EP0959383A1 - Matériau d'enregistrement photothermographique contenant des grains tabulaires et un composé d'hydrazine - Google Patents

Matériau d'enregistrement photothermographique contenant des grains tabulaires et un composé d'hydrazine Download PDF

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Publication number
EP0959383A1
EP0959383A1 EP98201649A EP98201649A EP0959383A1 EP 0959383 A1 EP0959383 A1 EP 0959383A1 EP 98201649 A EP98201649 A EP 98201649A EP 98201649 A EP98201649 A EP 98201649A EP 0959383 A1 EP0959383 A1 EP 0959383A1
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EP
European Patent Office
Prior art keywords
recording material
silver halide
photothermographic recording
alkyl group
aryl group
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Application number
EP98201649A
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German (de)
English (en)
Inventor
Hans c/o Agfa-Gevaert N.V. Strijckers
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to EP98201649A priority Critical patent/EP0959383A1/fr
Publication of EP0959383A1 publication Critical patent/EP0959383A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49818—Silver halides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/061—Hydrazine compounds

Definitions

  • the present invention relates to a photothermographic recording material with increased sensitivity containing photosensitive tabular silver halide grains and a hydrazine compound.
  • Thermal imaging or thermography is a recording process wherein images are generated by the use of imagewise modulated thermal energy.
  • Thermographic materials become photothermographic when a photosensitive agent is present which after exposure to UV, visible or IR light is capable of catalysing or participating in a thermographic process bringing about changes in colour or optical density.
  • Examples of photothermographic materials are the so called “Dry Silver” photographic materials of the 3M Company, which are reviewed by D.A. Morgan in “Handbook of Imaging Science", edited by A.R. Diamond, page 43, published by Marcel Dekker in 1991.
  • US-A 4,435,499 describes a photothermographic material wherein the material comprises a support bearing in reactive association photosensitive thin tabular exemplified silver bromoiodide grains having an average grain thickness of less than 0.3 ⁇ m and a photosensitive silver halide processing agent.
  • tabular silver halide grains in photothermographic materials because tabular grains have a higher light absorption and higher surface area available for spectral sensitization for a given coating weight of silver halide, despite the expected disadvantage of lower sensitivity according to the widely accepted Rutledge-Klosterboer model and the empirical evidence on which it is based.
  • a photothermographic recording material comprising a support and a photo-addressable thermally developable element containing a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith, photosensitive tabular silver halide grains in catalytic association with the substantially light-insensitive organic silver salt and a binder, characterized in that the photo-addressable thermally developable element further contains a hydrazine compound.
  • a recording process comprising the steps of bringing the above-described photothermographic recording material into the proximity of a source of actinic radiation; image-wise exposing the photothermographic recording material with the source of actinic radiation; bringing the image-wise exposed photothermographic recording material into the proximity of a heat source; uniformly heating the image-wise exposed photothermographic recording material; and removing the photothermographic recording material from the heat source.
  • the photo-addressable thermally developable element contains a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith, photosensitive tabular silver halide grains in catalytic association with the substantially light-insensitive organic silver salt, a binder and a hydrazine compound.
  • the element may comprise a layer system with the silver halide in catalytic association with the substantially light-insensitive organic silver salt ingredients, spectral sensitizer optionally together with a supersensitizer in intimate sensitizing association with the tabular silver halide particles and the other ingredients active in the thermal development process or pre- or post-development stabilization of the element being in the same layer or in other layers with the proviso that the organic reducing agent and the toning agent, if present, are in thermal working relationship with the substantially light-insensitive organic silver salt i.e. during the thermal development process the reducing agent and the toning agent, if present, are able to diffuse to the substantially light-insensitive organic silver salt, e.g. a silver salt of a fatty acid.
  • the substantially light-insensitive organic silver salt e.g. a silver salt of a fatty acid.
  • the photothermographic recording material according to the present invention further comprises a second photo-addressable thermally developable element on the opposite side of the support to the first photo-addressable thermally addressable element.
  • hydrazine compound for the purposes of this invention means hydrazine, substituted hydrazine compounds together with salts and complexes thereof.
