EP1258775A2 - Matériaux thermographiques et procédé d'enregistrement utilisant de tels matériaux - Google Patents

Matériaux thermographiques et procédé d'enregistrement utilisant de tels matériaux Download PDF

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Publication number
EP1258775A2
EP1258775A2 EP02100246A EP02100246A EP1258775A2 EP 1258775 A2 EP1258775 A2 EP 1258775A2 EP 02100246 A EP02100246 A EP 02100246A EP 02100246 A EP02100246 A EP 02100246A EP 1258775 A2 EP1258775 A2 EP 1258775A2
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EP
European Patent Office
Prior art keywords
group
silver
alkyl
recording material
photothermographic recording
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP02100246A
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German (de)
English (en)
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EP1258775A3 (fr
Inventor
Horst c/o AGFA-GEVAERT Friedel
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Agfa HealthCare NV
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Agfa Gevaert NV
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Publication date
Priority claimed from EP01000097A external-priority patent/EP1246001A1/fr
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP02100246A priority Critical patent/EP1258775A3/fr
Publication of EP1258775A2 publication Critical patent/EP1258775A2/fr
Publication of EP1258775A3 publication Critical patent/EP1258775A3/fr
Withdrawn legal-status Critical Current

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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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/015—Apparatus or processes for the preparation of 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49809—Organic silver compounds
    • 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
    • G03C2200/00—Details
    • G03C2200/42—Mixtures in general

Definitions

  • the present invention relates to photothermographic recording materials and recording processes therefor.
  • Thermal imaging or thermography is a recording process wherein images are generated by the use of image-wise modulated thermal energy.
  • thermography three approaches are known:
  • Thermographic materials of type 3 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.
  • DE-OS 27 21 828 discloses a thermally developable light-sensitive material, consisting of a support, which contains thereon or in one or more layers at least (a) an organic silver salt, (b) a photocatalyst and (c) a reducing agent, wherein the organic silver salt (a) contains at least a silver salt with an uneven number of 21 or more carbon atoms; and examples with mixtures of two and three organic silver salts of monocarboxylic acids precipitated together, but all with 20 or more carbon atoms.
  • US-P 5,459,028 discloses a heat-developable photographic recording material comprising: (a) at least one binder layer coated on a support, said binder layer comprising at least one light-sensitive silver halide and a light-insensitive silver salt of a fatty acid; (b) at least one reducing agent; and (c) at least one auxiliary layer containing a developed image stabilizer selected from the group consisting of hexamethylene tetramine and salts thereof, triazaadamantane and salts thereof and compounds derived from hexamethylene tetramine wherein the compounds are derived from hexamethylene tetramine by exchanging one -CH 2 - group with -S-, -SO-, or -SO 2 -; (d) wherein said reducing agent and said developed image stabilizers are in a reactive relationship with the light-insensitive silver salt.
  • US-P 5,677,121 discloses a heat-developable silver halide infrared ray-sensitive material comprising a support having on one side of the support an emulsion layer containing a binder, a nonsensitive silver salt, a reducing agent for silver ion and silver halide grains spectrally sensitized at a wavelength within the region of from 750 to 1400nm, wherein the nonsensitive silver salt comprises a mixture of silver salts of at least three organic carboxylic acids, one of the acids is behenic acid, and the content of the behenic acid in the acids is from not less than 35 to less than 90 mol %.
  • thermographic materials incorporating glutaric acid in the thermosensitive element have shown that, unlike substantially light-insensitive thermographic materials incorporating adipic acid or pimelic acid, silver glutarate could not be detected by X-ray diffraction spectroscopy during the thermal development process. Therefore there can be no question of incidental silver glutarate formation upon thermal development of substantially light-insensitive thermographic materials incorporating glutaric acid.
  • Photothermographic recording materials are required which are thermally processable at lower temperatures to enable a higher throughput to be realized and which are capable of providing images with a higher gradation.
