EP0851284B1 - Produit d'enrégistrement pouvant être couché à partir d'un milieu aqueux - Google Patents

Produit d'enrégistrement pouvant être couché à partir d'un milieu aqueux Download PDF

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Publication number
EP0851284B1
EP0851284B1 EP19970203816 EP97203816A EP0851284B1 EP 0851284 B1 EP0851284 B1 EP 0851284B1 EP 19970203816 EP19970203816 EP 19970203816 EP 97203816 A EP97203816 A EP 97203816A EP 0851284 B1 EP0851284 B1 EP 0851284B1
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EP
European Patent Office
Prior art keywords
silver
water
recording material
fatty acid
binder
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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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EP19970203816
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German (de)
English (en)
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EP0851284A1 (fr
Inventor
Herman Uytterhoeven
Johan Loccufier
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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Priority to EP19970203816 priority Critical patent/EP0851284B1/fr
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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
    • G03C1/49863—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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03558—Iodide content

Definitions

  • the present invention relates to a photothermographic recording material comprising a photo-addressable thermally developable element coatable from aqueous media.
  • Thermal imaging or thermography is a recording process wherein images are generated by the use of thermal energy.
  • direct thermal imaging a 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.
  • thermographic materials become photothermographic when a photosensitive agent is present 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 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-P 3,152,904 discloses an image reproduction sheet which comprises a radiation-sensitive heavy metal salt which can be reduced to free metal by a radiation wave length between an X-ray wave length and a five microns wave length and being distributed substantially uniformly laterally over the sheet, and as the image forming component an oxidation-reduction reaction combination which is substantially latent under ambient conditions and which can be initiated into reaction by the free metal to produce a visible change in colour comprising an organic silver salt containing carbon atoms and different from the heavy metal salt as an oxidizing agent and in addition an organic reducing agent containing carbon atoms, the radiation-sensitive heavy metal salt being present in an amount between about 50 and about 1000 parts per million of the oxidation-reduction reaction combination.
  • JP 54-156527 discloses a heat-developing photosensitive material containing (a) an oxidizing agent comprising non-photosensitive organic silver salt, (b) iodine, (c) a reducing agent for silver ions and (d) an N-containing organic base which may or may not have an acidic proton in a molecule and has a pKa of conjugated acid 0.5 to 10, with preferred (d) being, for example, pyridine, quinoline, quinazoline, phthalazine, their derivatives etc.
  • US-P 3,994,732 discloses a photosensitive, heat-developable, dry silver sheet material containing an image-forming system including a photosensitive silver halide catalyst-forming means and as heat image forming means, an organic silver compound and a reducing agent therefor, the oxidation reduction reaction of which to produce a visible image is accelerated by the catalyst, and sufficient toner to increase the density of the visible image, the improvement characterized by the toner being a mixture of (a) phthalazine and (b) at least one acid of the formula: R-A-R 1 wherein A is phenyl or naphthyl and R and R 1 are selected from -COOH and -CH 2 COOH, R and R 1 bonded respectively to the 2 and 3 positions of A, and anhydrides of the acid R-A-R 1 .
  • the mol% of silver iodide to silver halide present in the silver behenate emulsion layer was 80.4%.
  • US-P 4,105,451 discloses a method of preparing a photothermographic composition comprising sequentially mixing the following components: (1) a dispersion comprising a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound and a silver salt of a heterocyclic thione represented by the formula: wherein R represents atoms completing a five-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (2) a reducing agent solution comprising a reducing agent, (3) a binder, and (4) a silver halide photosensitive composition containing a spectral sensitizing dye.
