EP0903626B1 - Aminotriazin-Verbindungen für (photo)thermographische Materialien - Google Patents

Aminotriazin-Verbindungen für (photo)thermographische Materialien Download PDF

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Publication number
EP0903626B1
EP0903626B1 EP19980202643 EP98202643A EP0903626B1 EP 0903626 B1 EP0903626 B1 EP 0903626B1 EP 19980202643 EP19980202643 EP 19980202643 EP 98202643 A EP98202643 A EP 98202643A EP 0903626 B1 EP0903626 B1 EP 0903626B1
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group
substituted
recording material
compounds
thermographic
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French (fr)
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EP0903626A1 (de
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Carlo Uyttendaele
Ivan Hoogmartens
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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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
    • G03C1/49836—Additives
    • 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

Definitions

  • the present invention relates to photothermographic and substantially light-insensitive thermographic recording materials comprising a novel compound or or a reaction product thereof with a polymer having active hydrogen atoms.
  • Thermal imaging or thermography is a recording process wherein images are generated by the use of thermal energy.
  • thermography three approaches are known:
  • Thermographic materials of type 1 become photothermographic upon incorporating a photosensitive agent which after exposure to UV, visible or IR light is capable of catalyzing or participating in a thermographic process bringing about changes in colour or optical density.
  • 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.
  • JP 2000864 discloses a heat-developing photosensitive material comprising a heat-developing photosensitive component which contains at least a photosensitive silver halide, a dye donative material, a reducer and binder on a support and an image-receiving component which is piled with the photosensitive component at least on transferring of image.
  • EP-A 831 365 discloses an imaging element for use in an image-forming process; the imaging element comprising a support, an image-forming layer; and a transparent electrically conductive layer comprising polypyrrole/poly(styrene sulfonic acid).
  • thermographic materials based on a substantially light-insensitive organic silver salt and a reducing agent for the organic silver salt is that the organic silver salt is formed in an aqueous medium and is precipitated and dried before dispersion in an organic solvent medium from which the dispersion is coated.
  • This production method is very inefficient as the organic silver salt after formation in water has to be separated and dried before dispersion in a solvent medium, is environmentally unsound as evaporation of solvent takes place during the coating process and it involves lengthy utilization of plant during the preparation of the organic silver salt dispersion and coating requires costly plant due to the need for solvent explosion prevention measures and solvent recovery to prevent solvent emission to the environment.
  • WO 94/16361 addressees this problem and discloses a multilayer heat-sensitive material which comprises: a colour-forming layer comprising: a colour-forming amount of finely divided, solid colourless noble metal or iron salt of an organic acid distributed in a carrier composition; a colour developing amount of a cyclic or aromatic organic reducing agent, which at thermal copy and printing temperatures is capable of a colour-forming reaction with the noble metal or iron salt; and an image-toning agent; characterized in that (a) the carrier composition comprises a substantially water-soluble polymeric carrier and a dispersing agent for the noble metal or iron salt and (b) the material comprises a protective overcoating layer for the colour-forming layer.
  • WO 95/12495 discloses a method of recording an image by image-wise heating a recording layer, the recording material comprising on the same side of a support, called the heat-sensitive side, (1) one or more layers comprising an imaging composition essentially consisting of (i) a substantially light-insensitive organic silver salt being in thermal working relationship with (ii) a reducing agent, and (2) at same side covering the imaging composition a protective layer, characterized in that the image-wise heating proceeds with a thermal head contacting the heat-sensitive side and through the protective layer mainly comprising a cured polymer or cured polymer composition e.g.
  • hydrophilic polymers having active hydrogen atoms selected from the group of polyvinyl alcohol, partially hydrolyzed polyvinyl acetate and gelatin at least part of which has reacted with hardening agents selected from the group consisting of polyisocyanates, polyepoxides, aldehydes and hydrolysed tetraalkyl orthosilicates.
  • US 5,661,101 discloses a recording material with, on a support, at least a coloring layer containing a first coloring component which is substantially colorless and a second coloring component which is substantially colorless and is colored by reacting with the first coloring component, and a protective layer provided on the coloring layer and having a pigment and a binder as main components, wherein at least the protective layer contains a polyvinyl alcohol resin having a syndiotacticity of greater than or equal to 55 molar % as diad indication and a saponification degree of greater than or equal to 85 molar %.
  • the protective layer may contain, in addition to the polyvinyl alcohol resin, a cross-linking agent for cross-linking the polyvinyl alcohol resin e.g. epoxy compounds, blocked isocyanates, vinyl sulfone compounds, aldehyde compounds, methylol compounds, boric acid, carboxylic acid anhydrides, silane compounds, chelating compounds and halogenated compounds.
  • thermographic materials produced from aqueous media exhibited poor archivability and poor light stability.
  • thermographic materials with crosslinked protective layers coated from aqueous media according to the teaching of WO 95/12495 require the use of substantial quantities of water-miscible solvents, e.g. the use of hydrolyzed tetaalkyl orthosilicates, or involved products such as formaldehyde for which emission norms are extremely low.
  • thermographic recording materials exhibited poor archivability.
  • thermographic recording materials coated from aqueous media whose prints exhibit high maximum density and low minimum density levels and improved archivability and/or improved light stability.
  • thermographic materials which enables reliable transport and does not cause image faults, while avoiding the use of organic solvents and the emission of noxious agents.
  • thermographic and photothermographic recording materials coated from aqueous media substantially improves the archivability and/or the light stability of prints made with such materials.
  • compounds represented by formula (I) have been found to be useful hardening agents for the protective layers of thermographic and photothermographic recording materials not requiring solvent during the coating process and not producing noxious emissions during the coating process.
  • thermographic recording material comprising the steps of: preparing aqueous dispersions or solutions together containing the substantially light-insensitive organic silver salt, the organic reducing agent therefor, the binder and the compound represented by formula (I); coating the dispersions or solutions onto a support to form the one or more layers making up the thermosensitive element.
  • Process for producing a photothermographic recording material is still further provided according to the present invention comprising the steps of: preparing aqueous dispersions or solutions together containing the substantially light-insensitive organic silver salt, the organic reducing agent therefor, the photosensitive silver halide, the binder and the compound represented by formula (I); coating the dispersions or solutions onto a support to form the one or more layers making up the photo-addressable thermally developable element.
  • aqueous for the purposes of the present invention includes mixtures of water with water-miscible organic solvents such as alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol etc.; glycols e.g. ethylene glycol; glycerine; N-methyl pyrrolidone; methoxypropanol; and ketones e.g. 2-propanone and 2-butanone etc.
  • alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol etc.
  • glycols e.g. ethylene glycol
  • glycerine glycerine
  • N-methyl pyrrolidone methoxypropanol
  • ketones e.g. 2-propanone and 2-butanone etc.
  • substantially light-insensitive is meant not intentionally light sensitive.
  • substantially solvent-free aqueous medium is meant that solvent, if present, is present in amounts below 10% by volume of the aqueous medium.