  • thermo developability can be realized at lower temperatures without significant deterioration in other thermographic properties and images with higher gradation can be realized by using a mixture of particular substantially light-insensitive silver salts of monocarboxylic acids and particular light-insensitive silver salts of polycarboxylic acids. Particularly good results are obtained with a mixture of an equimolar mixture of silver glutarate and silver stearate.
  • a photothermographic recording material is also provided in an embodiment of the photothermographic recording material in which the photosensitive silver halide after exposure to UV, visible or IR light is capable of catalyzing or participating in photothermographic process.
  • a photothermographic recording process comprising the steps of: (i) providing a photothermographic recording material as referred to above; (ii) image-wise exposing the photo-addressable thermosensitive element with actinic radiation; (iii) bringing the image-wise exposed photothermographic recording material into proximity with a heat source; (iv) uniformly heating the image-wise exposed photothermographic recording material under substantially water-free conditions; and (v) removing the photothermographic recording material from the source.
  • mixture of substantially light-insensitive silver salts of organic carboxylic acids includes a physical mixture of separately produced substantially light-insensitive silver salts of organic carboxylic acids, coprecipitated substantially light-insensitive silver salts of organic carboxylic acids and mixed crystals of substantially light-insensitive silver salts of organic carboxylic acids.
  • alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl and 2-methyl-butyl etc.
  • Gradation is the rate at which image density changes in response to the logarithm of exposure in the case of photothermographic recording materials.
  • substantially light-insensitive is meant not intentionally light sensitive.
  • 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.
  • 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.
  • a photothermographic recording material comprising a support and a photo-addressable thermally developable element, the photo-addressable thermally developable element containing a mixture of substantially light-insensitive silver salts of organic carboxylic acids with one or more carboxylic acid groups, an organic reducing agent for the mixture of substantially light-insensitive organic silver salts in thermal working relationship therewith, a photosensitive silver halide and a binder, wherein the mixture of substantially light-insensitive organic silver salts contains a silver salt of a monocarboxylic acid and a compound represented by formula (I).
  • the compound according to formula (I) is present in a concentration of 30 to 70 mol% in the mixture of substantially light-insensitive silver salts.
  • a suspension of particles containing a substantially light-insensitive organic silver salt may be obtained by using processes disclosed in RD 17029, EP-A 754 969, US 5,891,616 and EP-A 848 286.
  • the substantially light-insensitive organic silver salt of a monocarboxylic acid in the mixture of substantially light-insensitive silver salts of organic carboxylic acids with one or more carboxylic acid groups is a silver salt of an aliphatic carboxylic acid known as a fatty acid, 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".
  • R 1 is an optionally substituted straight chain saturated or unsaturated hydrocarbon group with two carbon atoms according to formula (I) are:
  • R 1 is an optionally substituted straight chain saturated or unsaturated hydrocarbon group with three carbon atoms according to formula (I) are:
  • the compound according to formula (I) is selected from the group consisting of silver glutarate, silver 2-methyl glutarate, silver 3-methyl glutarate, silver 1,1-cyclopentane diacetic acetate, silver 1,1-cyclohexane diacetate, silver 1,3-cyclohexane dicarboxylate, silver citrate, silver citramalate, silver 2-methyl-succinate, silver 1,2-cyclohexane dicarboxylate, silver 3,3-tetramethylene-glutarate, silver 1,2-cyclopentane dicarboxylate, silver malate, silver tartarate, silver tetrahydrofuran-2,3,4,5-tetracarboxylate and silver itaconate.
  • No image could be obtained with photothermographic recording materials with a mixture of a silver salt of a monocarboxylic acid and silver succinate.
  • the compound according to formula (I) is selected from the group consisting of silver glutarate, silver 2-methyl succinate, silver 2,2-dimethylglutarate, silver 3-methylglutarate, silver tetrahydrofuran-2,3,4,5-tetracarboxylate and silver itaconate.
  • dicarboxylic acids of which compounds according to formula (I) are silver salts are commercially available. If such dicarboxylic acids are not commercially available such compounds can be prepared according to standard synthetic techniques known to organic chemists.
