EP1014179B1 - Matériau d'enregistrement thermographique à stabilité augmentée - Google Patents

Matériau d'enregistrement thermographique à stabilité augmentée Download PDF

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Publication number
EP1014179B1
EP1014179B1 EP19990204259 EP99204259A EP1014179B1 EP 1014179 B1 EP1014179 B1 EP 1014179B1 EP 19990204259 EP19990204259 EP 19990204259 EP 99204259 A EP99204259 A EP 99204259A EP 1014179 B1 EP1014179 B1 EP 1014179B1
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EP
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Prior art keywords
thermographic recording
recording material
protective layer
weight
material according
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German (de)
English (en)
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EP1014179A1 (fr
Inventor
Eddy c/o Agfa-Gevaert N.V. Michiels
Yvan c/o Agfa-Gevaert N.V. Gilliams
Geert C/O Agfa-Gevaert N.V. Defieuw
Ivan c/o Agfa-Gevaert N.V. 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
    • G03C1/49836—Additives
    • G03C1/49863—Inert additives, e.g. surfactants, binders
    • 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

Definitions

  • the present invention relates to thermographic recording materials with improved shelf-life, improved stability to incident light and improved archivability.
  • the visible image pattern is formed by imagewise heating of a recording material containing matter that by chemical or physical process changes colour or optical density.
  • Such direct thermal imaging materials can be rendered photothermographic by 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.
  • photothermographic materials are the so called “Dry Silver” photographic materials of the 3M Company, which arc reviewed by D. A. Morgan in "Handbook of Imaging Science", edited by A. R. Diamond, page 43, published by Marcel Dekker in 1991.
  • EP-A 692 391 discloses a heat-sensitive recording material being suited for use in direct thermal imaging and comprising in the order given:(i) a transparent polymeric support, (ii) a heat-sensitive imaging layer, and (iii) a protective layer characterized in that the protective layer is an opaque layer containing uniformly distributed in an organic hydrophilic polymeric binder at least one opacifying pigment in the form of particulate material some of which protrudes from the surface of said binder and has anti-stick properties with regard to a thermal print head, wherein the opacitv of layer (iii) corresponds with an absorption and/or scattering of at least 80% of the light of the visible wavelength range (400 to 700 nm).
  • the invention examples of EP-A 692 391 disclose a protective layer consisting of 11% by weight of gelatin and 89% by weight of opacifying anatase-type titanium dioxide particles.
  • WO95/12495 discloses a method of recording an image by image-wise heating a recording material, 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 the 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.
  • thermosensitive elements With a protective layer desirable.
  • water-based protective coatings for thermosensitive and photo-addressable thermally developable elements based on substantially light-insensitive organic silver salts and reducing agents with good adhesion and transport properties in a thermographic printer using a thermal head, but without deterioration in thermographic imaging characteristics such as maximum and minimum print densities.
  • thermographic recording materials with good transport and imaging properties.
  • thermographic recording material thermally developable under substantially water-free conditions, comprising a support and a thermosensitive element, the thermosensitive element being provided with a protective layer and the thermosensitive element containing a substantially light-insensitive silver salt of an organic carboxylic acid, a reducing agent therefor in thermal working relationship therewith and a binder, characterized in that the protective layer contains at least one proteinaceous binder and non-opacifying inorganic particles with a weight averaged diameter of less than 1 ⁇ m in a concentration of between 5 and 70% by weight with respect to the weight of the protective layer, wherein the proteinaceous binders in the protective layer together contain less than 300ppm of halide ions.
  • thermographic recording materials of the present invention are black and white thermographic recording materials.
  • 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.
  • non-opacifying inorganic particles inorganic particles which do not absorb and/or scatter at least 80% of the light of the visible wavelength range (400 to 700 nm) thereby rendering the layer in which they are present opaque i.e. preventing transmission of visible light by reflection or dispersion.
  • heat solvent 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.
  • Heating in a substantially water-free condition means heating at a temperature of 80 to 250°C.
  • substantially water-free condition means that the reaction system is approximately in equilibrium with water in the air, and water for inducing or promoting the reaction is not particularly or positively supplied from the exterior to the element. Such a condition is described in T. H. James, "The Theory of the Photographic Process", Fourth Edition, Macmillan 1977, page 374.