  • Preferred compounds represented by formula (I) are selected from the group consisting of: 2,4-diamino-1,3,5-triazine compounds, 2,4,6-triamino-1,3,5-triazine compounds, 2,6-diaminopyridine compounds, 2,4-diamino-pyrimidine compounds, 2,4,6-triamino-pyrimidine compounds, 2,5-diaminopyrrole compounds and 2,5-diamino-oxazole compounds.
  • Many 2,4-diamino-1,3,5-triazine compounds and 2,4,6-triamino-1,3,5-triazine compounds have been described in the literature: e.g.
  • 2,4-diamino-1,3,5-triazine compounds and 2,4,6-triamino-1,3,5-triazine compounds for use in the thermographic and photothermographic recording materials of the present invention are selected from the group of compounds consisting of: melamine compounds, ammeline compounds, melam compounds and guanamine compounds.
  • Suitable compounds according to formula (I) for use according to the present invention are:
  • thermographic recording material comprising a thermosensitive element including a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith and a binder.
  • the thermosensitive element may further comprise photosensitive silver halide in catalytic association with the organic silver salt, whereupon it becomes a photo-addressable thermally developable element and the material a photothermographic material.
  • thermosensitive or photo-addressable thermally developable element may comprise a layer system in which the ingredients are dispersed in different layers, with the proviso that the substantially light-insensitive organic silver salt and the organic reducing agent are in thermal working relationship with one another i.e. during the thermal development process the organic reducing agent must be present in such a way that it is able to diffuse to the substantially light-insensitive organic silver salt particles so that reduction of the organic silver salt can take place.
  • the thickness of the thermosensitive or photo-addressable thermally developable element is preferably in the range of 1 to 50 ⁇ m.
  • Preferred substantially light-insensitive organic silver salts for use in the photothermographic and thermographic recording materials of the present invention are silver salts of organic carboxylic acids and in particular 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”.
  • Silver salts of 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 may likewise be used to produce a thermally developable silver image. Combinations of different organic silver salts may be used in the thermographic recording materials according to the present invention.
  • a process for producing a suspension of particles containing a substantially light-insensitive organic silver salt is disclosed in EP-A 754 969.
  • the weight ratio of binder to organic silver salt weight used according to the present invention is preferably in the range of 0.2 to 6.
  • Suitable organic reducing agents for the reduction of the 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: catechol; hydroquinone; aminophenols; METOLTM; p-phenylenediamines; alkoxynaphthols, e.g. 4-methoxy-1-naphthol described in US-P 3,094,41; pyrazolidin-3-one type reducing agents, e.g.
  • PHENIDONETM 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.
  • Polyphenols such as the bisphenols used in the previous 3M DRY SILVERTM materials and current IMATION DRY SILVERTM materials, sulfonamide phenols such as used in the KODAK DACOMATICTM materials, and naphthols are particularly preferred for photothermographic materials on the basis of silver halide/organic silver salt/reducing agent.
  • auxiliary reducing agents are e.g. sterically hindered phenols, such as described in US-P 4,001,026; bisphenols, e.g. of the type described in US-P 3,547,648; or sulfonamidophenols as described in Research Disclosure 17842 published in February 1979, US-P 4,360,581, US-P 4,782,004 and in EP-A 423 891.
  • the auxiliary reducing agents may be present in the imaging layer or in a polymeric binder layer in thermal working relationship thereto.
  • auxiliary reducing agents that may be used in conjunction with the above mentioned primary reducing agents are hydrazides such as disclosed in EP-A 762 196, sulfonyl hydrazide reducing agents such as disclosed in US-P 5,464,738; trityl hydrazides and formyl-phenyl-hydrazides such as disclosed in US-P 5,496,695; trityl hydrazides and formyl-phenyl-hydrazides with diverse auxiliary reducing agents such as disclosed in US-P 5,545,505, US-P 5.545.507 and US-P 5,558,983; acrylonitrile compounds as disclosed in US-P 5,545,515 and US-P 5,635,339; 2-substituted malondialdehyde compounds as disclosed in US-P 5,654,130; and organic reducing metal salts, e.g. stannous stearate described in US-P 3,460,946 and 3,547,648.
  • Film-forming binders useful in the thermographic and photothermographic materials of the present invention may be solvent soluble or solvent dispersible or may be water soluble or water dispersible.
  • Film-forming binders suitable for materials coated from solvent dispersions or solutions can be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously or dissolved: e.g. polyesters, polyurethanes, polycarbonates, polymers derived from ⁇ , ⁇ -ethylenically unsaturated compounds such as after-chlorinated polyvinyl chloride, partially hydrolyzed polyvinyl acetate, polyvinyl alcohol, polyvinyl acetals, preferably polyvinyl butyral, and homopolymers and copolymers produced using monomers selected from the group consisting of: vinyl chloride, vinylidene chloride, acrylonitrile, acrylamides, methacrylamides; methacrylates, acrylates, methacrylic acid, acrylic acid, vinyl esters, styrenes, dienes and alkenes; or mixtures thereof.
  • Suitable water-soluble film-forming binders for use in thermographic and photothermographic materials according to the present invention are: polyvinyl alcohol, polyacrylamide, polymethacylamide, polyacrylic acid, polymethacrylic acid, polyvinylpyrrolidone, polyethyleneglycol, proteinaceous binders such as gelatin, modified gelatins such as phthaloyl gelatin, polysaccharides, such as starch, gum arabic and dextran and water-soluble cellulose derivatives.
  • a preferred water-soluble binder for use in the thermographic and photothermographic recording materials of the present invention is gelatin.
  • Suitable water-dispersible binders for use in the thermographic and photothermographic materials of the present invention may be any water-insoluble polymer.
  • Preferred water-dispersible binders for use in the thermographic and photothermographic recording materials of the present invention are polymer latexes.
  • Suitable polymer latexes for use according to the present invention are the CYDROTHANETM polyurethane dispersions from CYTEC-DYNO Industries, which are fully reacted, high molecular weight polyurethane-polyurea polymers dispersed in water by neutralizing the ionic groups in the prepolymer backbone, for example polymer latex numbers 1 to 7 given in table 1 below: polymer latex nr CYDROTHANETM polymer latex nr.
  • mixtures of polymers may be used, for example mixtures of water-soluble polymers, mixtures of water-dispersible polymers, or mixtures of water-soluble and water-dispersible polymers.
  • a protective layer containing a compound represented by formula (I) substantially as a reaction product with a polymer having active hydrogen atoms is meant that at least 90% of the compound according to formula (I) present in the protective layer is present as a reaction product with the polymer having active hydrogen atoms.
  • the quantity of the compound represented by formula (I) in the protective layer used in the present invention is preferably 1 to 80% by weight with respect to the polymer having active hydrogen atoms, particularly preferably 2 to 50% by weight with respect to the polymer having active hydrogen atoms and especially preferably 5 to 30% by weight with respect to the polymer having active hydrogen atoms.