  • Preferred hydrazine compounds are represented by fomula (I): R 1 -NR 2 -NR 3 -R 4 where R 1 and R 4 independently represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a formyl group, an oxo-alkyl group, an oxo-substituted alkyl group, an oxo-aryl group, an oxo-substituted aryl group, a sulfo-alkyl group, a sulfo-substituted alkyl group, a sulfo-aryl group, a sulfo-substituted aryl group, a phosphoryl-alkyl group, a phosphoryl-alkyl group,
  • the photo-addressable thermally developable element contains photosensitive tabular silver halide grains.
  • concentration of photosensitive tabular silver halide grains that may be used is usually in the range of 0.1 to 90 mole percent of the substantially light-insensitive organic silver salt, with the range from 0.2 to 50 mole % being preferred and the range from 0.5 to 35 mole percent being particularly preferred and the range from 1 to 12 mole percent of the substantially light-insensitive organic silver salt being especially preferred.
  • the photosensitive tabular silver halide grains in the in the photo-addressable thermally developable element of the photothermographic recording material of the present invention preferably have an average thickness of less than 0.3 ⁇ m and in particular an average thickness less than 0.15 ⁇ m.
  • the diameter of the photosensitive tabular silver halide grains is preferably greater than 0.3 ⁇ m and the aspect ratio of the photosensitive tabular silver halide grains is preferably in the range of 5:1 to 15:1.
  • the photosensitive tabular silver halide grains may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide etc.
  • Non-tabular photosensitive silver halide grains may be present in the photo-addressable thermally developable element in addition to the photosensitive tabular silver halide grains. These non-tabular photosensitive silver halide grains may be in any non-tabular form which is photosensitive including, but not limited to, cubic, orthorhombic, tetrahedral, octagonal etc. and may have epitaxial growth of crystals thereon and may also be chemically sensitized.
  • Photosensitive tabular silver halide grains preferably account for at least 50% of the projected area of the photosensitive silver halide grains in the photo-addressable thermally developable element of the photothermographic recording materials of the present invention and in a particularly preferred embodiment 70% of the projected area of the photosensitive silver halide grains.
  • Mixtures of emulsions having the same or different halide composition, crystal habit, crystal size, crystal size distribution and/or dopant(s) may be used in order to obtain improved sensitometry and image quality.
  • the silver halide used in the present invention may be employed without modification. However, it may be chemically sensitised with a chemical sensitising 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. Details of these procedures are described in T.H. James, "The Theory of the Photographic Process", Fourth Edition, Macmillan Publishing Co. Inc., New York (1977), Chapter 5, pages 149 to 169. If mixtures of silver halide emulsion crystals are used chemical sensitisation is preferably performed before mixing them in order to preserve an optimised chemical sensitisation.
  • a chemical sensitising agent such as a compound containing sulphur, selenium, tellurium etc., or a compound containing gold, platinum, palladium, iron, ruthenium,
  • 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 optionally.
  • Preferred cyanine dyes include those having a basic nucleus, such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus.
  • a basic nucleus such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus.
  • Preferred merocyanine dyes include those having not only the above described basic nuclei but also acid nuclei, such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus.
  • acid nuclei such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus.
  • imino groups or carboxyl groups are particularly preferred.
  • Suitable sensitizers of silver halide to infra-red radiation include those disclosed in EP-A's 465 078, 559 101, 616 014 and 635 756, JN's 03-080251, 03-163440, 05-019432, 05-072662 and 06-003763 and US-P's 4,515,888, 4,639,414, 4,713,316, 5,258,282 and 5,441,866.
  • Suitable supersensitizers for use with infra-red spectral sensitizers are disclosed in EP-A's 559 228 and 587 338 and in US-P's 3,877,943 and 4,873,184.
  • substantially light-insensitive is meant not intentionally light sensitive.
  • Preferred substantially light-insensitive organic silver salts are silver salts of organic carboxylic acids in particular 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 dodecyl sulphonate described in US-A 4,504,575; and silver di-(2-ethylhexyl)-sulfosuccinate described in EP-A 0 227 141.
  • Modified aliphatic carboxylic acids with thioether group as described e.g. in GB-P 1,111,492 and other organic silver salts as described in GB-P 1,439,478, e.g. silver benzoate and silver phthalazinone, may be used likewise to produce a thermally developable silver image.