  • the particle size of the non-opacifying inorganic particles having a weight averaged particle size of less than 1 ⁇ m used in the thermographic recording materials according to the present invention may be determined by such techniques as electron microscopy for particle sizes in the range 1 to 10,000 nm, photo-correlation spectroscopy, static light scattering for particle sizes in the range 300 to 1,500 nm, quasi-elastic light scattering (QELS) for the hydrodynamic diameters in the range 10 to 3,000 nm, light scattering particle size analyzers based on Mie scattering or Fraunhofer diffraction e.g. the COULTER" LS230 from COULTER CORP.
  • QELS quasi-elastic light scattering
  • Suitable non-opacifying inorganic particles include colloidal silica, china clay and kaolin.
  • thermosensitive element is provided with a protective layer, the protective layer containing at least one proteinaceous binder and non-opacifying inorganic particles with a weight averaged diameter of less than 1 ⁇ m, with non-opacifying inorganic particles with a weight averaged diameter 0.4 ⁇ m or less being preferred and those with a weight averaged diameter of 0.2 ⁇ m or less being particularly preferred.
  • concentration of the non-opacifying inorganic particles in the protective layer with respect to the weight of the protective layer is between 5 and 70% by weight, with 15 to 63% by weight being preferred and 20 to 50% by weight being particularly preferred.
  • the protective layer protects the thermosensitive 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 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 as well as excellent adhesion to the thermosensitive element which they protect.
  • the non-opacifying inorganic particles are preferably essentially colourless.
  • the protective layer preferably contains a non-cationic surfactant, and may contain a dissolved lubricating material and/or particulate material, e.g. talc particles, optionally protruding from the surface.
  • 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 proteinaceous binders include gelatin, modified gelatins such as phthaloyl gelatin, zein etc., with gelatin being preferred. It is preferred that the halide ion concentration in the proteinaceous binders present in the protective layer together do not exceed 150ppm, with not exceeding 100ppm being particularly preferred.
  • the alkali metal ion concentration in the proteinaceous binder(s) used in the protective layer of the thermographic and photothermographic recording materials of the present invention together preferably do not exceed 500ppm, with not exceeding 100ppm being particularly preferred and not exceeding 50ppm being especially preferred.
  • the halide ion concentration in organic materials can be determined by standard analytical techniques e.g. ion chromatography.
  • the following method using ion chromatography has been found to give reliable and reproducible values for halide ion concentration in proteinaceous binders: 1 ml of 0.1N silver nitrate is added to an accurately weighed sample weighing about 5 g in weight in a 100 ml beaker and then 5 ml of 70% nitric acid is added. The mixture is then boiled for about 15 minutes, whereupon the organic material is decomposed, the chloride ions are released into solution and then are bound by the silver ions forming a silver halide precipitate.
  • the suspension is filtered in a MilliporeTM and the residue thoroughly washed with deionized water.
  • the filter is then transferred to a test-tube with a stopper and 10 ml of 0.008% ammonium sulfide are added.
  • the mixture is then shaken for 20 minutes to convert the silver halide precipitate to a silver sulfide precipitate and release the halide ions into solution.
  • the solution is then injected, after dilution should this be necessary, into a DIONEXTM QIC ANALYSER with an AG3 guard column and an AS3 separator column and the halide ion concentration determined. Chloride ion concentrations down to 10 ⁇ g Cl - /ml sample can be detected using this technique.
  • Alkali metal ions in organic materials can be determined by digesting an accurately weighed ca. 500 mg sample with nitric acid and hydrogen peroxide in a closed destruction system. Then diluting to 25 ml with deionized water and injecting into an inductively coupled plasma to determine the alkali ion concentration.