  • the reaction product between a compound represented by formula (I) and a polymer having active hydrogen atoms is a crosslinked layer produced by acid-catalyzed reaction of the active hydrogen atoms of the polymer with the compound represented by formula (I).
  • Suitable acid catalysts include sulfonic acids e.g. methanesulfonic acid, para-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid and dinonylnaphthalenesulfonic acid.
  • Polymers having active hydrogen atoms containing hydroxy groups are preferred.
  • Suitable polymers having active hydrogen atoms for use in the present invention include: polyvinyl alcohol; gelatin and gelatin derivatives; dextran and dextran derivatives; polysaccharoses; acrylic resins with methylol-groups; methacrylic resins with methylol-groups; polyacrylamides; polymethacrylamides; hydroxycelluloses and hydroxyalkylcelluloses, with polyvinyl alcohol being particularly preferred.
  • thermosensitive and photo-addressable thermally developable elements in which the compound represented by formula (I) is exclusively present in the thermosensitive and photo-addressable thermally developable elements respectively.
  • thermosensitive element and photo-addressable thermally developable element protects the thermosensitive element and photo-addressable thermally developable element from atmospheric humidity and from surface damage by scratching etc. and prevents direct contact of printheads or heat sources with the recording layers.
  • Protective layers for thermosensitive and photo-addressable thermally developable elements which come into contact with and have to be transported past a heat source under pressure, have to exhibit resistance to local deformation and good slipping characteristics during transport past the heat source during heating.
  • the protective layer may contain one or more binders which may be hydrophilic or hydrophobic.
  • Suitable hydrophilic binders include: polyvinyl alcohol, gelatin and gelatin derivatives and other water-soluble polymers and polymer latexes.
  • the protective layer may also contain finely divided inorganic particles (i.e. average particle size of less than 1 ⁇ m) which modify the mechanical properties of the layer.
  • finely divided inorganic particles include: colloidal silica, kieselsol, Boehmite and aluminium oxide, with colloidal silica being particularly preferred.
  • the protective layer may further contain a dissolved lubricating material and/or particulate material, e.g. talc particles, optionally protruding therefrom.
  • suitable lubricating materials are a surface active agent, a liquid lubricant, a solid lubricant or mixtures thereof, which may be used with or without a polymeric binder.
  • Suitable slipping layer compositions are described, for example, in US 5,587,350, US 5,536,696, US 5,547,914, WO 95/12495, EP-A 775 592 and EP-A 775 595.
  • 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 a solid state in the recording layer at temperatures below 50°C, but upon heating becomes a plasticizer for the recording layer and/or a liquid solvent for at least one of the redox-reactants.
  • thermographic and photothermographic recording materials may contain one or more toning agents.
  • the toning agents should be in thermal working relationship with the substantially light-insensitive organic silver salt and reducing agents during thermal processing. Any known toning agent from thermography or photothermography may be used. Suitable toning agents are the phthalimides and phthalazinones within the scope of the formulae described in US-P 4,082,901 and the toning agents described in US-P 3,074,809, US-P 3,446,648 and US-P 3,844,797.
  • Particularly useful toning agents are the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type described in GB-P 1,439,478, US-P 3,951,660 and US-P 5,599,647.
  • thermographic and photothermographic recording materials of the present invention may contain one or more surfactants, which may be anionic, non-ionic or cationic surfactants and/or one or more dispersants.
  • surfactants which may be anionic, non-ionic or cationic surfactants and/or one or more dispersants.
  • suitable surfactants are:
  • Suitable dispersants are natural polymeric substances, synthetic polymeric substances and finely divided powders.
  • fine powder dispersants are finely divided non-metallic inorganic powders such as silica.
  • stabilizers and antifoggants may be incorporated into the thermographic and photothermographic materials of the present invention.
  • thermographic and photothermographic material may contain other additives such as free fatty acids, silicone oil, ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, silica, and/or optical brightening agents.
  • the support for the thermographic and photothermographic materials according to the present invention may be transparent, translucent or opaque 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.
  • the support may be in sheet, ribbon or web form and subbed if needs be to improve the adherence to the heat-sensitive recording layer coated thereon.
  • the support may be made of an opacified resin composition.
  • the photothermographic material of the present invention comprises photosensitive silver halide in catalytic association with the substantially light-insensitive organic silver salt.
  • the photosensitive silver halide used in the present invention may be employed in a range of 0.1 to 100 mole percent; preferably, from 0.2 to 80 mole percent; particularly preferably from 0.3 to 50 mole percent; especially preferably from 0.5 to 35 mole %; and especially from 1 to 12 mole % of substantially light-insensitive organic silver salt.
  • the silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide etc.
  • the silver halide may be in any form which is photosensitive including, but not limited to, cubic, orthorhombic, tabular, tetrahedral, octagonal etc. and may have epitaxial growth of . crystals thereon.
  • the silver halide used in the present invention may be employed without modification. However, it may be chemically sensitized with a chemical sensitizing agent such as a compound containing sulphur, selenium, tellurium etc., or a compound containing gold, platinum, palladium, iron, ruthenium, rhodium or iridium etc., a reducing agent such as a tin halide etc., or a combination thereof.
  • a chemical sensitizing agent such as a compound containing sulphur, selenium, tellurium etc., or a compound containing gold, platinum, palladium, iron, ruthenium, rhodium or iridium etc.
  • a reducing agent such as a tin halide etc.
  • the photo-addressable thermally developable element of the photothermographic material may contain a spectral sensitizer for the photosensitive silver halide, optionally together with a supersensitizer.
  • the photosensitive silver halide may be spectrally sensitized with various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes optionally, particularly in the case of sensitization to infra-red radiation, in the presence of a so-called supersensitizer.
  • thermographic and photothermographic recording materials 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, USA.
  • Thermographic imaging is carried out by the image-wise application of heat either in analogue fashion by direct exposure through an image of by reflection from an image, or in digital fashion pixel by pixel either by using an infra-red heat source, for example with a Nd-YAG laser or other infra-red laser, or by 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 via the Joule effect into heat, which is transferred to the surface of the thermographic material, wherein the chemical reaction resulting in the development of a black and white image takes place.
  • Such thermal printing heads may be used in contact or close proximity with the recording layer.
  • 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 less than 1.0 ms, the pressure contact of the thermal printhead with the recording material being e.g. 200-500g/cm 2 to ensure a good transfer of heat.
  • the image-wise heating of the recording layer with the thermal printing heads may proceed through a contacting but removable resin sheet or web wherefrom during the heating no transfer of recording material can take place.
  • the image signals for modulating the laser beam or current in the micro-resistors of a thermal printhead are obtained directly or from an intermediary storage means.
  • EP-A 654 355 describes a method for making an image by image-wise heating by means of a thermal head having energizable heating elements, wherein the activation of the heating elements is executed duty cycled pulsewise.
  • the thermographic materials are not suitable for reproducing images with fairly large number of grey levels as is required for continuous tone reproduction.