  • a suspension of particles containing a substantially light-insensitive organic silver salt may be obtained by using a process, comprising simultaneous metered addition of an aqueous solution or suspension of an organic carboxylic acid or its salt; and an aqueous solution of a silver salt to an aqueous liquid, as described in EP-A 0 754 969.
  • the silver halide emulsion grains described above may be added to the photo-addressable thermally developable element in any fashion which places it in catalytic proximity to the substantially light-insensitive organic silver salt.
  • Silver halide and the substantially light-insensitive organic silver salt which are separately formed, i.e. ex-situ or "preformed", in a binder can be mixed prior to use to prepare a coating solution, but it is also possible to obtain the required intimate contact with the large specific surface area of the tabular grains by blending them for a long period of time in order.
  • a particularly preferred mode of preparing the emulsion of organic silver salt and photosensitive silver halide for coating of the photo-addressable thermally developable element from solvent media, according to the present invention is that disclosed in US-A 3,839,049, but other methods such as those described in Research Disclosure, June 1978, item 17029 and US-A 3,700,458 may also be used.
  • a particularly preferred mode of preparing the emulsion of organic silver salt and photosensitive silver halide for coating of the photo-addressable thermally developable element from aqueous media is that disclosed in unpublished Application PCT/EP 96/02579, filed June 13, 1996, which discloses a production method for a photothermographic recording material comprising the steps of: (i) providing a support; (ii) coating the support with a photo-addressable thermally developable element comprising a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association with the substantially light-insensitive organic silver salt, a reducing agent in thermal working relationship with the substantially light-insensitive organic silver salt and a binder, characterised in that the photosensitive silver halide is formed by reacting an aqueous emulsion of particles of the substantially light-insensitive organic silver salt with at least one onium salt with halide or polyhalide anion(s) and that the photo-addressable thermally developable element is
  • Suitable organic reducing agents for the reduction of the substantially light-insensitive organic silver salts in photo-addressable thermally developable element are organic compounds containing at least one active hydrogen atom linked to O, N or C, such as is the case with, mono-, bis-, tris- or tetrakis-phenols; mono- or bis-naphthols; di- or polyhydroxy-naphthalenes; di- or polyhydroxybenzenes; hydroxymonoethers such as alkoxynaphthols, e.g. 4-methoxy-1-naphthol described in US-A 3,094,41; pyrazolidin-3-one type reducing agents, e.g.
  • PHENIDONE (tradename); pyrazolin-5-ones; indan-1,3-dione derivatives; hydroxytetrone acids; hydroxytetronimides; 3-pyrazolines; pyrazolones; reducing saccharides; aminophenols e.g. METOL (tradename); p-phenylenediamines, hydroxylamine derivatives such as for example described in US-A 4,082,901; reductones e.g. ascorbic acids; hydroxamic acids; hydrazine derivatives; amidoximes; n-hydroxyureas; and the like, see also US-A 3,074,809, 3,080,254, 3,094,417 and 3,887,378.
  • Polyphenols such as the bisphenols used in the 3M DRY SILVERTM materials, sulfonamide phenols such as used in the Kodak DACOMATICTM materials, and naphthols are particularly preferred for photothermographic recording materials with photo-addressable thermally developable elements on the basis of photosensitive silver halide/organic silver salt/reducing agent.
  • the film-forming binder for the photo-addressable thermally developable element according to the present invention may be coatable from a solvent or aqueous dispersion medium.
  • the film-forming binder for the photo-addressable thermally developable element coatable from a solvent dispersion medium may be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously: e.g.
  • polymers derived from ⁇ , ⁇ -ethylenically unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl acetals that are made from polyvinyl alcohol as starting material in which only a part of the repeating vinyl alcohol units may have reacted with an aldehyde, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, polystyrene and polyethylene or mixtures thereof.
  • a particularly suitable polyvinyl butyral containing a minor amount of vinyl alcohol units is marketed by MONSANTO USA under the trade names BUTVARTM B76 and BUTVARTM B79 and provides a good adhesion to paper and properly subbed polyester supports.
