoms without a nitrogen atom with a hydrogen atom (comparative examples 4 and 5).
  • the substantially non-photosensitive recording materials of invention example 3 and comparative examples 6 to 10 were produced as described for invention examples 1 and 2 and comparative examples 2 to 5 except that compounds C03, C04, S02 were used instead of compounds C01, C02 and S01.
  • the substantially non-photosensitive recording material of comparative example 6 was produced as described for comparative example 1.
  • the compositions of the resulting layers are given in table 4.
  • Table 6 shows that the materials of comparative examples 6, 9 and 10 exhibit significantly higher D min -values after 3 days lightbox exposure than that for invention example 3 after 3 days lightbox.
  • the material of invention example 3 also exhibits a background with a higher degree of colour neutrality as adjudged by their a*- and b*-values after 3 days and 6 days lightbox exposure than those of comparative examples 6, 9 and 10, which fall outside the values required for visually acceptable colour neutrality given above.
  • the materials of comparative examples 6, 9 and 10 all exhibit backgrounds with a too yellow tone, comparative examples 6, 9 and 10 also exhibit a too green tone and comparative example 8 exhibits a too red tone.
  • Comparative examples 6 to 10 show by comparison with invention examples 1 to 3 that substantially non-photosensitive recording materials comprising a thermosensitive element comprising a substituted or unsubstituted 1,2,4-triazole compound with at least one of the nitrogen atoms having a hydrogen atom and none of the carbon atoms being part of a thione-group, the compound not being annulated with an aromatic ring system, exhibit images with superior stability and images and background with superior colour neutrality compared with materials without such compounds (comparative example 6), materials with C03, an unsaturated 5-membered heterocyclic ring consisting of nitrogen and carbon atoms without a nitrogen with a hydrogen atom substituted with a -SH group (comparative examples 7 and 8) and materials with C04, an unsaturated 5-membered heterocyclic ring with an oxygen ring atom substituted with a -SH group (comparative examples 9 and 10).
  • the substantially non-photosensitive recording materials of comparative examples 11 to 13 were produced as described for invention examples 1 and 2 and comparative examples 2 to 5 except that compound C05 was used instead of compounds C01, C02, S01, S02, S03 and S04.
  • the substantially non-photosensitive recording material of comparative example 11 was produced as described for comparative example 1.
  • the compositions of the resulting layers are given in table 7.
  • Comparative examples 11 to 13 show by comparison with invention examples 1 to 3 that substantially non-photosensitive recording materials comprising a thermosensitive element comprising a substituted or unsubstituted 1,2,4-triazole compound with at least one of the nitrogen atoms having a hydrogen atom and none of the carbon atoms being part of a thione-group, the compound not being annulated with an aromatic ring system, exhibit images with superior stability and images and background with superior colour neutrality compared with materials without such compounds (comparative example 11) and materials with C05, an unsaturated 5-membered heterocyclic ring consisting of nitrogen and carbon atoms without a nitrogen atom with a hydrogen atom (comparative examples 12 and 13).
  • the substantially non-photosensitive recording materials of comparative examples 14 and 15 were produced as described for invention examples 1 and 2 and comparative examples 2 to 5 except that compound C06 was used instead of compounds C01, C02 and S01.
  • the compositions of the resulting layers for comparative examples 14 and 15 are given in table 10 with the composition of the layer of the material of comparative example 6 being included for the sake of comparison.
  • Table 12 shows that all the materials after 3 days exposure in the lightbox at 30°C and 85% relative humidity exhibited poor colour neutrality with a very strong yellow tone as indicated by high positive b*-values and a fairly strong green tone as indicated by the moderately high negative a*-values.
  • Comparative examples 6, 14 and 15 show by comparison with invention examples 1 to 3 that substantially non-photosensitive recording materials comprising a thermosensitive element comprising a substituted or unsubstituted 1,2,4-triazole compound with at least one of the nitrogen atoms having a hydrogen atom and none of the carbon atoms being part of a thione-group, the compound not being annulated with an aromatic ring system, exhibit images with superior stability and images and background with superior colour neutrality compared with materials without such compounds (comparative example 6) and materials with C06, an unsaturated 5-membered heterocyclic ring with a sulphur ring atom substituted with a -SH group (comparative examples 14 and 15).