  • a dispersion comprising a 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole or 2-mercaptobenzoselenazole compound and a silver salt of a heterocyclic thione represented by the formula
  • US-P 4,201,582 discloses in a photothermographic element comprising a support having thereon a) photographic silver halide in association with (b) an image-forming combination comprising i) a silver salt of a heterocyclic thione, said heterocyclic thione being represented by the formula: wherein R represents atoms completing a 5-member heterocyclic nucleus, Z is alkylene containing 1 to 30 carbon atoms, (ii) an organic reducing agent, and (c) a toner,the improvement wherein said toner comprises a mercapto heterocyclic compound which is selected from the group consisting of 3-mercapto-1H-1,2,4-triazole, 3-imino-5-thiourazole, 4-methyl-3,5-dithiourazole, 4-phenyl-3,5-dithiourazole, 4-(p-methoxyphenyl)-3,5-dithiourazole, 2,4-dimercaptopyrimidine, 8-mercaptopurine and 2,
  • US-P 4,743,534 discloses a photosensitive material consisting essentially of radiation-sensitive silver halide grains and a dry binder resin entrapping said grains said binder resin of said photosensitive material capable of being dissolved so that said photosensitive material can be added directly to a photothermographic system comprising a light-insensitive reducible metal compound and a reducing agent therefor, said silver halide grains having been formed by a process wherein ionizable silver salt and ionizable halide are introduced into a solution comprising said binder resin and an inert organic solvent to form initial silver halide nuclei, and additional ionizable silver salt and additional ionizable halide are introduced into said solvent in at least one incremental addition at such a rate that additional silver halide nuclei will not form more rapidly than the initial silver nuclei can grow.
  • US-P 5,350,669 discloses a photothermographic element comprising a support bearing at least one heat-developable, photosensitive, image-forming photothermographic emulsion layer comprising: (a) a photosensitive silver halide; (b) a non-photosensitive, reducible source of silver comprising a silver-carboxylate/1,2-diazine coordination compound of the formula: means and, as heat sensitive image forming means, an organic silver wherein: R 1 is either an alkyl, aralkyl, cycloalkyl, and alkenyl group of up to 29 carbon atoms; or an aryl group of up to 14 carbon atoms; and R 2 represents either hydrogen, an alkyl group, a cycloalkyl group fused to the 1,2-diazine ring, or the atoms necessary to complete a 5- or 6-membered aromatic ring fused to the 1,2-diazine ring; (c) a reducing agent for said non-photosensitive, reducible source
  • US 4,585,734 discloses in a photosensitive, heat-developable, dry silver sheet material containing an image-forming system including a preformed photosensitive silver halide catalyst-forming compound and a reducing agent therefor, the oxidation reduction reaction of which to produce a visible image is accelerated by said catalyst, and sufficient toner to increase the density of said visible image, the improvement characterized by said toner being a mixture of (a) phthalazine and (b) at least one active hydrogen containing heterocyclic compound comprising a 5-, 6-, or 7-membered heterocyclic ring having only C, N, S, O, and Se ring atoms.
  • WO-A 97/48014, WO-A 97/48015, WO-A 97/04355, WO-A 97/04356 and WO-A 97/04357 attempt to remedy this deficiency, but the materials have unsatisfactory post-processing stability.
  • It is a second object of the invention to provide a photothermographic recording material comprising a photo-addressable thermally developable element based on a substantially light-insensitive silver salt of a fatty acid, photosensitive silver halide in catalytic association therewith and an organic reducing agent for the silver salt of a fatty acid, which is producible without necessitating intermediate drying of the silver salt of an organic carboxylic acid.
  • It is another object of the invention to provide a photothermographic recording material comprising a photo-addressable thermally developable element based on a substantially light-insensitive silver salt of a fatty acid, photosensitive silver halide in catalytic association therewith and an organic reducing agent for the silver salt of a fatty acid, which is coatable from an aqueous medium.
  • a process for producing a photothermographic recording material having a support and a photo-addressable thermally developable element containing photosensitive silver halide in catalytic association with a substantially light-insensitive silver salt of a fatty acid, an organic reducing agent for the substantially light-insensitive silver salt of a fatty acid in thermal working relationship therewith, a surfactant and a binder including a water-soluble binder, a water-dispersible binder or a mixture of a water-soluble binder and a water-dispersible binder, comprising the steps of: (i) producing an aqueous dispersion or aqueous dispersions containing photosensitive silver halide, a substantially light-insensitive silver salt of a fatty acid, an organic reducing agent for the substantially light-insensitive silver salt of a fatty acid and a binder including a water-soluble binder, a water-dispersible binder or a mixture of a water-soluble binder and a water
  • a photothermographic recording material comprising a support and a photo-addressable thermally developable element containing photosensitive silver halide in catalytic association with a substantially light-insensitive silver salt of a fatty acid, an organic reducing agent for the substantially light-insensitive silver salt of a fatty acid in thermal working relationship therewith and a binder including a water-soluble binder, a water-dispersible binder or a mixture of a water-soluble binder and a water-dispersible binder, characterized in that at least 80mol% of the photosensitive silver halide is silver iodide and the photo-addressable thermally developable element further contains a surfactant and phthalazine or a substituted phthalazine compound.