  • the film-forming binder for the photo-addressable thermally developable developable element coatable from an aqueous dispersion medium may be all kinds of transparent or translucent water-dispersible or water soluble natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously for example proteins, such as gelatine and gelatine derivatives (e.g.
  • phthaloyl gelatine cellulose derivatives, such as carboxymethylcellulose, poly-saccharides, such as dextran, starch ethers, galactomannan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, homo-or co-polymerized acrylic or methacrylic acid, latex's of water dispersible polymers, with or without hydrophilic groups, or mixtures thereof.
  • Polymers with hydrophilic functionality for forming an aqueous polymer dispersion (latex) are described in US-A 5,006,451, but serve therein for forming a barrier layer preventing unwanted diffusion of vanadium pentoxide present as an antistatic agent.
  • the binder to organic silver salt weight ratio is preferably in the range of 0.2 to 6, whereas the thickness of the photo-addressable thermally developable element is preferably in the range of 5 to 50 ⁇ m.
  • binders or mixtures thereof may be used in conjunction with waxes or "heat solvents” also called “thermal solvents” or “thermosolvents” improving the reaction speed of the redox-reaction at elevated temperature.
  • heat solvent in this invention is meant a non-hydrolyzable organic material which is in solid state in the recording layer at temperatures below 50°C but becomes a plasticizer for the recording layer in the heated region and/or liquid solvent for at least one of the redox-reactants, e.g. the reducing agent for the organic silver salt, at a temperature above 60°C.
  • the photo-addressable thermally developable element may contain a so-called toning agent known from thermography or photothermography.
  • Suitable toning agents are succinimide and the phthalimides and phthalazinones within the scope of the general formulae described in US-A 4,082,901. Further reference is made to the toning agents described in US-A 3,074,809, 3,446,648 and 3,844,797.
  • Other particularly useful toning agents are the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type as described in GB-P 1,439,478, US-A 3,951,660 and US-A 5,599,647.
  • stabilizers and antifoggants may be incorporated into the photothermographic materials of the present invention.
  • suitable stabilizers and antifoggants and their precursors include the thiazolium salts described in US-P 2,131,038 and 2,694,716; the azaindenes described in US-P 2,886,437 and 2,444,605; the urazoles described in US-P 3,287,135; the sulfocatechols described in US-P 3,235,652; the oximes described in GB-P 623,448; the thiuronium salts described in US-P 3,220,839; the palladium, platinum and gold salts described in US-P 2,566,263 and 2,597,915; the tetrazolyl-thio-compounds described in US-P 3,700,457; the mesoionic 1,2,4-triazolium-3
  • surfactants for photo-addressable thermally developable elements coated from aqueous media are surfactants for photo-addressable thermally developable elements coated from aqueous media
  • Non-ionic, cationic or anionic surfactants may be used separately or as mixtures, according to the present invention, to produce dispersions of particles of the substantially light-insensitive organic silver salt in aqueous media and to disperse water-dispersible binders, such as polymer latex's, in aqueous media.
  • the photo-addressable thermally developable element may contain other additives such as free fatty acids, surface-active agents, antistatic agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H, silicone oil, e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY), ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, silica, colloidal silica, fine polymeric particles [e.g. of poly(methyl methacrylate)] and/or optical brightening agents.
  • antistatic agents e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
  • silicone oil e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY)
  • the photothermographic 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 photo-addressable thermally developable element or in any other layer of the photographic material of the present invention.
  • the support for the photothermographic recording material according to the present invention is a transparent resin film, e.g. made of a cellulose ester, e.g. cellulose triacetate, corona and flame treated polypropylene, polystyrene, polymethacrylic acid ester, polycarbonate or polyester, e.g. polyethylene terephthalate or polyethylene naphthalate as disclosed in GB 1,293,676, GB 1,441,304 and GB 1,454,956.
  • a transparent resin film e.g. made of a cellulose ester, e.g. cellulose triacetate, corona and flame treated polypropylene, polystyrene, polymethacrylic acid ester, polycarbonate or polyester, e.g. polyethylene terephthalate or polyethylene naphthalate as disclosed in GB 1,293,676, GB 1,441,304 and GB 1,454,956.