  • the photo-addressable thermally developable element comprises a mixture of a substantially light-insensitive silver salt of a monocarboxylic acid and a compound according to formula (I), an organic reducing agent therefor in thermal working relationship therewith, a photosensitive silver halide in catalytic association with the mixture of a substantially light-insensitive silver salt of a monocarboxylic acid and a compound according to formula (I) and a binder.
  • the element may comprise a layer system in which the ingredients may be dispersed in different layers, with the provisos that the substantially light-insensitive organic silver salts and the organic reducing agent are in thermal working relationship with one another i.e.
  • the 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, and that the photosensitive silver halide is in catalytic association with the mixture of a substantially light-insensitive silver salt of a monocarboxylic acid and a compound according to formula (I) so that the photosensitive silver halide after exposure to UV, visible or IR light is capable of catalyzing or participating in a photothermographic process7.
  • Suitable organic reducing agents for the reduction of the mixture of a substantially light-insensitive silver salt of a monocarboxylic acid and a compound according to formula (I) 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.
  • the organic reducing agent is a 1,2-dihydroxybenzene derivative, 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-dihydroxybenzoic acid esters.
  • 1,2-dihydroxybenzene derivative 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-dihydroxybenzoic acid esters.
  • the organic reducing agent is a polyphenol such as the bisphenols used in the 3M Dry SilverTM materials, a sulfonamide phenol such as used in the Kodak DacomaticTM materials or a naphthol.
  • Combinations of reducing agents may also be used that on heating become reactive partners in the reduction of the substantially light-insensitive organic silver salts.
  • 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 at least one layer comprising the photo-addressable thermally developable element coating from solvent media 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 butyrals containing a minor amount of vinyl alcohol units are marketed under the trade name BUTVARTM B76 and BUTVARTM B79 of Monsanto USA and provides a good adhesion to paper and properly subbed polyester supports
  • the film-forming binder for the at least one layer comprising the photo-addressable thermally developable element coatable from aqueous media 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 gelatin and gelatin derivatives (e.g.
  • phthaloyl gelatin cellulose derivatives, such as carboxymethylcellulose, polysaccharides, such as dextran, starch ethers etc., galactomannan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, homo- or co-polymerized acrylic or methacrylic acid, latexes of water dispersible polymers, with or without hydrophilic groups, or mixtures thereof.
  • 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.
  • the photo-addressable thermally developable element further contains a so-called toning agent in order to obtain a neutral black image tone in the higher densities and neutral grey in the lower densities.
  • Suitable toning agents are the phthalimides and phthalazinones within the scope of the general formulae described in US 4,082,901 and the toning agents described in US 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 disclosed in GB 1,439,478, US 3,951,660 and US 5,599,647 and pyridazone as disclosed in DE 19516349.
  • Aromatic polycarboxylic acids and anhydrides thereof are Aromatic polycarboxylic acids and anhydrides thereof.
  • the photo-addressable thermally developable element may comprise at least one aromatic polycarboxylic acid and/or anhydride such as ortho-phthalic acid, 3-nitro-phthalic acid and tetrachlorophthalic acid and anhydrides thereof.
  • Antifoggants may be incorporated into the photothermographic recording materials of the present invention in order to obtain improved shelf-life and reduced fogging.
  • the photo-addressable thermally developable element further contains at least one antifoggant selected from the group consisting of hexamethylene tetramine (see EP 557 859 and US 5,459,028), substituted pyridazones (see DE 195 16350), benzotriazole, substituted benzotriazoles, tetrazoles and mercaptotetrazoles.
  • at least one antifoggant selected from the group consisting of hexamethylene tetramine (see EP 557 859 and US 5,459,028), substituted pyridazones (see DE 195 16350), benzotriazole, substituted benzotriazoles, tetrazoles and mercaptotetrazoles.
  • the photo-addressable thermally developable element further contains hexamethylene tetramine.
  • the photosensitive silver halide used in the present invention may be employed in a range of 0.75 to 25 mol percent and, preferably, from 2 to 20 mol percent 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 recording material may contain a spectral sensitizer, optionally together with a supersensitizer, for the silver halide.
  • the 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.
  • Useful 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.
  • Useful merocyanine dyes which are preferred 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 effective.