  • aqueous for the purposes of the present invention includes mixtures of water with water-miscible organic solvents such as alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol etc.; glycols e.g. ethylene glycol; glycerine; N-methyl pyrrolidone; methoxypropanol; and ketones e.g. 2-propanone and 2-butanone etc.
  • alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol etc.
  • glycols e.g. ethylene glycol
  • glycerine N-methyl pyrrolidone
  • methoxypropanol and ketones e.g. 2-propanone and 2-butanone etc.
  • diazine compound includes heterocyclic ring systems with at least two azine groups, which may be in the same or in different heterocyclic rings annulated with one another as well as substituted diazine compounds and annulated diazine compounds which may themselves be substituted.
  • Suitable substituting groups are, for example, alkyl, substituted alkyl, hydroxy, alkoxy, carboxy and carboxy-ester groups.
  • the diazine compound may also be present as a complex, for example as the silver-carboxylate disclosed in US-P 5,350,669, as a metal salt, as an amine-complex or as a complex with inorganic salts.
  • the diazine compound may be present in the same layer of the photo-addressable thermally developable element as the silver salt of an organic carboxylic acid or in a different layer such that it is in thermal working relationship therewith. It may also be incorporated as a dispersion in a dispersion medium which substantially prevents its diffusion during production and storage of the photothermographic material of the present invention, but which allows diffusion thereof during thermal development so that it can participate in the thermal development process.
  • the diazine compound is a 1,2-diazine compound or a substituted 1,2-diazine compound and in a particularly preferred embodiment the diazine compound is phthalazine or a substituted phthalazine.
  • Suitable diazine compounds are: phthalazine, pyridazine, cinnoline, benzo(c)cinnoline, naphthyridine, pyrimidine, pyrazine, quinazoline, quinoxaline, purine and substituted derivatives therefrom.
  • preferred substituted diazine compounds are: 1(2H)-phthalazinone, substituted substituted 1(2H)-phthalazinones, 2,3-dihydro-1,4-phthalazinedione, substituted 2,3-dihydro-1,4-phthalazinediones and the like.
  • the photo-addressable thermally developable element includes a binder comprising a water-soluble binder, a water-dispersible binder or a mixture of a water soluble binder and a water-dispersible binder.
  • the binder is a polymer latex.
  • the water-dispersible binder can be any water-insoluble polymer e.g. water-insoluble cellulose derivatives, polymers derived from ⁇ , ⁇ -ethylenically unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl alcohol, polyvinyl acetals that are made from polyvinyl alcohol as starting material in which only a part of the repeating vinyl alcohol units may have reacted with an aldehyde, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, polystyrene and polyethylene or mixtures thereof. It should be noted that there is no clear cut transition between a polymer dispersion and a poly
  • Suitable water-soluble polymers are: gelatin, gelatin derivatives, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polymethacrylic acid, polyethyleneglycol, polysaccharides, such as starch, gum arabic and dextran and water-soluble cellulose derivatives.
  • plasticizers can be incorporated into the polymers, water-miscible solvents can be added to the dispersion medium and mixtures of water-soluble polymers, mixtures of water-dispersible polymers, or mixtures of water-soluble and water-dispersible polymers may be used.
  • the photo-addressable thermally developable element contains photosensitive silver halide in catalytic association with a substantially light-insensitive silver salt of a fatty acid, an organic reducing agent for the substantially light-insensitive silver salt of a fatty acid in thermal working relationship therewith and a binder including a water-soluble binder, a water-dispersible binder or a mixture of a water-soluble binder and a water-dispersible binder, characterized in that at least 80mol% of the photosensitive silver halide is silver iodide and the photo-addressable thermally developable element further contains a diazine compound.
  • the element may comprise a layer system with the silver halide in catalytic association with the substantially light-insensitive silver salt of a fatty acid, spectral sensitizer optionally together with a supersensitizer in sensitizing association with the 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, is in thermal working relationship with the substantially light-insensitive silver salt of a fatty acid i.e. during the thermal development process the reducing agent are able to diffuse to the substantially light-insensitive silver salt of a fatty acid.
  • the aliphatic carbon chain of the fatty acid corresponding to the light-insensitive silver salt of a fatty acid preferably has 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".
  • substantially light-insensitive silver salt of a fatty acid for the purposes of the present invention also includes mixtures of silver salts of fatty acids.