  • EP-A 622 217 discloses a method for making an image using a direct thermal imaging element producing improvements in continuous tone reproduction.
  • Image-wise heating of the thermographic material can also be carried out using an electrically resistive ribbon incorporated into the material.
  • Image- or pattern-wise heating of the thermographic material may also proceed by means of pixel-wise modulated ultrasound, using e.g. an ultrasonic pixel printer as described e.g. in US-P 4,908,631.
  • Photothermographic recording materials may be exposed with radiation of wavelength between an X-ray wavelength and a 5 microns wavelength with the image either being obtained by pixel-wise exposure with a finely focused light source, such as a CRT light source; a UV, visible or IR wavelength laser, such as a He/Ne-laser or an IR-laser diode, e.g. emitting at 780nm, 830nm or 850nm; or a light emitting diode, for example one emitting at 659nm; or by direct exposure to the object itself or an image therefrom with appropriate illumination e.g. with UV, visible or IR light.
  • a finely focused light source such as a CRT light source
  • a UV, visible or IR wavelength laser such as a He/Ne-laser or an IR-laser diode, e.g. emitting at 780nm, 830nm or 850nm
  • a light emitting diode for example one
  • any sort of heat source can be used that enables the recording materials to be uniformly heated to the development temperature in a time acceptable for the application concerned e.g. contact heating with for example a heated roller or a thermal head, radiative heating, microwave heating etc.
  • Thermographic and photothermographic materials according to the present invention may be used for both the production of transparencies, for example in the medical diagnostic field in which black-imaged transparencies are widely used in inspection techniques operating with a light box, and reflection type prints, for example in the graphics hard copy field.
  • the support will be transparent or opaque, i.e. having a white light reflecting aspect.
  • the base may be colourless or coloured, e.g. with a blue colour for medical diagnostic applications.
  • a 0.34mm thick polyethylene terephthalate sheet was first coated to a wet thickness of 7 ⁇ m with a composition which after drying and longitudinal and transverse stretching produced a 175 ⁇ m thick support coated with a sub-layer with the composition:
  • the coating dispersion was prepared by adding with stirring to 26.25g of a 17.6% aqueous solution of K7598 at 40°C: 17.5g of the aqueous silver behenate dispersion, deionized water (see table 3 for the quantities for the particular recording materials), a melamine compound (see table 3 for compound used and quantity used for the particular recording material), 2g of a 9.4% solution of Surfactant Nr. 3 and ethanol (for quantity see table 3).
  • the silver behenate emulsion layers were overcoated with a solution containing 2.64g of K7598, 0.65g of R01 dissolved in 61.05g of deionized water to which 0.3g of a 1.4% solution of Surfactant Nr. 4 had been added and dried producing a R01 coating weight of 0.65g/m 2 .
  • 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 the slipping layer (anti-friction layer) giving a ribbon with a total thickness of 6 ⁇ m.
  • 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 this 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 1.6 mJ/dot being sufficient to obtain maximum optical density in each of the thermographic materials of COMPARATIVE EXAMPLE 1 and INVENTION EXAMPLES 1.& 2.
  • the maximum densities, D max , and minimum densities D min , of the prints were measured through a blue filter with a MACBETHTM TR924 densitometer in the grey scale step corresponding to data levels of 255 and 0 respectively and are given in table 4.
  • the stability of the image background of the prints made with the thermographic materials of COMPARATIVE EXAMPLE 1 and INVENTION EXAMPLES 1 & 2 was evaluated on the basis of the change in minimum (background) density measured through a blue filter using a MACBETHTM TR924 densitometer, ⁇ D min , upon exposure on top of the white PVC window of a specially constructed light-box placed for 3 days in a VOTSCH conditioning cupboard set at 30°C and a relative humidity (RH) 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.
  • Table 4 The results are summarized in table 4.
  • thermographic recording materials of INVENTION EXAMPLES 1 & 2 with the compounds according to formula (I) CYMELTM385 and CYMELTM328, according to the present invention exhibited superior archivability [i.e. a lower ⁇ D min (blue)]to the thermographic recording material in the absence of a compound according to formula (I)].
  • the thermographic recording material of INVENTION EXAMPLE 1 also exhibited superior light box stability [i.e. a lower ⁇ D min (blue)] to the thermographic recording material of COMPARATIVE EXAMPLE 1.
  • the aqueous silver behenate dispersion was prepared as described for COMPARATIVE EXAMPLE 1 and INVENTION EXAMPLES 1 & 2.
  • the silver behenate emulsion layers of the recording materials of COMPARATIVE EXAMPLE 2 and INVENTION EXAMPLE 3 were prepared by adding with stirring to 15.67g of a 33.5% dispersion of polymer latex nr. 5: 17.5g of the aqueous silver behenate dispersion, then deionized water (see table 5 for the quantities for the particular recording materials), a melamine compound, if applicable, (see table 5 for the compound and quantity used for the particular recording material), 2g of a 9.4% solution of Surfactant Nr. 3 and 3g of ethanol.
  • thermographic recording material of INVENTION EXAMPLE 3 with CYMELTM385, a compound according to formula (I), according to the present invention exhibited superior archivability [i.e. a lower ⁇ D min (blue)] and superior light box stability [i.e. a lower ⁇ D min (blue)] to the thermographic recording material of COMPARATIVE EXAMPLE 2, in the absence of a compound according to formula (I).
  • the aqueous silver behenate dispersion was prepared as described for COMPARATIVE EXAMPLE 1 and INVENTION EXAMPLES 1 & 2.
  • the silver behenate emulsion layers of the recording materials of COMPARATIVE EXAMPLE 3 and INVENTION EXAMPLE 4 were prepared by adding with stirring to 17.5g of a 30% dispersion of polymer latex nr. 8: 17.5g of the aqueous silver behenate dispersion, then deionized water (see table 7 for the quantities for the particular recording materials), a melamine compound, if applicable, (see table 7 for compound and quantity used for the particular recording material) and 2g of a 9.4% solution of Surfactant Nr. 3.
  • thermographic recording material of INVENTION EXAMPLE 4 with CYMELTM385, a compound according to formula (I), according to the present invention exhibited much superior archivability [i.e. a lower ⁇ D min (blue)] and superior light box stability [i.e. a lower ⁇ D min (blue)] to the thermographic recording material of COMPARATIVE EXAMPLE 3, in the absence of a compound according to formula (I).
  • a subbed blue pigmented polyethylene terephthalate support having a thickness of 175 ⁇ m was coated with a coating composition containing 2-butanone as a solvent and the following ingredients so as to obtain thereon, after drying for 1 hour at 50°C, a layer containing:
  • thermosensitive element was coated with this dispersion to a wet layer thickness of 85 ⁇ m and the layer dried at 40°C for 15 minutes and then hardened at 45°C for 7 days, thereby producing the thermographic recording material of COMPARATIVE EXAMPLE 4.