Claims (6)

  1. Ein wesentlich strahlungsunempfindliches Schwarz-Weiß-Aufzeichnungsmaterial mit einem auf einen Träger aufgetragenen wärmeempfindlichen Element, das ein wesentlich lichtunempfindliches organisches Silbersalz, ein organisches Reduktionsmittel dafür in thermischer wirksamer Beziehung dazu und ein Bindemittel enthält, dadurch gekennzeichnet, dass das wärmeempfindliche Element des weiteren in reaktiver Beziehung zu dem wesentlich lichtunempfindlichen organischen Silbersalz und dem organischen Reduktionsmittel eine gegebenenfalls substituierte 1,2,4-Triazolverbindung enthält, wobei zumindest eines der Stickstoffatome eine Bindung an ein Wasserstoffatom aufweist, keines der Kohlenstoffatome Teil einer Thiongruppe ist und die Verbindung nicht an ein aromatisches Ringsystem anelliert ist.
  2. Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, dass die 1,2,4-Triazolverbindung an einem Kohlenstoffatom mit einer gegebenenfalls substituierten Alkylgruppe, einer gegebenenfalls substituierten Alkarylgruppe oder einer gegebenenfalls substituierten Arylthioethergruppe substituiert ist.
  3. Aufzeichnungsmaterial nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das wesentlich lichtunempfindliche organische Silbersalz ein wesentlich lichtunempfindliches Silbersalz einer Fettsäure ist.
  4. Aufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das wärmeempfindliche Element mit einer Schutzschicht überzogen ist.
  5. Ein durch die nachstehenden Schritte gekennzeichnetes thermisches Bilderzeugungsverfahren : (i) Bereitstellen eines wesentlich strahlungsunempfindlichen Schwarz-Weiß-Aufzeichnungsmaterials nach einem der Ansprüche 1 bis 4, (ii) Anordnen einer Außenschicht des Aufzeichnungsmaterials in der Nähe einer Heizquelle, (iii) bildmäßige Beaufschlagung des Aufzeichnungsmaterials mit von der Heizquelle gelieferter Wärme zur Herstellung eines Bildes, wobei das Aufzeichnungsmaterial in der Nähe der Heizquelle gehalten wird, und (iv) Entfernen des Aufzeichnungsmaterials von der Heizquelle.
  6. Thermisches Bilderzeugungsverfahren nach Anspruch 5, dadurch gekennzeichnet, dass die Heizquelle ein Thermokopf ist.
EP19970201458 1996-05-21 1997-05-15 Thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton Expired - Lifetime EP0809144B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19970201458 EP0809144B1 (de) 1996-05-21 1997-05-15 Thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP96201375 1996-05-21
EP96201375 1996-05-21
EP19970201458 EP0809144B1 (de) 1996-05-21 1997-05-15 Thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton

Publications (2)

Publication Number Publication Date
EP0809144A1 EP0809144A1 (de) 1997-11-26
EP0809144B1 true EP0809144B1 (de) 2004-04-07

Family

ID=26142809

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19970201458 Expired - Lifetime EP0809144B1 (de) 1996-05-21 1997-05-15 Thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton

Country Status (1)

Country Link
EP (1) EP0809144B1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6348308B1 (en) 1997-09-03 2002-02-19 Agfa-Gevaert Substantially light-insensitive thermographic recording material with improved stability and image-tone
EP1006403B1 (de) * 1998-11-30 2004-10-20 Agfa-Gevaert Verwendung eines ein organisches Silbersalz enthaltenden direkten thermischen transparenten Bildaufzeichnungsmaterials zur Herstellung von Etiketten
EP1484641A1 (de) * 2003-06-06 2004-12-08 Agfa-Gevaert Bindemittel zur Verwendung in wärmeempfindlichen Elementen von thermographischen Aufzeichnungsmaterialien, die im wesentlichen lichtunempfindlich sind
US7348296B2 (en) 2003-06-06 2008-03-25 Agfa Healthcare Binders for use in the thermosensitive elements of substantially light-insensitive thermographic recording materials
EP1484642A1 (de) * 2003-06-06 2004-12-08 Agfa-Gevaert Binder für lichtunempfindliche thermographische Aufzeichnungsmaterialien
EP1484640B1 (de) * 2003-06-06 2009-09-16 Agfa HealthCare NV Netzmittel für lichtunempfindliche thermographische Aufzeichnungsmaterialien