  • Particles of the silver salts of fatty acids are prepared by the reaction of a soluble silver salt with the fatty acid or a salt thereof.
  • the aqueous dispersion or the aqueous dispersions comprise an aqueous suspension of particles of a substantially light-insensitive silver salt of a fatty acid produced by simultaneous metered addition of an aqueous solution or suspension of a fatty acid, or its salt, and an aqueous solution of a silver salt to an aqueous liquid and the metered addition of the aqueous solution or suspension of the fatty acid or its salt; and/or the aqueous solution of the silver salt is regulated by the concentration of silver ions or the concentration of anions of the silver salt in the aqueous liquid.
  • a process for producing a photothermographic recording material is also provided by the present invention, wherein the process further comprises the step of producing particles of the photosensitive silver iodide from excess silver ions associated with particles of the substantially light-insensitive silver salt of a fatty acid.
  • the photosensitive silver halide used in the present invention may be employed in a range of 0.1 to 35 mol percent of substantially light-insensitive silver salt of a fatty acid, with the range of 0.5 to 20 mol percent being preferred and the range of 1 to 12 mol percent being particularly preferred.
  • at least 90mol% of the photosensitive silver halide is silver iodide.
  • the silver iodide may be present in any form which is photosensitive including, ⁇ -, ⁇ - and ⁇ -phases.
  • 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. Detailsof 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.
  • the silver halide may be added to the photo-addressable thermally developable element in any fashion which places it in catalytic proximity to the substantially light-insensitive silver salt of a fatty acid.
  • Silver halide and the substantially light-insensitive silver salt of a fatty acid 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 effective to blend both of them for a long period of time.
  • particles of the photosensitive silver halide in the photo-addressable thermally developable element are uniformly distributed over and between particles of the substantially light-insensitive silver salt of a fatty acid, at least 80% by number of the photosensitive silver halide particles having a diameter, determined by transmission electron microscopy, of ⁇ 40nm.
  • production of the suspension of particles containing a substantially light-insensitive silver salt is immediately followed by the production of silver halide "in-situ" in the same recipient, thereby producing a photosensitive suspension.
  • the aqueous emulsion of the silver salt of a fatty acid optionally including photosensitive silver halide can, according to the present invention, also be produced from particles of the silver salt of a fatty acid optionally containing photosensitive silver halide by dispersing the particles in water in the presence of non-ionic or anionic surfactants or a mixture of non-ionic and anionic surfactants using any dispersion technique known to one skilled in the art such as ball milling, dispersion in a impingement mill (rotor-stator mixer), dispersion in a microfluidizer etc.
  • a combination of dispersion techniques may also be used, for example using a first technique to produce a predispersion and a second technique to produce a fine dispersion.
  • photosensitive silver halide particles may be produced by reacting an aqueous dispersion of particles of the substantially light-insensitive silver salt of a fatty acid with at least one halide conversion agent.
  • Suitable halide conversion agents are: water-soluble inorganic halides, such as
  • the onium salts are present in quantities of between 0.1 and 35mol % with respect to the quantity of substantially light-insensitive silver salt of a fatty acid, with quantities between 0.5 and 20mol% being preferred and with quantities between 1 and 12mol % being particularly preferred.
  • halide conversion agents may be added as solids or solutions or may in the case of onium salts be formed in the aqueous dispersion of particles of the substantially light-insensitive silver salt by metathesis between a salt with halide or polyhalide anions and onium salts with anions other than iodide or polyiodide.
  • Suitable organic reducing agents for the reduction of the substantially light-insensitive silver salt of a fatty acid are organic compounds containing at least one active hydrogen atom linked to O, N or C.
  • Particularly suitable organic reducing agents for the reduction the substantially light-insensitive silver salt of a fatty acid are non-sulfo-substituted 6-membered aromatic or heteroaromatic ring compounds with at least three substituents one of which is a hydroxy group at a first carbon atom and a second of which is a hydroxy or amino-group substituted on a second carbon atom one, three or five ring atoms removed in a system of conjugated double bonds from the first carbon atom in the compound, in which (i) the third substituent may be part of an annulated carbocyclic or heterocyclic ring system; (ii) the third substituent or a further substituent is not an aryl- or oxo-aryl-group whose aryl group is substituted with hydroxy-, thiol- or amino-
  • Particularly preferred reducing agents are substituted catechols or substituted hydroquinone with 3-(3',4'-dihydroxyphenyl)propionic acid, 3',4'-dihydroxy-butyrophenone, methyl gallate, ethyl gallate and 1,5-dihydroxy-naphthalene being especially preferred.