  • An aqueous dispersion was produced by adding the following solutions and dispersions with mixing to 130g of deionized water: 20g of a 5% solution of Surfactant Nr. 7, 625g of a 4.55% solution of purified polyvinyl alcohol, 184.7g of 0.254% aqueous solution of p-toluenesulfonic acid, 45g of an aqueous dispersion containing 2.4% of SYLOIDTM 72, 2% of SERVOXYL VPDZ 3/100, 2% of SERVOXYL VPAZ 100, 1.2% of MICROACETM TYPE P3 and 3% of purified polyvinyl alcohol, 32g of a 5% aqueous dispersion of RILANIT GMS, 60g of a 15% aqueous dispersion of ammonium colloidal SiO 2 and a mixture of 7.2g of 1N nitric acid and 15g of deionized water.
  • the coating dispersion for the protective layer was produced by heating the resulting aqueous dispersion to about 36°C and adding 6g of a RESIMENETM AQ7550 and 50g of deionized water with stirring just before coating.
  • the thermosensitive element was coated with the protective layer dispersion to a wet layer thickness of 85 ⁇ m by doctor blade coating, dried at 40°C for 15 minutes and then hardened at 45°C for 7 days, thereby producing the thermographic recording material of INVENTION EXAMPLE 5.
  • thermographic recording materials of COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 were then carried out with a commercially available AGFA DRYSTARTM 2000 (thermal head) printer with a maximum electrical input energy per dot of 63mW to produce an image over the whole width of the thermal head consisting of 11 blocks each printed at different electrical energies per dot and each with a non-printed strip in the middle thereof 2mm wide in the printing direction and 18cm long lateral to the printing direction, while printing the 2mm wide and 2cm long strips either side thereof.
  • AGFA DRYSTARTM 2000 (thermal head) printer with a maximum electrical input energy per dot of 63mW to produce an image over the whole width of the thermal head consisting of 11 blocks each printed at different electrical energies per dot and each with a non-printed strip in the middle thereof 2mm wide in the printing direction and 18cm long lateral to the printing direction, while printing the 2mm wide and 2cm long strips either side thereof.
  • the degree to which the print obtained distinguished between these 2mm wide laterally adjoining non-printed and printed strips was used as a measure of the image quality attained i.e. whether or not the two 2mm wide and 2cm long printed strips either side of the 2mm wide and 18cm long non-printed strip had been faithfully reproduced. Any non-uniform transport along the thermal head will result in the printed strips either side of the long non-printed strip not being faithfully reproduced with in the case of extremely non-uniform transport none of the 2mm wide strips being printed i.e. additional thick white lines being observed.
  • the prints were visually evaluated on a scale of 5 to 0 according to the following criteria:
  • thermographic recording materials of COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 was further evaluated by modifying an AGFA DRYSTARTM 2000 (thermal head) printer by incorporating a strain gauge so that the sideways strain generated by the recording materials in contact with the thermal head during the printing process could be determined.
  • the electrical signal generated by the strain gauge coupled to the thermal head at load, L, of 330g/cm of the thermal head and a transport speed of 4.5mm/s is a relative measure of the dynamic frictional coefficient.
  • the relative dynamic frictional coefficients were monitored during the printing of an image over the whole width of the thermal head consisting of 11 blocks each printed at different energies per dot and each with a non-printed strip in the middle thereof 2mm wide in the printing direction and 18cm long lateral to the printing direction, while printing the 2mm wide and 2cm long strips either side thereof.
  • the gauge response as a function of printing time during the printing of the thermographic recording materials of COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 are shown in figures 1 and 2 respectively. It can be seen that the printing performance of the thermographic recording materials of COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 are identical within experimental error.
  • protective layers coated from an aqueous medium substantially free of solvent and in the absence of water-soluble toxic aldehydes such as formaldeyde using "binders having active hydrogen atoms" and hardeners represented by formula I according to the present invention can achieve the performance of prior art protective layers according to the teaching of WO 95/12495, with the same mix of performance promoting additives, coated from an aqueous medium containing alcohols in which "hydrophilic binders having active hydrogen atoms" are hardened with hydrolyzed tetramethyl orthosilicate. It is therefore possible to avoid the environmentally undesirable emission of alcohols during coating without adversely affecting transport performance during printing.
  • An aqueous dispersion was produced by adding 2.92g of an aqueous dispersion containing 20% of T01 and 12.5% of GEL01 to 23.69g of deionized water and then stirring for 60 minutes at 50°C.
  • the coating dispersion for the thermosensitive element was produced by adding with stirring the following dispersions and solutions to the resulting dispersion: 1.11g of an aqueous dispersion containing 24.3% silver behenate and 2.91% ammonium salt of dodecylphenylsulfonate followed by 15 minutes stirring, then 19.1g of the aqueous dispersion containing 24.3% silver behenate and 2.91% ammonium salt of dodecylphenylsulfonate followed by 15 minutes stirring, then 4.18g of GEL01 followed by 60 minutes stirring while maintaining a temperature of 50°C, then adjusting the pH to 5.0 with 1N nitric acid and cooling the dispersion to 36°C and then just before coating 5g of an aqueous solution
  • the coating dispersion was then coated to a wet layer thickness of 56 ⁇ m on a subbed 175 ⁇ m thick polyethylene terephthalate support producing after drying the thermosensitive element of the thermographic recording material of INVENTION EXAMPLE 6 with 4.93g/m 2 of silver behenate and 3.97g/m 2 of gelatin.
  • thermographic recording material of INVENTION EXAMPLE 6 was produced by coating the thermosensitive element with the protective layer of INVENTION EXAMPLE 5. Printing of the thermographic recording material of INVENTION EXAMPLE 6 was carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results.
  • thermographic recording material of INVENTION EXAMPLE 7 was produced as described for the thermographic recording material of INVENTION EXAMPLE 6 except that except that the 6g of RESIMENETM AQ7550 and 50g of deionized water were added at the coating station itself.
  • Printing of the thermographic recording material of INVENTION EXAMPLE 7 was carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results. This demonstrates that the mode of addition of the compound represented by formula (I) which reacts with purified polyvinyl alcohol, a polymer having active hydrogen atoms, has little influence upon the print quality and the archivability of the prints.
  • thermographic recording material of INVENTION EXAMPLE 8 was produced as described for the thermographic recording material of INVENTION EXAMPLE 5 except that the 6g of RESIMENETM AQ7550 and 50g of deionized water were added at the coating station itself. Printing of the thermographic recording material of INVENTION EXAMPLE 8 was carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results. These results confirm the results obtained with the thermographic recording material of INVENTION EXAMPLE 7.
  • aqueous dispersions used in the preparation of the protective layers of the thermographic recording materials of INVENTION EXAMPLES 9 to 17 were produced by adding the following solutions and dispersions with mixing to 150g of deionized water: 20g of a 5% solution of Surfactant Nr.
  • the coating dispersion for the protective layer was produced by heating the resulting aqueous dispersions to about 36°C and adding crosslinking agent (for quantity and type used for the particular coating emulsions used in the preparation of the thermographic recording materials of INVENTION EXAMPLES 9 to 17 type see table 9), 50g of deionized water with stirring just before coating.