  • the photothermographic recording material of the present invention may contain anti-halation or acutance dyes which absorb light which has passed through the photosensitive layer, thereby preventing its reflection.
  • Such dyes may be incorporated into the photo-addressable thermally developable element or in any other layer comprising the photothermographic recording material of the present invention.
  • the photo-addressable thermally developable element may contain other additives such as free fatty acids, surface-active agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H, silicone oil, e.g. BAYSILONETM ⁇ l A (from BAYER AG, GERMANY), ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, silica, colloidal silica, fine polymeric particles [e.g. of poly(methylmethacrylate)] and/or optical brightening agents.
  • surface-active agents e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
  • silicone oil e.g. BAYSILONETM ⁇ l A (from BAYER AG, GERMANY)
  • ultraviolet light absorbing compounds e
  • the support for the photothermographic recording material according to the present invention may be transparent or translucent and is a thin flexible carrier made of transparent resin film, e.g. made of a cellulose ester, cellulose triacetate, polypropylene, polycarbonate or polyester, e.g. polyethylene terephthalate.
  • transparent resin film e.g. made of a cellulose ester, 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 thereon coated photo-addressable thermally developable element. Suitable pretreatments of supports are, for example, treatment with a corona discharge and/or attack by solvent(s), thereby providing a micro-roughening.
  • the support may be pigmented with a blue pigment as in so-called blue-base.
  • One or more backing layers may be provided to control physical properties such as curl and static.
  • the photo-addressable thermally developable element is provided with a protective layer to avoid local deformation of the photo-addressable thermally developable element and to improve resistance against abrasion.
  • the photo-addressable thermally developable element is provided with a protective layer comprising a binder, which may be solvent-soluble, solvent-dispersible, water-soluble or water- dispersible.
  • the photo-addressable thermally developable element is provided with a protective layer comprising solvent-soluble polycarbonates as binders as described in EP-A 614 769.
  • the photo-addressable thermally developable element is provided with a protective layer comprising a water-soluble or water-dispersible binder, 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.
  • the protective layer according to the present invention may be crosslinked.
  • Crosslinking can be achieved by using crosslinking agents such as described in WO 95/12495.
  • Solid or liquid lubricants or combinations thereof are suitable for improving the slip characteristics of the photothermographic recording materials according to the present invention.
  • the photo-addressable thermally developable element is provided with a protective layer comprising a solid thermomeltable lubricant such as those described in WO 94/11199.
  • the protective layer of the photothermographic recording material according to the present invention may comprise a matting agent.
  • the photo-addressable thermally developable element is provided with a protective layer comprising a matting agent such as described in WO 94/11198, e.g. talc particles, and optionally protrude from the protective layer.
  • any layer of the photothermographic recording materials of the present invention may proceed by any thin-film coating technique known in the art.
  • slide hopper coating is used advantageously, but other coating techniques such as dip coating and air knife coating may also be used. Details about such coating techniques can be found in "Modern Coating and Drying Technology" by Edward D. Cohen and Edgar B. Gutoff, published by VCH Publishers, Inc. 220 East 23rd Street, Suite 909 New York, NY 10010.
  • 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 focussed 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 aspect itself or an image therefrom with appropriate illumination e.g. with UV, visible or IR light.
  • a finely focussed 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
  • 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.
  • the photothermographic recording materials of the present invention can be used for both the production of transparencies and reflection type prints.
  • the support will be transparent or opaque, e.g. having a white light reflecting aspect.
  • the base may be colourless or coloured, e.g. has a blue colour.
  • Application of the present invention is envisaged in the fields of both graphics images requiring high contrast images with a very steep print density applied dot energy dependence and continuous tone images requiring a weaker print density applied dot energy dependence, such as required in the medical diagnostic field.
  • Solution A was prepared by mixing 1000g of deionized water, 85g (0.5 moles) of silver nitrate, 15g of 6.5% nitric acid and 2.0g of mercuric nitrate at 60°C.
  • Solution B was prepared by mixing 2000g of deionized water, 26.4g (0.2 moles) of glutaric acid and 22.7g (0.57 moles) of sodium hydroxide and 50.0g of stearic acid (0.176 moles) at 70°C and had a pH of 8.8.