  • the support may be in sheet, ribbon or web form and subbed if need be to improve the adherence to the thereon coated thermally developable recording layer.
  • the support may be made of an opacified resin composition, e.g. polyethylene terephthalate opacified by means of pigments and/or micro-voids and/or coated with an opaque pigment-binder layer, and may be called synthetic paper, or paperlike film; information about such supports can be found in EP-A's 0 194 106 and 0 234 563 and US-A's 3,944,699, 4,187,113, 4,780,402 and 5,059,579. Should a transparent base be used, the base may be substantially colourless or coloured, e.g. having a blue colour.
  • One or more backing layers may be provided to control physical properties such as curl or static.
  • the outermost layer of the photothermographic recording material may in different embodiments of the present invention be the outermost layer of the photo-addressable thermally developable element, a protective layer applied to the photo-addressable thermally developable element or a layer on the opposite side of the support to the photo-addressable thermally developable element.
  • the photo-addressable thermally developable element is coated with a protective layer to avoid local deformation of the photo-addressable thermally developable element and to improve resistance against abrasion.
  • the protective layer preferably comprises a binder, which may be solvent-soluble, solvent-dispersible, water-soluble or water-dispersible.
  • a binder which may be solvent-soluble, solvent-dispersible, water-soluble or water-dispersible.
  • solvent-soluble binders polycarbonates as described in EP-A 614 769 are particularly preferred.
  • water-soluble or water-dispersible binders are preferred for the protective layer, as coating can be performed from an aqueous composition and mixing of the protective layer with the immediate underlayer can be avoided by using a solvent-soluble or solvent-dispersible binder in the immediate underlayer.
  • a protective layer according to the present invention may comprise in addition a thermomeltable particle optionally with a lubricant present on top of the protective layer as described in WO 94/11199.
  • a thermomeltable particle optionally with a lubricant present on top of the protective layer as described in WO 94/11199.
  • at least one solid lubricant having a melting point below 150°C and at least one liquid lubricant in a binder is present, wherein at least one of the lubricants is a phosphoric acid derivative.
  • the outermost layer according to the present invention may be crosslinked.
  • Crosslinking can be achieved by using crosslinking agents such as described in WO 95/12495 for protective layers, e.g. tetra-alkoxysilanes, polyisocyanates, zirconates, titanates, melamine resins etc., with tetraalkoxysilanes such as tetramethylorthosilicate and tetraethylorthosilicate being preferred.
  • the outermost layer of the thermographic recording material according to the present invention may comprise a matting agent.
  • Suitable matting agents are described in WO 94/11198 and include e.g. talc particles and optionally protrude from the outermost layer.
  • Solid or liquid lubricants or combinations thereof are suitable for improving the slip characteristics of the thermographic recording materials according to the present invention.
  • Solid lubricants which can be used according to the present invention are polyolefin waxes, ester waxes, polyolefin-polyether block copolymers, amide waxes, polyglycols, fatty acids, fatty alcohols, natural waxes and solid phosphoric acid derivatives.
  • Preferred solid lubricants are thermomeltable particles such as those described in WO 94/11199.
  • Liquid lubricants which can be used according to the present invention according to the present invention are fatty acid esters such as glycerine trioleate, sorbitan monooleate and sorbitan trioleate, silicone oil derivatives and phosphoric acid derivatives.
  • an antistatic layer is applied to the outermost layer on the side of the support not coated with the photo-addressable thermally developable element.
  • Suitable antistatic layers therefore are described in EP-A's 0 444 326, 0 534 006 and 0 644 456, US-A's 5,364,752 and 5,472,832 and DE-OS 4 125 758.
  • any layer of the photothermographic recording material of the present invention may proceed by any coating technique e.g. such as described in Modern Coating and Drying Technology, edited by Edward D. Cohen and Edgar B. Gutoff, (1992) VCH Publishers Inc. 220 East 23rd Street, Suite 909 New York, NY 10010, U.S.A.
  • a method of preparing a photothermographic material comprises the steps of coating on a support a photo-addressable thermally developable element and optionally overcoating with a protective layer.
  • Photothermographic 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 emit
  • 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.