  • the reducing agent must be present in such a way that it is able to diffuse to the substantially light-insensitive silver salt of a fatty acid particles so that reduction of the substantially light-insensitive silver salt of a fatty acid can take place.
  • auxiliary reducing agents may be used in conjunction with so-called auxiliary reducing agents.
  • auxiliary reducing agents organic reducing metal salts, e.g. stannous stearate described in US-P 3,460,946 and 3,547,648.
  • the photo-addressable thermally developable element of the photothermographic recording material further comprises a dye with maximum absorbance in the wavelength range 600 to 1100nm.
  • 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. Cyanine and merocyanine dyes with imino groups or carboxyl groups are particularly effective.
  • Suitable sensitizers of silver halide to infra-red radiation include those disclosed in the EP-A's 465 078, 559 101, 616 014 and 635 756, the JN's 03-080251, 03-163440, 05-019432, 05-072662 and 06-003763 and the 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 the US-P's 3,877,943 and 4,873,184.
  • binders or mixtures thereof may be used in conjunction with waxes or "heat solvents” also called “thermal solvents” or “thermosolvents” improving the reaction speed of the redox-reaction at elevated temperature.
  • heat solvent in this invention is meant a non-hydrolyzable organic material which is in a solid state in the recording layer at temperatures below 50°C, but becomes a plasticizer for the recording layer where thermally heated and/or a liquid solvent for at least one of the redox-reactants, e.g. the reducing agent for the substantially light-insensitive silver salt of a fatty acid, at a temperature above 60°C.
  • photothermographic materials according to the present invention may contain one or more toning agents.
  • the toning agents should be in thermal working relationship with the substantially light-insensitive silver salts and reducing agents during thermal processing. Any known toning agent from thermography or photothermography may be used.
  • 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
  • Non-ionic, cationic or anionic surfactants may be used, according to the present invention, to produce dispersions of particles of substantially light-insensitive silver salt of a fatty acid and water-dispersible binders, such as polymer latexes, in aqueous media.
  • the photothermographic recording material may contain other additives such as free organic carboxylic acids, antistatic agents, silicone oil, e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY), ultraviolet (UV) light absorbing compounds, white light reflecting and/or UV radiation reflecting pigments, silica, and/or optical brightening agents.
  • free organic carboxylic acids e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY)
  • UV light absorbing compounds e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY)
  • white light reflecting and/or UV radiation reflecting pigments e.g. BAYER AG - GERMANY
  • UV light absorbing compounds e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY)
  • white light reflecting and/or UV radiation reflecting pigments e.g. BAYER AG - GERMANY
  • the photothermographic recording material of the present invention may contain antihalation 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 anti-halation dye may also be bleached either thermally during the thermal development process, or photo-bleached after removable after the thermal development process, as disclosed in the US-P's 3,984,248, 3,988,154, 3,988,156, 4,111,699 and 4,359,524.
  • anti-halation layer may be contained in a layer which can be removed subsequent to the exposure process, as disclosed in US-P 4,477,562 and EP-A 491 457.
  • Suitable antihalation dyes for use with infra-red light are described in the EP-A's 377 961 and 652 473, the EP-B's 101 646 and 102 781 and the US-P's 4,581,325 and 5,380,635.
  • the support for the photothermographic 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. a cellulose ester, polypropylene, polystyrene, polymethacrylic acid ester, polycarbonate or polyester, e.g. polyethylene terephthalate or polyethylene naphthalate.
  • the support may be in sheet, ribbon or web form and subbed if needs be to improve the adherence to the thereon coated heat-sensitive recording layer.
  • Suitable subbing layers for improving the adherence of the photo-addressable thermally developable element and the antistatic layer outermost backing layer of the present invention for polyethylene terephthalate supports are described e.g. in GB-P 1,234,755, US-P 3,397,988; 3,649,336; 4,123,278, US-P 4,478,907 and in Research Disclosure published in Product Licensing Index, July 1967, p. 6.
  • Suitable pretreatments of hydrophobic resin supports are, for example, treatment with a corona discharge and/or attack by solvent(s), thereby providing a micro-roughening.