  • the thermosensitive element of the thermographic recording material of INVENTION EXAMPLE 6 were coated with the protective layer dispersions to a wet layer thickness of 85 ⁇ m by doctor blade coating, dried at 40°C for 15 minutes and then hardened at 45°C for 7 days, thereby producing the thermographic recording materials of INVENTION EXAMPLES 9 to 17.
  • thermographic recording materials of INVENTION EXAMPLES 9 to 17 were carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results.
  • Crosslinking agent Image quality archivability of print type quantity [g] 9 7.2 RESIMENE AQ-7550 4.0 1 very good 10 7.2 RESIMENE AQ-7550 6.0 1 very good 11 7.2 RESIMENE AQ-7550 8.0 1 very good 12 7.2 RESIMENE AQ-7550 10.0 1 very good 13 6.0 MADURITETM MW815 6.0 1 very good 14 5.5 MAPRENALTM VMF3921W 5.5 1 very good 15 7.2 MAPRENALTM MF920 6.0 1 very good 16 2.0 CYMELTM 373 5.5 1 very good 17 7.2 CYMELTM 385 6.0 1 very good
  • Table 9 show that the results of the thermographic evaluation of the thermographic recording materials of INVENTION EXAMPLES 9 to 17 summarized
  • thermographic recording materials of INVENTION EXAMPLES 18 to 22 correspond to the thermographic recording materials of INVENTION EXAMPLES 13 to 17 respectively differing only in that the thermosensitive element which was coated was that of the thermographic recording material of INVENTION EXAMPLE 5 instead of the thermosensitive element of the thermographic recording material of INVENTION EXAMPLE 6.
  • thermographic recording materials of INVENTION EXAMPLES 18 to 22 were carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results. These results confirmed the results obtained with the thermographic recording materials of INVENTION EXAMPLES 13 to 17.
  • thermographic recording material of INVENTION EXAMPLE 23 was produced as described for INVENTION EXAMPLE 6 except that LEVASILTM VP AC 4055 was used instead of a 15% aqueous dispersion of ammonium colloidal SiO 2 .
  • Printing of the thermographic recording materials of INVENTION EXAMPLE 23 was carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results.
  • thermographic recording material of INVENTION EXAMPLE 24 was produced as described for INVENTION EXAMPLE 5 except that LEVASILTM VP AC 4055 was used instead of a 15% aqueous dispersion of ammonium colloidal SiO 2 .
  • Printing of the thermographic recording materials of INVENTION EXAMPLE 24 was carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results.
  • the results of the thermographic evaluation of the thermographic recording materials of INVENTION EXAMPLES 41 to 46 summarized in table 13 show that the prints produced with thermographic recording materials containing a reaction product of a compound represented by formula (I) with different polymers having active hydrogen atoms in the protective layer have a very good print quality and exhibit very good archivability.
  • aqueous dispersions used in the preparation of the protective layers of the thermographic recording materials of INVENTION EXAMPLES 25 to 30 were produced by adding the following solutions and dispersions with mixing to 115g of deionized water: surfactant (for the type, quantity and concentration used, see table 10), 680g of a 4.55% solution of purified polyvinyl alcohol, 184.7g of 0.254% aqueous solution of p-toluenesulfonic acid, 45g of an aqueous dispersion containing 2.4% of SYLOIDTM 72, 2% of SERVOXYLTM VPDZ 3/100, 2% of SERVOXYLTM VPAZ 100, 1.2% of MICROACETM TYPE P3 and 3% of purified polyvinyl alcohol, 32g of a 5% aqueous dispersion of RILANITTM GMS, 60g of a 15% aqueous dispersion of ammonium colloidal SiO 2 and a mixture of 7.2g of 1N
  • the coating dispersions for the protective layers were produced by heating the resulting aqueous dispersions to about 36°C and adding 6g of RESIMENETM AQ-7550 and 50g of deionized water with stirring just before coating. The pH of the coating dispersions was about 3.7.
  • the thermosensitive element of the thermographic recording material of INVENTION EXAMPLE 6 was coated with the protective layer dispersions to a wet layer thickness of 85 ⁇ m by doctor blade coating, dried at 40°C for 15 minutes and then hardened at 45°C for 7 days, thereby producing the thermographic recording materials of INVENTION EXAMPLES 25 to 30.
  • thermographic recording materials of INVENTION EXAMPLES 25 to 30 were carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results.
  • Invention example number Surfactant used Image quality archivability of print Nr concentration [%] quantity [g] 25 7 5 15 1 very good 26 7 5 10 1 very good 27 7 5 5 1 very good 28 7 5 15 1 very good 29 8 5 15 1 very good 30 9 5 15 1 very good.
  • the results of the thermographic evaluation of the thermographic recording materials of INVENTION EXAMPLES 25 to 30 summarized in table 10 show that the prints produced with thermographic recording materials containing a reaction product of a compound represented by formula (I) with purified polyvinyl alcohol, a polymer having active hydrogen atoms, in the protective layer with different and different quantities of surfactants have a very good print quality and exhibit very good archivability.
  • thermographic recording materials of INVENTION EXAMPLES 31 to 35 were produced by adding the following solutions and dispersions with mixing to 150g of deionized water: 20g of a 5% aqueous solution of Surfactant Nr.
  • the coating dispersions for the protective layer was produced by heating the resulting aqueous dispersions to about 36°C and adding 24g of RESIMENETM AQ-7550 and 240g of deionized water with stirring just before coating.
  • the pH of the coating dispersion was about 3.9.
  • the thermosensitive element of the thermographic recording material of INVENTION EXAMPLE 6 was coated with the protective layer dispersions to a wet layer thickness of 85 ⁇ m by doctor blade coating, dried at 40°C for 15 minutes and then hardened at 45°C for 7 days, thereby producing the thermographic recording materials of INVENTION EXAMPLES 31 to 35.
  • thermographic recording materials of INVENTION EXAMPLES 31 to 35 were carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results.
  • Invention example number quantity of aqueous dispersion containing 2.4% of SYLOID 72, 2% of SERVOXYL VPDZ 3/100, 2% of SERVOXYL VPAZ 100, 1.2% of MICROACE TYPE P3 and 3% of purified polyvinyl alcohol [g] Quantity of 5% dispersion of RILANIT GMS [g] Image quality Archivability of print 31 50 40 1 very good 32 45 36 1 very good 33 45 32 1 very good 34 40 32 1 very good 35 40 28 1 very good
  • Table 11 show that the prints produced with thermographic recording materials containing a reaction product of a compound represented by formula (I) with purified polyvinyl alcohol, a polymer having active hydrogen atoms, in
  • aqueous dispersions used in the preparation of the protective layers of the thermographic recording materials of INVENTION EXAMPLES 36 & 37 were produced by adding the following solutions and dispersions with mixing to 280g of deionized water: 60g of a 5% aqueous solution of Surfactant Nr.