  • Table 1 shows that the chloride ion concentration present in gelatin as determined by ion chromatography using a DIONEX QIC ANALYSER ion chromatograph varies according to gelatin type from 5300 to 17ppm and the sodium ion concentration varies between less than 100ppm to 2600ppm: GELATIN type general description chloride ion concentration [ppm] sodium ion concentration [ppm] GEL01 low viscosity 5300 - GEL02 hydrolyzed gelatin 2900 1700 GEL03 calcium-free, low viscosity 1270 - GEL04 calcium-free, medium viscosity 17 ⁇ 100 GEL05 calcium-free, low viscosity ⁇ 40 2600 GEL06 calcium-free, low viscosity ⁇ 40 ⁇ 100 GEL07 calcium-containing, medium viscosity ⁇ 250 - GEL08 calcium-free, high viscosity ⁇ 200 - GEL09 calcium-free, medium viscosity ⁇ 150 - GEL10 calcium-containing, low
  • Gelatin can be present in two forms dependent upon amongst other things upon the conditions under which it is dried. Above a temperature of 40°C a gelatin solution behaves as a normal polyelectrolyte. Upon gelation triple helices are formed. With increasing gelation temperature, the thermostabilization of the gel structures increases slightly because of increasing mobility of the gelatin segments with lead to an ever more perfect triple helix structure as can be seen by the increase in melting point. Upon drying the already formed aggregates of helices orientate in a planar manner, due to adhesion to the support layer. This results in the strong vertical swelling, several hundred % and smaller lateral swelling of layers separated from a support.
  • the layer temperature is higher, fewer gel structures form and the lateral swelling is greater [see Photographic Gelatin, R. J. Croome and F. G. Clegg, Focal Press, London (1965)]. If the layer temperature is 10 to 15°C during the drying process, the so-called gel-form of gelatin is produced with a pronounced triple helix structure as characterized by X-ray diffraction spectra [see Nature 168, 837 (1951)], whereas drying at temperatures of 20 to 30°C produces so-called sol-gelatin in which the triple helix structure is substantially absent.
  • the thermosensitive element contains a substantially light-insensitive silver salt of an organic carboxylic acid, a reducing agent therefor in thermal working relationship therewith and a binder.
  • thermal working relationship with one another is meant that during the thermal development process the reducing agent must be present in such a way that it is able to diffuse to the particles of substantially light-insensitive silver salt of an organic carboxylic acid so that reduction thereof can take place.
  • the thickness of the thermosensitive element is preferably in the range of 1 to 50 ⁇ m.
  • thermosensitive element further contains a photosensitive silver halide, making the thermographic recording material photothermographic.
  • Preferred substantially light-insensitive silver salts of an organic carboxylic acid used in the present invention are silver salts of aliphatic carboxylic acids known as fatty acids, wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, which silver salts are also called "silver soaps".
  • Other silver salts of an organic carboxylic acid 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 silver salt of an organic carboxylic acids may also be used in the present invention.
  • thermosensitive element Auxiliary film-forming binders of the thermosensitive element
  • Suitable water-dispersible binders for use as auxiliary binders in the thermographic and photothermographic recording materials of the present invention may be any water-insoluble polymer. It should be noted that there is no clear cut transition between a polymer dispersion and a polymer solution in the case of very small polymer particles resulting in the smallest particles of the polymer being dissolved and those slightly larger being in dispersion.
  • Preferred water-dispersible binders for use according to the present invention are water-dispersible film-forming polymers with covalently bonded ionic groups selected from the group consisting of sulfonate, sulfinate, carboxylate, phosphate, quaternary ammonium, tertiary sulfonium and quaternary phosphonium groups.
  • Further preferred water-dispersible binders for use according the present invention are water-dispersible film-forming polymers with covalently bonded moieties with one or more acid groups.
  • 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.
  • Suitable organic reducing agents for the reduction of silver salt of an organic carboxylic acid particles 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; METOLTM; p-phenylene-diamines; 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.
  • Catechol-type reducing agents i.e. reducing agents containing at least one benzene nucleus with two hydroxy groups (-OH) in ortho-position, such as 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 are preferred, with those described in EP 692 733 and EP-A 903 625 being particularly preferred.
  • Other suitable reducing agents are sterically hindered phenols, bisphenols and sulfonamidophenols.
  • Combinations of reducing agents may also be used that on heating become reactive partners in the reduction of the substantially light-insensitive silver salt or an organic carboxylic acid.
  • combinations of sterically hindered phenols with 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; and 2-substituted malonodialdehyde compounds as disclosed in US-P 5,654,130
  • 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 silver salt of an organic carboxylic acid 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 general 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 recording materials of the present invention In order to obtain improved shelf-life and reduced fogging, stabilizers and antifoggants may be incorporated into the thermographic recording materials of the present invention.