  • the photothermographic recording materials of the present invention can be used for the production of transparencies, which are widely used in graphics applications, e.g. in masks or for display purposes, and in the medical diagnostic field in which black-imaged transparencies are widely used in inspection techniques operating with a light box.
  • a silver halide emulsion consisting of 3.11% by weight of silver halide particles consisting of 97mol% silver bromide and 3 mol% silver iodide with an weight average particle size of 50nm, 0.47% by weight of R16875 as dispersing agent in deionized water was prepared using conventional silver halide preparation techniques such as described, for example, in T.H. James, " The Theory of the Photographic Process " , Fourth Edition, Macmillan Publishing Co. Inc., New York (1977), Chapter 3, pages 88-104.
  • tabular silver halide particles consisting of 99 mol% silver bromide and 1 mol% silver iodide with an weight average particle size of 325nm and an average thickness of 100nm.
  • the emulsion was washed with water and desalted.
  • the emulsion of silver behenate and silver halide emulsion A was prepared by adding a solution of 6.8 kg of behenic acid in 67L of 2-propanol at 65°C to a 400L vessel heated to maintain the temperature of the contents at 65°C, converting 96% of the behenic acid to sodium behenate by adding with stirring 76.8L of 0.25M sodium hydroxide in deionized water, then adding with stirring 10.5kg of the above described silver halide emulsion A at 40°C and finally adding with stirring 48L of a 0.4M solution of silver nitrate in deionized water. Upon completion of the addition of silver nitrate the contents of the vessel were allowed to cool and the precipitate filtered off, washed, slurried with water, filtered again and finally dried at 40°C for 27 hours.
  • the emulsion layer coating compositions for the photothermographic recording materials of COMPARATIVE EXAMPLES 1 & 2 and INVENTION EXAMPLE 1 were prepared by adding the following solutions of liquids to 40.86g of the above-mentioned silver behenate/silver halide emulsion in the following sequence with stirring: 10.87g of 2-butanone, 0.75g of a 9% solution of TMABP in methanol followed by 2 hours stirring, 1.3g of 2-butanone, 0.2g of a 11% solution of calcium bromide in methanol and 1.3 g of 2-butanone followed by 30 minutes stirring, a solution consisting of 0.21g of LOWINOXTM 22IB46, 0.5g of TMPS and 9.24g of 2-butanone followed by 10 minutes stirring and finally 4.35g of B76 were added followed by 45 minutes of stirring and then 6.42 g of 2-butanone.
  • the PET-support subbed and coated with a backside layer as described above was then doctor blade-coated at a blade setting of 150 ⁇ m on the side of the support not coated with a backside layer with the coating composition to a wet layer thickness of 80 ⁇ m followed by drying for 5 minutes at 80°C on an aluminium plate in a drying cupboard.
  • An overcoat layer coating composition for the photothermographic recording materials of COMPARATIVE EXAMPLES 1 & 2 and INVENTION EXAMPLE 1 was prepared by dissolving 4.08g of CAB and 0.16g of PMMA in 36.3g of 2-butanone and 4.16g of methanol adding the following solids or solution with stirring in the following sequence: 0.5g of phthalazine, 0.2g of 4-methylphthalic acid, 0.1g of tetrachlorophthalic acid, 0.2g of tetrachlorophthalic anhydride and a solution of 2.55g of LOWINOXTM 22IB46 in 5.95g 2-butanone.
  • the emulsion layer was then doctor blade-coated at a blade setting of 100 ⁇ m with the protective layer coating composition to a wet layer thickness of 57 ⁇ m, which after drying for 8 minutes at 80°C on an aluminium plate in a drying cupboard produced a layer with the following composition: CAB 4.08g/m 2 PMMA 0.16g/m 2 Phthalazine 0.50g/m 2 4-methylphthalic acid 0.20g/m 2 tetrachlorophthalic acid 0.10g/m 2 tetrachlorophthalic acid anhydride 0.20g/m 2 LOWINOXTM 22IB46 2.55g/m 2
  • the photothermographic recording materials of COMPARATIVE EXAMPLES 1 & 2 and INVENTION EXAMPLE 1 were exposed for 1 s to a 750W lamp through a wedge filter varying between 0 and 3.0 in steps of 0.15.