  • the photo-addressable thermally developable element is provided with a protective layer to avoid local deformation of the photo-addressable thermally developable element, to improve its resistance against abrasion and to prevent its direct contact with components of the apparatus used for thermal development.
  • the protective layer preferably comprises a binder, which may be solvent soluble (hydrophobic), solvent dispersible, water soluble (hydrophilic) or water dispersible.
  • a binder which may be solvent soluble (hydrophobic), solvent dispersible, water soluble (hydrophilic) or water dispersible.
  • hydrophobic binders polycarbonates as described in EP-A 614 769 are particularly preferred.
  • Suitable hydrophilic binders are, for example, gelatin, polyvinylalcohol, cellulose derivatives or other polysaccharides, hydroxyethylcellulose, hydroxypropylcellulose etc., with hardenable binders being preferred.
  • a 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 for protective layers.
  • a protective layer according to the present invention may comprise in addition at least one solid lubricant having a melting point below 150°C and at least one liquid lubricant in a binder, wherein at least one of the lubricants is a phosphoric acid derivative, further dissolved lubricating material.
  • Such protective layers may also comprise particulate material, e.g. talc particles, optionally protruding from the protective outermost layer as described in WO 94/11198.
  • Other additives can also be incorporated in the protective layer e.g. colloidal particles such as colloidal silica.
  • Suitable slipping layer compositions are described in e.g. EP 138483, EP 227090, US-P 4,567,113, 4,572,860 and 4,717,711 and in EP-A's 311 841, 492 411 and 501 072.
  • 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 therefor are described in EP-A's 444 326, 534 006 and 644 456, US-P's 5,364,752 and 5,472,832 and DOS 4125758.
  • any layer of the photothermographic 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, U.S.A.
  • 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 both the production of transparencies and reflection type prints.
  • the support will be transparent or opaque, e.g. having a white light reflecting aspect.
  • a paper base substrate is present which may contain white reflecting pigments, optionally also applied in an interlayer between the recording material and the paper base substrate. Should a transparent base be used, the base may be colourless or coloured, e.g. has a blue colour.
  • the photothermographic recording materials of COMPARATIVE EXAMPLES 1 and 2 comprise a photo-addressable thermally developable layer coated from a solvent dispersion to demonstrate the specificity of the present invention to photothermographic recording materials comprising a photo-addressable thermally developable element coated from an aqueous dispersion.
  • a silver behenate emulsion was prepared by adding a solution of 6.8kg of behenic acid in 67L of 2-propanol at 65°C to a 400L vessel heated to maintain the temperature of its 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 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 45°C for 12 hours.
  • 281.25g of the dried powder containing 4 mol% behenic acid with respect to silver behenate were predispersed in a solution of 281.25g of ButvarTM B79 in 1937.5g of 2-butanone using conventional dispersion techniques and the resulting dispersion homogenized in a MICROFLUIDICSTM M-110Y high pressure microfluidizer at a jet pressure of 400bar.
  • the coating dispersion of COMPARATIVE EXAMPLE 1 was prepared by adding with stirring 0.16g of a 5% by weight solution of phthalazine in 2-butanone, followed by 0.74g of a 20% by weight solution of LOWINOXTM 22IB46 in 2-butanone and finally 1.2g of 2-butanone to the PC03-containing dispersion of silver behenate.
  • the coating dispersion of COMPARATIVE EXAMPLE 2 was prepared by adding with stirring 0.6g of a 5% by weight solution of phthalazine in 2-butanone, followed by 0.74g of a 20% by weight solution of LOWINOXTM 22IB46 in 2-butanone and finally 0.85g of 2-butanone to the PC03-containing dispersion of silver behenate.
  • the resulting dispersions at a temperature of 30°C, were then doctor blade coated onto a 100 ⁇ m thick subbed polyethylene terephthalate (PET) support to a wet thickness of 80 ⁇ m and were allowed to dry on the coating bed for several minutes at 40°C and then were dried for 1 hour in a hot air oven at 50°C to produce the photo-thermographic recording materials of COMPARATIVE EXAMPLES 1 and 2.
  • PET polyethylene terephthalate
  • the photothermographic recording materials of COMPARATIVE EXAMPLES 1 and 2 were then exposed to ultra-violet light through a test original in contact with the material in an Agfa-GevaertTM DL 2000 exposure apparatus. Thermal development was carried out in pressure contact with a metal block whose temperature could be varied between 95 and 150°C. Thermal development was carried out on the photothermographic recording materials after maximum exposure and without exposure and the corresponding optical densities, D max and D min , were determined in transmission with a MacBethTM TR924 densitometer with a visual filter. The optical densities obtained with the photothermographic recording materials of COMPARATIVE EXAMPLES 1 and 2 are given in table 1 together with the thermal development conditions used.