  • the thermosensitive element may comprise in addition at least one polycarboxylic acid and/or anhydride thereof in a molar percentage of at least 15 with respect to all the silver salt of an organic carboxylic acid(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. These acids may be substituted e.g. with alkyl, hydroxyl, nitro or halogen. They may be used in anhydride form or partially esterified on the condition that at least two free carboxylic acids remain or are available in the heat recording step.
  • thermographic and photothermographic recording materials of the present invention may contain anionic, non-ionic or amphoteric surfactants e.g.:
  • Suitable dispersants are natural polymeric substances, synthetic polymeric substances and finely divided powders, for example finely divided non-metallic inorganic powders such as silica.
  • the substantially light-insensitive thermographic recording 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 and/or optical brightening agents.
  • the support for the substantially light-insensitive thermographic recording material 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.
  • the support may be subbed with a subbing layer. It may also be made of an opacified resin composition.
  • the photosensitive silver halide used in the present invention may be employed in a range of 0.1 to 100 mol percent; preferably, from 0.2 to 80 mol percent; particularly preferably from 0.3 to 50 mol percent; especially preferably from 0.5 to 35 mol %; and especially from 1 to 12 mol % 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 photosensitive silver halide in the photo-addressable thermally developable element of the photothermographic recording material may be spectrally sensitized with a spectral sensitizer, optionally together with a supersensitizer.
  • a spectral sensitizer optionally together with a supersensitizer.
  • suitable spectral sensitizers including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes.
  • thermographic recording materials used in the present invention may also contain antihalation or acutance dyes which absorb light which has passed through the photosensitive thermally developable photographic material, thereby preventing its reflection. Such dyes may be incorporated into the photosensitive thermally developable photographic material or in any other layer of the photographic material of the present invention.
  • thermographic recording material of the present invention an antistatic layer is applied to an outermost layer.
  • any layer of the substantially light-insensitive thermographic 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. Heating takes place in a substantially water-free condition.
  • 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 recording 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 e.g. from opto-electronic scanning devices or from an intermediary storage means, optionally linked to a digital image work station wherein the image information can be processed to satisfy particular needs.
  • Activation of the heating elements can be power-modulated or pulse-length modulated at constant power.
  • 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.
  • thermographic recording materials When used in thermographic recording operating with thermal printheads the thermographic recording 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 recording material can also be carried out using an electrically resistive ribbon incorporated into the material.
  • Image- or pattern-wise heating of the thermographic recording material may also proceed by means of pixelwise modulated ultra-sound, 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, radiative heating, microwave heating etc.
  • Thermographic recording 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 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.
  • thermosensitive element ingredients in addition to those mentioned above:
  • Colloidal silica with any acid groups upon acidification substantially neutralized with ammonium ions was prepared from LEVASILTM VP AC 4055 in a two step process.
  • 10L of the acidic ion exchange resin LEWATITTM S100MB was added to a mixture of 12L of deionized water and 4L of a 26% aqueous ammonia solution.
  • the dispersion was then stirred for 90 minutes thereby converting the ion exchange resin into its ammonium form.
  • the converted ion exchange resin in the ammonium form was then filtered off and washed with deionized water until the wash-water was neutral.
  • thermosensitive elements of COMPARATIVE EXAMPLES 1 & 3 AND INVENTION EXAMPLES 1 to 6 175 ⁇ m thick subbed blue pigmented polyethylene terephthalate support was coated with an aqueous coating composition which upon drying produced a thermosensitive element containing the composition given in table 1.
  • thermosensitive elements of COMPARATIVE EXAMPLE 2 and INVENTION EXAMPLE 7 175 ⁇ m thick subbed blue pigmented polyethylene terephthalate support was coated with an aqueous coating composition and dried at 13 tc 20°C for 93s in a stream of air with a flow rate of 950kg/min to produce the thermosensitive element containing the composition given in table 1.