  • Thermal processing was carried out with the side of the support provided with a silver behenate/silver halide emulsion layer in contact with a heated drum for 10s at different drum temperatures.
  • the optical densities of the resulting images were measured in transmission with a MACBETHTM TR924 densitometer through a visible filter to produce a sensitometric curve for the photothermographic recording materials from which the maximum and minimum optical densities, D max and D min , and the relative sensitivities for D min + 1.0 determined.
  • the photothermographic recording materials of COMPARATIVE EXAMPLES 3 to 5 and INVENTION EXAMPLE 2 & 3 demonstrate that the increase in speed and D max can also be realised with spectrally sensitized silver halide emulsions.
  • the silver halide emulsions of COMPARATIVE EXAMPLES 1 & 2 and INVENTION EXAMPLE 1 were optimally spectrally sensitized for green light using Dye S-1.
  • the photothermographic recording materials of COMPARATIVE EXAMPLES 3 to 5 and INVENTION EXAMPLES 2 & 3 were exposed for 1 s to a 750W lamp through a L519-filter and a wedge filter varying between densities of 0 and 3.0 in steps of 0.15. Thermal processing was carried out with the side of the support provided with a silver behenate/silver halide emulsion layer in contact with a heated drum.
  • the photothermographic recording materials according to the present invention combining the present of silver halide tabular grains with hydrazides provided higher sensitivities and high Dmax.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP98201649A 1998-05-15 1998-05-15 Matériau d'enregistrement photothermographique contenant des grains tabulaires et un composé d'hydrazine Withdrawn EP0959383A1 (fr)

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EP98201649A EP0959383A1 (fr) 1998-05-15 1998-05-15 Matériau d'enregistrement photothermographique contenant des grains tabulaires et un composé d'hydrazine

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1122593A2 (fr) * 2000-01-20 2001-08-08 Konica Corporation Produit photothermographique
US6352819B1 (en) 2000-12-01 2002-03-05 Eastman Kodak Company High contrast thermally-developable imaging materials containing barrier layer

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4435499A (en) * 1983-01-31 1984-03-06 Eastman Kodak Company Photothermographic silver halide material and process
US5496695A (en) * 1995-01-06 1996-03-05 Minnesota Mining And Manufacturing Company Hydrazide compounds useful as co-developers for black-and-white photothermographic elements
US5667945A (en) * 1995-02-21 1997-09-16 Fuji Photo Film Co., Ltd. Color developing agent, silver halide photographic light-sensitive material and image forming method
EP0805376A2 (fr) * 1996-04-30 1997-11-05 Fuji Photo Film Co., Ltd. Matériau photothermographique
EP0807850A1 (fr) * 1996-05-17 1997-11-19 Fuji Photo Film Co., Ltd. Matériau photothermographique
EP0844514A1 (fr) * 1996-11-21 1998-05-27 Agfa-Gevaert N.V. Matériau d'enregistrement photothermographique contenant des grains tabulaires

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4435499A (en) * 1983-01-31 1984-03-06 Eastman Kodak Company Photothermographic silver halide material and process
US5496695A (en) * 1995-01-06 1996-03-05 Minnesota Mining And Manufacturing Company Hydrazide compounds useful as co-developers for black-and-white photothermographic elements
US5667945A (en) * 1995-02-21 1997-09-16 Fuji Photo Film Co., Ltd. Color developing agent, silver halide photographic light-sensitive material and image forming method
EP0805376A2 (fr) * 1996-04-30 1997-11-05 Fuji Photo Film Co., Ltd. Matériau photothermographique
EP0807850A1 (fr) * 1996-05-17 1997-11-19 Fuji Photo Film Co., Ltd. Matériau photothermographique
EP0844514A1 (fr) * 1996-11-21 1998-05-27 Agfa-Gevaert N.V. Matériau d'enregistrement photothermographique contenant des grains tabulaires

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1122593A2 (fr) * 2000-01-20 2001-08-08 Konica Corporation Produit photothermographique
EP1122593A3 (fr) * 2000-01-20 2003-09-03 Konica Corporation Produit photothermographique
US6352819B1 (en) 2000-12-01 2002-03-05 Eastman Kodak Company High contrast thermally-developable imaging materials containing barrier layer

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