  • the dried powder containing 4 mol% behenic acid with respect to silver behenate prepared as described in COMPARATIVE EXAMPLES 1 and 2 was predispersed in deionized water with the anionic dispersion agents UltravonTM W and MersolatTM H to produce by rapid mixing with a high speed impingement mill (rotor-stator mixer) to obtain a paste and the resulting dispersion homogenized in a MICROFLUIDICSTM M-110Y high pressure microfluidizer at a jet pressure of 400bar to produce an aqueous dispersion containing 16.7% by weight of silver behenate, 0.5% by weight of behenic acid, 2.1% by weight of UltravonTM W and 0.203% by weight of MersolatTM H.
  • the pH of the dispersion was adjusted to about 6.5.
  • each of the dispersions produced 1.5g of a 30% by weight concentration of BINDER 01 in deionized water at a pH of 4, 3g of a 1.22% by weight aqueous solution of PC03, corresponding to a concentration of 8 mol% of PC03 with respect to silver behenate, to accomplish in situ conversion of part of the silver behenate to silver iodide at a pH of 4, 0.5g of a 6.57% by weight aqueous solution of phthalazine and 1.5g of a 5.4% by weight aqueous solution of R01 at a pH of 4.
  • a subbed polyethylene terephthalate support having a thickness of 100 ⁇ m was then doctor blade-coated with the silver behenate/silver iodide dispersion to a wet layer thickness of 90 ⁇ m. After drying for several minutes at 40°C on the coating bed, the emulsion layer was dried for 1 hour in a hot air oven at 50°C.
  • the photothermographic recording materials of INVENTION EXAMPLE 2 to 6 were produced as described for that of INVENTION EXAMPLE 1 except that 0.5g of aqueous solutions of phthalazine with different concentrations as given in table 2 for the particular INVENTION EXAMPLE were substituted for the 0.5g of a 6.57% by weight aqueous solution of phthalazine.
  • the phthalazine concentration in the resulting photothermographic recording materials, also given in table 2 varies between 5 and 30mol% with respect to silver behenate.
  • the photothermographic recording material of INVENTION EXAMPLE 7 was produced as described for that of INVENTION EXAMPLE 2 except that 2.7g of a 1.22% by weight aqueous solution of PC03 and 0.15g of a 2.44% by weight solution of PC02 was added instead of 3g of a 1.22% by weight aqueous solution of PC03.
  • the photothermographic recording material of COMPARATIVE EXAMPLE 3 was produced as described for that of INVENTION EXAMPLE 1 except that 3g of a 1.11% by weight solution of PC02 was added instead of 3g of a 1.22% by weight aqueous solution of PC03.
  • the photothermographic recording material of COMPARATIVE EXAMPLE 4 was produced as described for that of COMPARATIVE EXAMPLE 3 except that 0.5g of a 2.6% by weight aqueous solution of phthalazine was added instead of 0.5g of a 6.57% by weight aqueous solution of phthalazine and therefore contains 10mol% of phthalazine with respect to silver behenate compared with the 25mol% of phthalazine with respect to silver behenate of the photothermographic recording material of COMPARATIVE EXAMPLE 1.
  • the photothermographic recording material of COMPARATIVE EXAMPLE 5 was produced as described for that of INVENTION EXAMPLE 1 except that 0.5g of deionized water was added instead of 0.5g of a 6.57% by weight aqueous solution of phthalazine and therefore contains 0mol% of phthalazine with respect to silver behenate compared with the 25mol% of phthalazine with respect to silver behenate of the photothermographic recording material of INVENTION EXAMPLE 1.
  • the light-box contained a number of evenly spaced fluorescent lamps arranged in such a way that a uniform light flux of 5800Lux at a colour temperature of 5000K could be obtained in the area of the glass window on which the materials being evaluated for post-processing light stability were placed.
  • the photothermographic recording materials of INVENTION EXAMPLES 8 to 13 were produced as described for that of INVENTION EXAMPLE 2 except that the 3g of a 1.22% by weight aqueous solution of PC03 was replaced with solutions of other iodide-containing conversion agents as given in table 3 below.