  • Solution A at 60°C was added to solution B at 70°C in 10s and the resulting Mixture 01 stirred for 2 minutes and then cooled to room temperature.
  • the precipitate was then filtered off, washed and dried yielding 120g of solids consisting of silver glutarate, silver stearate, stearic acid, glutaric acid and mercuric stearate-glutarate.
  • Solution C was prepared by mixing 1000g of deionized water, 85g (0.5 moles) of silver nitrate, 15g of 6.5% nitric acid and 2.0g of mercuric nitrate at 60°C.
  • Solution D was prepared by mixing 2000g of deionized water, 8.5g (0.14 moles) of glutaric acid and 22.7g (0.57 moles) of sodium hydroxide and 79.7g of stearic acid (0.28 moles) at 70°C and had a pH of 9.0.
  • Solution C at 60°C was added to solution D at 70°C in 10s and the resulting mixture stirred for 2 minutes and then cooled to room temperature.
  • the precipitate was then filtered off, washed and dried yielding 122.5g of solids consisting of silver glutarate, silver stearate, stearic acid, glutaric acid and mercuric stearate-glutarate.
  • a mixture of 76 mol% of silver behenate and 24 mol% of silver glutarate was produced by adding 0.75M aqueous sodium hydroxide to a mixture of 0.456 mol of behenic acid and 0.144 mol of glutaric acid in 750 mL to a pH of 8.7 and a UAg of 167mV and then converting the resulting sodium salts into silver salts by adding 0.8M aqueous silver nitrate until a UAg of 425mV and pH of 6.08 was realized, whereupon the mixture of silver salts precipitated out was washed and dried producing Mixture 03. The yield was 100%.
  • a mixture of 66.7 mol% of silver behenate and 33.3 mol% of silver glutarate was produced by adding 0.75M aqueous sodium hydroxide to a mixture of 0.375 mol of behenic acid and 0.1875 mol of glutaric acid in 750 mL to a pH of 8.5 and a UAg of 207mV and then converting the resulting sodium salts into silver salts by adding 0.8M aqueous silver nitrate until a UAg of 422mV and pH of 6.7 was realized, whereupon the mixture of silver salts precipitated out was washed and dried producing Mixture 03. The yield was 100%.
  • X-ray diffraction spectra carried out on Mixtures 01 to 04 showed the presence of the silver salt of a monocarboxylic acid (i.e. silver stearate in the cases of Mixtures 01 and 02 and silver behenate in the cases of Mixtures 03 and 04 and that of silver glutarate (characterized by a 2 ⁇ peak at 8.53°) and provided no evidence for the presence of mixed salts. Furthermore, the crystallinity of the mixtures of silver stearate and silver glutarate and silver behenate and silver glutarate was fairly low.
  • An emulsion for the first layer of the photo-addressable thermally developable elements of INVENTION EXAMPLES 1 and 2 was prepared by mixing the following ingredients and solvents in the following order: Mixture 01: silver stearate/silver glutarate/stearic acid/glutaric acid/mercuric stearate-glutarate mixture 120g Methanol 720g TRITONTM X100 4.8g behenic acid 3.6g 5-nitro-indazole 1.2g phthalic anhydride 16.8g Polyvinylpyrrolidone K30 30g Methanol 90g mercuric bromide 0.48g Methanol 20g and then pearl milling the resulting mixture at 0°C for 8 hours.
  • the photo-addressable thermally developable emulsion was then coated onto a subbed polyethylene terephthalate support to a wet layer thickness of 100 ⁇ m thereby producing after drying the first layer of the photo-addressable thermally developable element.