  • the coating dispersion for the protective layer was produced by heating the resulting aqueous dispersions to about 36°C and adding 24g of RESIMENETM AQ-7550 and 80g of deionized water with stirring just before coating.
  • the thermosensitive elements of the thermographic recording materials of INVENTION EXAMPLES 5 and 6 were coated with the protective layer dispersions to a wet layer thickness of 40 ⁇ m by doctor blade coating, dried at 40°C for 15 minutes and then hardened at 45°C for 7 days, thereby producing the thermographic recording materials of INVENTION EXAMPLES 36 & 37.
  • thermographic recording materials of INVENTION EXAMPLES 36 & 37 were carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results. These results show that the prints produced with thermographic recording materials containing a reaction product of a compound represented by formula (I) with a different type pf polyvinyl alcohol, a polymer having active hydrogen atoms, in the protective layer had a very good print quality and exhibit very good archivability.
  • aqueous dispersions used in the preparation of the protective layers of the thermographic recording materials of INVENTION EXAMPLES 38 to 40 were produced by adding the following solutions and dispersions with mixing to 150g of deionized water: 30g of a 5% aqueous solution of Surfactant Nr.
  • thermographic recording materials of INVENTION EXAMPLES 38 to 40 were produced by heating the resulting aqueous dispersions to about 36°C and adding 7g of RESIMENETM AQ-7550.
  • the thermosensitive element of the thermographic recording materials of INVENTION EXAMPLE 6 was coated with the protective layer dispersions to a wet layer thickness of 85 ⁇ m by doctor blade coating, dried at 40°C for 15 minutes and then hardened at 45°C for 7 days, thereby producing the thermographic recording materials of INVENTION EXAMPLES 38 to 40.
  • thermographic recording materials of INVENTION EXAMPLES 38 to 40 were carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results.
  • Table 12 show that the prints produced with thermographic recording materials containing a reaction product of a compound represented by formula (I) with purified polyvinyl alcohol, a polymer having active hydrogen atoms, in the protective layer together with a polymer latex in different concentrations have a very good print quality and exhibit very good archivability.
  • aqueous dispersions used in the preparation of the protective layers of the thermographic recording materials of INVENTION EXAMPLES 41 to 46 were produced by adding the following solutions and dispersions with mixing to 150g of deionized water: 30g of a 5% aqueous solution of Surfactant Nr.
  • thermographic recording materials of INVENTION EXAMPLES 41 to 46 were produced by heating the resulting aqueous dispersions to about 36°C and adding 7g of RESIMENETM AQ-7550.
  • the thermosensitive element of the thermographic recording materials of INVENTION EXAMPLE 6 was coated with the protective layer dispersions to a wet layer thickness of 85 ⁇ m by doctor blade coating, dried at 40°C for 15 minutes and then hardened at 45°C for 7 days, thereby producing the thermographic recording materials of INVENTION EXAMPLES 41 to 46.
  • thermographic recording materials of INVENTION EXAMPLES 41 to 46 were carried out as described for COMPARATIVE EXAMPLE 4 and INVENTION EXAMPLE 5 with similar results.
  • Invention example number binder Image quality archivability of print 41 GEL01 1 very good 42 NATROSOL 250LR 1 very good 43 DEXTRAAN T70 1 very good 44 CULMINAL M42 1 very good 45 CYANAMERE P26 1 very good 46 PVP K-60 1 very good
  • Table 13 show that the prints produced with thermographic recording materials containing a reaction product of a compound represented by formula (I) with different polymers having active hydrogen atoms in the protective layer have a very good print quality and exhibit very good archivability.

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Claims (14)

  1. Ein wesentlich lichtunempfindliches thermografisches Aufzeichnungsmaterial mit einem wärmeempfindlichen Element, das ein wesentlich lichtunempfindliches organisches Silbersalz, ein Reduktionsmittel dafür in thermischer wirksamer Beziehung dazu und ein Bindemittel enthält, dadurch gekennzeichnet, dass das thermografische Aufzeichnungsmaterial keine Polypyrrol/Poly(styrolsulfonsäure) in einer elektrisch leitfähigen Schicht enthält und ferner eine Verbindung der Formel (I) oder ein Reaktionsprodukt davon mit einem Polymer mit aktiven Wasserstoffatomen enthält :
    Figure 00470001
    in der bedeuten :
    R1 und R3 unabhängig voneinander ein Wasserstoffatom, eine Hydroxyalkylgruppe, eine substituierte Hydroxyalkylgruppe, eine Alkoxyalkylgruppe, eine substituierte Alkoxyalkylgruppe, eine Alkylgruppe, eine substituierte Alkylgruppe, eine -(C=O)R5-Gruppe, eine substituierte Alkenylgruppe oder eine Alkenylgruppe, und
    R2 und R4 unabhängig voneinander eine Hydroxyalkylgruppe, eine substituierte Hydroxyalkylgruppe, eine Alkoxyalkylgruppe, eine substituierte Alkoxyalkylgruppe, eine Alkylgruppe, eine substituierte Alkylgruppe, eine -(C=O)R5-Gruppe, eine Alkenylgruppe oder eine substituierte Alkenylgruppe, oder
    R1 und R2 zusammen und R3 und R4 zusammen unabhängig voneinander die zum Schließen eines heterocyclischen, gegebenenfalls substituierten Ringes benötigten Atome,
    R5 eine Arylgruppe, eine substituierte Arylgruppe, eine Alkylgruppe oder eine substituierte Alkylgruppe, und
    Z die zum Vervollständigen eines gegebenenfalls substituierten, 5 oder 6 Ringatome enthaltenden heteroaromatischen Ringes benötigten Atome,
    wobei entweder das wärmeempfindliche Element mit einer Schutzschicht überzogen ist und die Schutzschicht die Verbindung der Formel (I) im wesentlichen als Reaktionsprodukt mit dem Polymer mit aktiven Wasserstoffatomen enthält oder die Verbindung der Formel (I) ausschließlich im wärmeempfindlichen Element enthalten ist.
  2. Thermografisches Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, dass der 5 oder 6 Ringatome enthaltende heteroaromatische Ring substituiert ist durch Wasserstoff, Chlor, Fluor, Iod, Brom oder eine Hydroxyl-, Alkoxy-, Aryloxy-, Mercapto-, Thioalkoxy-, -(C=O)R6-, Aryl-, Alkyl- oder -NR1R2-Gruppe oder eine Verbindungsgruppe zwischen zwei oder mehr Diamin-1,3,5-triazingruppen, wobei R6 ein Wasserstoffatom oder eine Alkyl-, Aryl-, Aryloxy-, Alkoxy-, Amino- oder Hydroxylgruppe bedeutet und all diese Gruppen substituiert sein können.