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5332015A (en) * 1976-09-07 1978-03-25 Fuji Photo Film Co Ltd Thermodevelopable photosensitive material
US5328799A (en) * 1992-07-31 1994-07-12 Polaroid Corporation Thermographic and photothermographic imaging materials

Also Published As

Publication number Publication date
EP0809144A1 (de) 1997-11-26

Similar Documents

Publication Publication Date Title
US5599647A (en) New toning agents for thermographic and photothermographic materials and process
EP0903625B1 (de) Thermographischen Aufzeichnungsmaterialien
EP0809144B1 (de) Thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton
EP0752616B1 (de) Neuer Tönungsmittel für thermographische und photothermographische Materialien und Prozesse
EP0901040B1 (de) Im wesentlichen lichtunempfindliches thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton
EP0809142B1 (de) Herstellungsverfahren für ein thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton
US6348308B1 (en) Substantially light-insensitive thermographic recording material with improved stability and image-tone
US5817598A (en) Thermal image forming process with improved slip performance therein
US5854174A (en) Substantially non-photosensitive thermographic recording material with improved stability and image-tone
US5885765A (en) Thermographic recording material with improved tone reproduction
EP0782043B1 (de) Wärmeempfindliches Aufzeichnungsmaterial mit verbesserter Tonwiedergabe
US7033743B2 (en) Barrier layers for use in substantially light-insensitive thermographic recording materials
US6306573B1 (en) Production process for a benzotriazole-containing thermographic recording material with improved stability and image-tone
EP0809143A1 (de) Thermographisches Aufzeichnungsmaterial mit erhöhter Stabilität und verbessertem Bildton
EP0903627B1 (de) Haftvermittlungsschichten für die Verwendung in thermographischen Materialien
EP0903624B1 (de) Bindemittel für thermographische Materialien
EP0775592B1 (de) Wärmeempfindliches Bildaufzeichnungsverfahren
US6207614B1 (en) Substantially light-insensitive black and white monosheet thermographic recording material with improved image tone
EP0903626B1 (de) Aminotriazin-Verbindungen für (photo)thermographische Materialien
EP0903622B1 (de) (Photo)thermographisches Aufzeichnungsmaterial
EP0921434B1 (de) Thermographisches Aufzeichnungsmaterial mit verbesserter Bilddichte und/oder Gradation bei der thermischen Entwicklung
US6306572B1 (en) Binders for thermographic materials
EP1431059B1 (de) Sperrschichten für im wesentlichen lichtunempfindliche thermographische Aufzeichnungsmaterialien
EP0903623B1 (de) Bindemittel für thermographische Materialien
EP0663301B1 (de) Aufzeichnungsmaterial für ein Direktbildverfahren durch Wärme

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

17P Request for examination filed

Effective date: 19980526

17Q First examination report despatched

Effective date: 19990920

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: AGFA-GEVAERT

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

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

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

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040407

Ref country code: BE

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: 20040407

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69728468

Country of ref document: DE

Date of ref document: 20040513

Kind code of ref document: P

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

EN Fr: translation not filed
26N No opposition filed

Effective date: 20050110

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

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

Ref country code: DE

Payment date: 20070430

Year of fee payment: 11

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

Ref country code: GB

Payment date: 20070501

Year of fee payment: 11

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

Effective date: 20080515

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

Ref country code: DE

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

Effective date: 20081202

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

Ref country code: GB

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

Effective date: 20080515