  • thermosensitive elements of the thermographic recording materials of INVENTION EXAMPLES 1 to 7 and COMPARATIVE EXAMPLES 1 to 3 were then coated with a protective layer having the compositions given in table 2. coverage in g/m 2 Invention example nr Comparative example nr 1-5 6 7 1 2 3 GEL06 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Colloidal silica in ammonium form 0.5 0.5 0.5 0.5 0.5 0.5 HCHO 0.2 0.4 0.87 0.4 0.87 0.4 STEAMICTM OOS 0.045 0.045 0.045 0.045 0.045 0.045 0.045 SYLOIDTM 72 0.09 0.09 0.09 0.09 0.09 0.09 RILANITTM GMS 0.135 0.135 0.135 0.135 0.135 0.135 0.135 SERVOXYLTM VPAZ 100 0.06 0.06 0.06 0.06 0.06 0.06 0.06 SERVOXYLTM VPDZ 3/100 0.075 0.075 0.075 0.075 0.075 0.075 0.075 Surfactant
  • thermographic recording materials with dimensions of 0.3 x 2cm 2
  • the layer combination on the side of the thermographic recording material coated with the thermosensitive element was detached from the support and its swelling behaviour in water monitored.
  • the increase in length of the thermographic recording materials of INVENTION EXAMPLES 1 to 7 and COMPARATIVE EXAMPLES 1 to 3 was measured This is expressed in table 3 as the % swelling.
  • thermographic recording materials of INVENTION EXAMPLES 1 to 7 and COMPARATIVE EXAMPLES 1 to 3 were investigated in a thermographic printer.
  • the printer was equipped with a thin film thermal head with a resolution of 300 dpi and was operated with a line time of 19ms (the line time being the time needed for printing one line). During this line time the printhead 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 substantially light-insensitive thermographic recording materials of INVENTION EXAMPLES 1 to 7.
  • the print quality was visually evaluated on the basis of the following print characteristics: printing characteristics print quality protective layer scoured off by the printing head poor printing quality good, appearance of protective layer acceptable good printing quality good, appearance of protective layer good excellent
  • the degree of lateral swelling of the layer composition of the thermographic recording materials of COMPARATIVE EXAMPLES 1 to 3 of above 15% are characteristic of gelatin in the sol-form, whereas that of the layer composition of the thermographic recording material of INVENTION EXAMPLES 3, 6 and 7 with a lateral swelling of 13% is characteristic of a mixture of gelatin in the gel-form with gelatin in the sol-form and that of the layer composition of the thermographic recording material of INVENTION EXAMPLES 1, 2, 4 and 5 with a lateral swelling of between 6 and 10% is characteristic of gelatin substantially in the gel-form.
  • thermographic recording materials of COMPARATIVE EXAMPLES 1 to 3 exhibited poor print quality due to the protective layer becoming detached from the thermosensitive element whereas the thermographic recording materials of INVENTION EXAMPLES 1 to 7 exhibited an excellent print quality. It is therefore evident that for protective layer thicknesses of about 3 ⁇ m, the adhesion of protective layers with exclusively sol-gelatin is poor, whereas it is satisfactory with gelatin consisting either of a mixture of sol and gel gelatin or of substantially gel-gelatin.
  • thermosensitive elements of INVENTION EXAMPLES 8 to 10 were coated on a 175 ⁇ m thick subbed polyethylene terephthalate support coated with the following composition: AgBeh 4.92g/m 2 GEL06 3.96g/m 2 formaldehyde 0.2g/m 2 Surfactant Nr. S01 0.39g/m 2 Surfactant Nr. S02 0.004g/m 2 R01 1.0g/m 2 T01 0.55g/m 2 boric acid 0.085g/m 2 (NH 4 ) 2 B 4 O 7 .10H 2 O 0.242g/m 2
  • thermosensitive elements of the thermographic recording materials of INVENTION EXAMPLES 8 to 10 were then coated with an aqueous coating composition and dried at an air temperature of 12°C to produce protective layers with the compositions given in table 4.
  • the protective layers of INVENTION EXAMPLES 1 to 7 and COMPARATIVE EXAMPLES 1 to 3 were dried to produce protective layers about 7 ⁇ m thick.
  • thermographic recording materials were printed as described for the thermographic recording materials of COMPARATIVE EXAMPLES 1 to 3 and INVENTION EXAMPLES 1 to 7.
  • the minimum densities, D min , of the prints given in table 5 were measured through a blue filter with a MACBETHTM TR924 densitometer in the grey scale step corresponding to data levels of 0.