  3. Thermografisches Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, dass die Verbindung der Formel (I) eine 2,4-Diamin-1,3,5-triazin-Verbindung, 2,4,6-Triamin-1,3,5-triazin-Verbindung, 2,6-Diaminpyridin-Verbindung, 2,4-Diaminpyrimidin-Verbindung, 2,4,6-Triaminpyrimidin-Verbindung, 2,5-Diaminpyrrol-Verbindung oder 2,5-Diaminoxazol-Verbindung ist.
  4. Thermografisches Aufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Bindemittel ein polymerer Latex ist.
  5. Thermografisches Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Bindemittel Gelatine ist.
  6. Thermografisches Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, dass das Polymer mit aktiven Wasserstoffatomen Hydroxylgruppen enthält.
  7. Fotothermografisches Aufzeichnungsmaterial, das ein fotoadressierbares, wärmeentwickelbare Element auf der Basis von einem wesentlich lichtunempfindlichen organischen Silbersalz, einem Reduktionsmittel dafür in thermischer wirksamer Beziehung dazu, strahlungsempfindlichem Silberhalogenid in katalytischer Beziehung zum wesentlich lichtunempfindlichen organischen Silbersalz und einem Bindemittel enthält, dadurch gekennzeichnet, dass das fotoadressierbare wärmeentwickelbare Element kein Farbstoffdonormaterial enthält und das fotothermografische Aufzeichnungsmaterial keine Polypyrrol/Poly(styrolsulfonsäure) in einer elektrisch leitfähigen Schicht enthält und ferner eine Verbindung der Formel (I) oder ein Reaktionsprodukt davon mit einem Polymer mit aktiven Wasserstoffatomen enthält :
    Figure 00490001
    in der bedeuten :
    R1 und R3 unabhängig voneinander ein Wasserstoffatom, eine Hydroxyalkylgruppe, eine substituierte Hydroxyalkylgruppe, eine Alkoxyalkylgruppe, eine substituierte Alkoxyalkylgruppe, eine Alkylgruppe, eine substituierte Alkylgruppe, eine -(C=O)R5-Gruppe, eine substituierte Alkenylgruppe oder eine Alkenylgruppe, und
    R2 und R4 unabhängig voneinander eine Hydroxyalkylgruppe, eine substituierte Hydroxyalkylgruppe, eine Alkoxyalkylgruppe, eine substituierte Alkoxyalkylgruppe, eine Alkylgruppe, eine substituierte Alkylgruppe, eine -(C=O)R5-Gruppe, eine Alkenylgruppe oder eine substituierte Alkenylgruppe, oder
    R1 und R2 zusammen und R3 und R4 zusammen unabhängig voneinander die zum Schließen eines heterocyclischen, gegebenenfalls substituierten Ringes benötigten Atome,
    R5 eine Arylgruppe, eine substituierte Arylgruppe, eine Alkylgruppe oder eine substituierte Alkylgruppe, und
    Z die zum Vervollständigen eines gegebenenfalls substituierten, 5 oder 6 Ringatome enthaltenden heteroaromatischen Ringes benötigten Atome,
    wobei entweder das fotoadressierbare wärmeentwickelbare Element mit einer Schutzschicht überzogen ist und die Schutzschicht die Verbindung der Formel (I) im wesentlichen als Reaktionsprodukt mit dem Polymer mit aktiven Wasserstoffatomen enthält oder die Verbindung der Formel (I) ausschließlich im wärmeempfindlichen Element enthalten ist.
  8. Fotothermografisches Aufzeichnungsmaterial nach Anspruch 7, dadurch gekennzeichnet, dass der 5 oder 6 Ringatome enthaltende heteroaromatische Ring substituiert ist durch Wasserstoff, Chlor, Fluor, Iod, Brom oder eine Hydroxyl-, Alkoxy-, Aryloxy-, Mercapto-, Thioalkoxy-, -(C=O)R6-, Aryl-, Alkyl- oder -NR1R2-Gruppe oder eine Verbindungsgruppe zwischen zwei oder mehr Diamin-1,3,5-triazingruppen, wobei R6 ein Wasserstoffatom oder eine Alkyl-, Aryl-, Aryloxy-, Alkoxy-, Amino- oder Hydroxylgruppe bedeutet und all diese Gruppen substituiert sein können.
  9. Fotothermografisches Aufzeichnungsmaterial nach Anspruch 7, dadurch gekennzeichnet, dass die Verbindung der Formel (I) eine 2,4-Diamin-1,3,5-triazin-Verbindung, 2,4,6-Triamin-1,3,5-triazin-Verbindung, 2,6-Diaminpyridin-Verbindung, 2,4-Diaminpyrimidin-Verbindung, 2,4,6-Triaminpyrimidin-Verbindung, 2,5-Diaminpyrrol-Verbindung oder 2,5-Diaminoxazol-Verbindung ist.
  10. Fotothermografisches Aufzeichnungsmaterial nach einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass das Bindemittel ein polymerer Latex ist.
  11. Fotothermografisches Aufzeichnungsmaterial nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass das Bindemittel Gelatine ist.
  12. Fotothermografisches Aufzeichnungsmaterial nach Anspruch 7, dadurch gekennzeichnet, dass das Polymer mit aktiven Wasserstoffatomen Hydroxylgruppen enthält.
  13. Ein durch die nachstehenden Schritte gekennzeichnetes Verfahren zur Herstellung eines thermografischen Aufzeichnungsmaterials nach einem der Ansprüche 1 bis 6 : Anfertigung von wässrigen Dispersionen oder Lösungen, die zusammen das wesentlich lichtunempfindliche organische Silbersalz, das organische Reduktionsmittel dafür, das Bindemittel und die Verbindung der Formel (I) enthalten, und Auftrag der Dispersionen oder Lösungen auf einen Träger, um die eine oder mehreren, das wärmeempfindliche Element bildenden Schichten zu bilden.
  14. Ein durch die nachstehenden Schritte gekennzeichnetes Verfahren zur Herstellung eines fotothermografischen Aufzeichnungsmaterials nach einem der Ansprüche 7 bis 12 : Anfertigung von wässrigen Dispersionen oder Lösungen, die zusammen das wesentlich lichtunempfindliche organische Silbersalz, das organische Reduktionsmittel dafür, das strahlungsempfindliche Silberhalogenid, das Bindemittel und die Verbindung der Formel (I) enthalten, und Auftrag der Dispersionen oder Lösungen auf einen Träger, um die eine oder mehreren, das fotoadressierbare wärmeentwickelbare Element bildenden Schichten zu bilden.
EP19980202643 1997-09-17 1998-08-06 Aminotriazin-Verbindungen für (photo)thermographische Materialien Expired - Lifetime EP0903626B1 (de)

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JPH11129629A (ja) † 1997-10-27 1999-05-18 Fuji Photo Film Co Ltd 記録材料およびその製造方法
EP1484641A1 (de) * 2003-06-06 2004-12-08 Agfa-Gevaert Bindemittel zur Verwendung in wärmeempfindlichen Elementen von thermographischen Aufzeichnungsmaterialien, die im wesentlichen lichtunempfindlich sind

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