  • the emulsion for the second layer of the photo-addressable thermally developable elements of INVENTION EXAMPLES 1 and 2 were prepared by mixing: INVENTION EXAMPLE 1 INVENTION EXAMPLE 2 Ethyl acetate 480g 480g Cellulose propionate 40g 40g isobutanol 160g 160g Hexamethylene tetramine - 12g FC 430, a non-ionic fluorosurfactant 1g 1g bis(2-hydroxy-3,5-dimethyl-phenyl)methane 14g 14g Pyridazone 5g 5g Hydrazino-methylene-malonic acid ester 2.5g 2.5g Phthalic acid 2.5g 2.5g then coating the mixture on the first layer of the photo-addressable thermally developable element to a wet thickness of 100 ⁇ m and finally drying to form the second layer of the photo-addressable thermally developable element thereby producing a photothermographic recording material.
  • the photothermographic recording materials of INVENTION EXAMPLES 1 and 2 were exposed through a wedge in a KLINSCH VACUPRINTTM apparatus fitted with a mercury lamp to UV light for 10s and then the exposed material was uniformly heated at 105°C for 15s to produce a wedge image.
  • An emulsion for the first layer of the photo-addressable thermally developable element of the high sensitivity photothermographic recording material was prepared by adding 10g of a 52.2% by weight emulsion with respect to silver of 0.1 ⁇ m edge-length cubic silver bromide grains in which the gelatin had been removed by degradation beforehand by enzymatic degradation using the enzyme trypsin, which was obtained from MERCK.
  • the resulting emulsion was coated onto a subbed polyethylene terephthalate support to a wet thickness of 100 ⁇ m. After drying it was overcoated as described in INVENTION EXAMPLE 2 to a wet thickness of 100 ⁇ m.
  • Solution A was prepared by mixing 1000g of deionized water, 85g (0.5 moles) of silver nitrate, 15g of 6.5% nitric acid and 2.0g of mercuric nitrate at 60°C.
  • Solution B was prepared by mixing 2000g of deionized water, 162.0g of stearic acid (0.57 moles) and 22.7g (0.57 moles) of sodium hydroxide at 70°C and had a pH of 9.0.
  • Solution A at 60°C was added to solution B at 70°C in 10s and the resulting mixture stirred for 2 minutes and then cooled to room temperature.
  • the precipitate was then filtered off, washed and dried yielding 120g of solids consisting of silver stearate, stearic acid, and mercuric stearate.
  • the photo-addressable thermally developable element of the high sensitivity photothermographic recording material was prepared as described in INVENTION EXAMPLE 3 except that the above-described silver stearate emulsion was used instead of the silver stearate/silver glutarate emulsion of INVENTION EXAMPLES 1 and 2.
  • D max was significantly lower in the absence of silver glutarate, D min significantly higher and the gradation, ⁇ , significantly lower, indicating the benefit of the use of a mixture of silver stearate and silver glutarate over the use of silver stearate alone.
  • COMPARATIVE EXAMPLE 1 was repeated with silver palmitate and silver glutarate being used respectively instead of silver stearate.
  • the photothermographic recording material of COMPARATIVE EXAMPLE 2 with silver palmitate was grey and fogged after 3 days in the refrigerator.
  • the photothermographic recording material of COMPARATIVE EXAMPLE 3 with silver glutarate was difficult to prepare because the silver glutarate is formed in large crystals which are difficult to grind. Furthermore, although the fresh photothermographic recording material had a high D max and normal speed, after aging for 7 days only a very low D max of ca. 0.5 could be attained after prolonged processing (ca, 30-60s at 105°C).

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  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP02100246A 2001-03-29 2002-03-13 Matériaux thermographiques et procédé d'enregistrement utilisant de tels matériaux Withdrawn EP1258775A3 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1953592A1 (fr) 2007-02-02 2008-08-06 Konica Minolta Medical & Graphic, Inc. Matériau photothermographique

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0964300A1 (fr) * 1998-06-08 1999-12-15 Agfa-Gevaert N.V. Matériau d'enregistrement thermographique noir et blanc ayant un ton de l'image amélioré

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0964300A1 (fr) * 1998-06-08 1999-12-15 Agfa-Gevaert N.V. Matériau d'enregistrement thermographique noir et blanc ayant un ton de l'image amélioré

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1953592A1 (fr) 2007-02-02 2008-08-06 Konica Minolta Medical & Graphic, Inc. Matériau photothermographique

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