  • the D min values of the prints produced with the thermographic recording materials of INVENTION EXAMPLES 8 to 10 were found to be strongly dependent upon the type of gelatin used in the protective layer and in particular upon the chloride ion concentration in the gelatin as can be seen from the results in table 5.
  • thermosensitive element described for INVENTION EXAMPLES 8 to 10 was coated with an aqueous coating composition and dried at an air temperature of 12°C to produce the thermographic recording materials of INVENTION EXAMPLES 11 to 14 and COMPARATIVE EXAMPLES 4 & 5 having protective layers with the compositions given in table 6.
  • thermosensitive element described for INVENTION EXAMPLES 8 to 10 was coated with an aqueous coating composition and dried at an air temperature of 12°C to produce the thermographic recording materials of INVENTION EXAMPLES 15 to 21 having protective layers with the compositions given in table 8.
  • thermosensitive element described for INVENTION EXAMPLES 8 to 10 was coated with an aqueous coating composition and dried at an air temperature of 12°C to produce the thermographic recording materials of INVENTION EXAMPLES 22 to 27 having protective layers with the compositions given in table 12.
  • a 175 ⁇ m thick polyethylene terephthalate support coated on both sides with subbing layer 01 was coated on one side with backside layer B01 with the following composition: KELZANTM S 10mg/m 2 polyethylenedioxythiophene 5mg/m 2 polystyrene sulfonic acid 10mg/m 2 Surfactant Nr. S04 21mg/m 2 PERAPRETTM PE40 10mg/m 2 KIESOLSOLTM 100F 20mg/m 2 PMMA latex 200mg/m 2 LATEX02 30mg/m 2
  • a 175 ⁇ m thick polyethylene terephthalate support coated on both sides with subbing layer 01 was also coated on one side with backside layer packet B02.
  • First a layer with the following composition was coated: GEL07 380mg/m 2 KIESELSOL 300F 340.7mg/m 2 Surfactant Mr. S04 13.3mg/m 2 Surfactant Nr. S05 6.7mg/m 2 2-methyl-2,4-pentanediol 22.2mg/m 2 Trimethylolpropane 11.1mg/m 2 PMMA latex 1mg/m 2 then with a layer with the following composition: GEL05 300mg/m 2 LATEX 03 450mg/m 2 Surfactant Mr. S07 3mg/m 2 Surfactant Mr.
  • thermographic recording material of INVENTION EXAMPLE 28 A 175 ⁇ m thick polyethylene terephthalate support with an uncoated subbing layer 01 on one side and backing layer B01 on the other was used for the thermographic recording material of INVENTION EXAMPLE 28 and a 175 ⁇ m thick polyethylene terephthalate support with uncoated subbing layer 01 on one side and backing layer B02 on the other was used for the thermographic recording material of INVENTION EXAMPLE 29.
  • thermosensitive element of the following composition was applied in each case to the side coated with subbing layer 01: thermosensitive element of INVENTION EXAMPLE 28 thermosensitive element of INVENTION EXAMPLE 29 AgB 5.031g/m 2 5.268g/m 2 Surfactant Nr. S01 0.503g/m 2 0.527g/m 2 GEL05 2.660g/m 2 2.785g/m 2 LATEX 01 1.843g/m 2 1.929g/m 2 R01 0.956g/m 2 1.001g/m 2 T01 1.132g/m 2 1.185g/m 2 Boric acid 0.325g/m 2 0.340g/m 2 HCHO 0.192g/m 2 0.201g/m 2
  • thermosensitive elements of the thermographic recording materials of INVENTION EXAMPLES 28 and 29 were then coated with a protective layer with the following composition: GEL06 4.29g/m 2 colloidal silica in ammonium form 1.34g/m 2 STEAMICTM OOS 0.08g/m 2 SYLOIDTM 72 0.15g/m 2 RILANITTM GMS 0.23g/m 2 SERVOXYLTM VPDZ 3/100 0.10g/m 2 SERVOXYLTM VPAZ 100 0.13g/m 2 Surfactant Nr. S03 0.13g/m 2 Surfactant Nr. S02 0.19g/m 2 Formaldehyde 0.34g/m 2
  • thermographic recording material with the gelatin backing layer INVENTION EXAMPLE 29 exhibits significantly less curl than the thermographic recording material with the polymethylmethacrylate-based backing layer of INVENTION EXAMPLE 28.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (12)

  1. Matériau d'enregistrement thermographique, thermiquement développable dans des conditions essentiellement anhydres, comprenant un support et un élément thermosensible, ledit élément thermosensible étant muni d'une couche de protection et ledit élément thermosensible contenant un sel d'argent essentiellement non photosensible d'un acide carboxylique organique, un agent de réduction pour ledit sel en relation de travail thermique avec lui et un liant, caractérisé en ce que ladite couche de protection contient au moins un liant protéique et des particules organiques non opacifiantes possédant un diamètre moyen en poids inférieur à 1 µm en une concentration entre 5 et 70 % en poids par rapport au poids de ladite couche de protection, lesdits liants protéiques dans ladite couche de protection contenant ensemble moins de 300 ppm d'ions halogénure.
  2. Matériau d'enregistrement thermographique selon la revendication 1, dans lequel lesdites particules inorganiques non opacifiantes possèdent un diamètre moyen en poids de 0,5 µm ou moins.
  3. Matériau d'enregistrement thermographique selon la revendication 1 ou 2, dans lequel lesdites particules inorganiques non opacifiantes possèdent un diamètre moyen en poids de 0,2 µm ou moins.
  4. Matériau d'enregistrement thermographique selon la revendication 1, dans lequel ladite concentration desdites particules inorganiques non opacifiantes dans ladite couche de protection s'élève entre 15 et 63 % en poids par rapport au poids de ladite couche de protection.
  5. Matériau d'enregistrement thermographique selon la revendication 1, dans lequel ladite concentration desdites particules inorganiques non opacifiantes dans ladite couche de protection s'élève entre 20 et 50 % en poids par rapport au poids de ladite couche de protection.
  6. Matériau d'enregistrement thermographique selon l'une quelconque des revendications précédentes, dans lequel ledit ion halogénure est un ion chlorure.
  7. Matériau d'enregistrement thermographique selon l'une quelconque des revendications précédentes, dans lequel ledit ou lesdits liants protéiques dans ladite couche de protection contiennent ensemble une concentration d'ions métalliques alcalins de 500 ppm ou moins.
  8. Matériau d'enregistrement thermographique selon l'une quelconque des revendications précédentes, dans lequel au moins un desdits liants protéiques dans ladite couche de protection est de la gélatine.
  9. Matériau d'enregistrement thermographique selon la revendication 9, dans lequel ladite gélatine se présente sous la forme d'un gel, à concurrence d'au moins 20 %.
  10. Matériau d'enregistrement thermographique selon l'une quelconque des revendications précédentes, dans lequel ledit liant est un deuxième liant protéique.
  11. Matériau d'enregistrement thermographique selon l'une quelconque des revendications précédentes, dans lequel ledit matériau d'enregistrement thermographique est muni d'une couche contenant un troisième liant protéique sur le côté opposé dudit support audit élément thermosensible.
  12. Matériau d'enregistrement thermographique selon l'une quelconque des revendications précédentes, dans lequel ledit élément thermosensible contient en outre un halogénure d'argent photosensible.
EP19990204259 1998-12-23 1999-12-08 Matériau d'enregistrement thermographique à stabilité augmentée Expired - Lifetime EP1014179B1 (fr)

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US6667148B1 (en) * 2003-01-14 2003-12-23 Eastman Kodak Company Thermally developable materials having barrier layer with inorganic filler particles
EP1484641A1 (fr) * 2003-06-06 2004-12-08 Agfa-Gevaert Liants pour emploi dans les éléments sensibles à la chaleur de matériaux d' enregistrement thermographiques sensiblement non-sensibles à la lumière

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WO1995012495A1 (fr) * 1993-11-06 1995-05-11 Agfa-Gevaert Naamloze Vennootschap Procede de thermographie directe au moyen d'un materiau d'enregistrement thermosensiblle et protege
DE69505605T2 (de) * 1994-07-13 1999-05-27 Agfa-Gevaert N.V., Mortsel Wärmeempfindliches Aufzeichnungsmaterial

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