  • the photothermographic recording material used in INVENTION EXAMPLES 14 to 19 were produced as described for that of INVENTION EXAMPLE 2 except that 1.5g of deionized water was substituted for 1.5g of a 5.4% by weight aqueous solution of R01 at a pH of 4.
  • the photothermographic recording material was then doctor blade-coated to wet layer thickness of 30 ⁇ m with solutions of the reducing agents given below in table 4 in the solvents and at the concentrations also given below in table 4 and the resulting photothermographic recording materials of INVENTION EXAMPLES 14 to 19 dried on the coating bed for several minutes at 40°C followed by 1 hour in a hot air drying cupboard at 50°C.
  • the photothermographic recording material of INVENTION EXAMPLE 20 was produced as described for that of INVENTION EXAMPLE 1 except that 2.0g of deionized water was substituted for 0.5g of a 6.57% by weight aqueous solution of phthalazine and 1.5g of a 5.4% by weight aqueous solution of reducing agent R01 at a pH of 4 and the layer containing silver behenate was further coated to a wet layer thickness of 30 ⁇ m with a mixture of 0.5g of a 6.57% by weight aqueous solution of phthalazine, 1.87g of a 5.4% by weight solution of reducing agent R01, 1.48g of deionized water and several drops of a 8.5% by weight aqueous solution of UltravonTM W.
  • the resulting material which contained 20mol% of phthalazine with respect to silver behenate, was dried on the coating bed for several minutes at 40°C and then for 1 hour in a hot air drying cupboard at 50°C.
  • results in table 5 show that whether the reducing agent and diazine compound are directly incorporated into the silver behenate-containing layer, such as in the photothermographic recording material of INVENTION EXAMPLE 2, or whether they are applied to the silver behenate-containing layer in an aqueous solution subsequently, such as in the photothermographic recording material of INVENTION EXAMPLE 20, had only a marginal effect on the post-processing light stability of these photothermographic recording materials comprising 8mol% of silver iodide and 20mol% of phthalazine with respect to silver behenate, according to the present invention.
  • the photothermographic recording material of INVENTION EXAMPLE 21 was produced as described for that of INVENTION EXAMPLE 3 except that the layer containing silver behenate was further coated to a wet layer thickness of 40 ⁇ m with a mixture of 2.0g of a 3.83% by weight aqueous solution of phthalazine, 0.3g of BINDER 02 and 1.7g of deionized water, resulting in a photothermographic recording material with an overall concentration of phthalazine of 75mol% with respect to silver behenate.
  • the photothermographic recording material of INVENTION EXAMPLE 22 was produced as described for that of INVENTION EXAMPLE 3 except that the layer containing silver behenate was further coated to a wet layer thickness of 40 ⁇ m with a mixture of 1.5g of a 3.83% by weight aqueous solution of phthalazine, 0.3g of BINDER 02 and 2.2g of deionized water, resulting in a photothermographic recording material with an overall concentration of phthalazine of 60mol% with respect to silver behenate.
  • the photothermographic recording material of INVENTION EXAMPLE 23 was produced as described for that of INVENTION EXAMPLE 2 except that 3.75g of a 2% by weight aqueous solution of hydroxyalkyl-cellulose was added instead of 1.5g of a 30% by weight concentration of BINDER 01 in deionized water at a pH of 4.

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  • 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)

Claims (9)

  1. Procédé pour préparer un matériau d'enregistrement photothermographique possédant un support et un élément photo-adressable et développable par voie thermique contenant un halogénure d'argent photosensible en association catalytique avec un sel d'argent essentiellement non photosensible d'un acide gras, un agent de réduction organique pour ledit sel d'argent essentiellement non photosensible d'un acide gras en relation opératoire thermique avec ledit sel, un agent tensioactif et un liant englobant un liant soluble dans l'eau, un liant apte à être dispersé dans l'eau ou un mélange d'un liant soluble dans l'eau et d'un liant apte à être dispersé dans l'eau, comprenant les étapes consistant à : (i) préparer une dispersion aqueuse ou des dispersions aqueuses contenant un halogénure d'argent photosensible, un sel d'argent essentiellement non photosensible d'un acide gras, un agent de réduction organique pour ledit sel d'argent essentiellement non photosensible d'un acide gras et un liant englobant un liant soluble dans l'eau, un liant apte à être dispersé dans l'eau ou un mélange d'un liant soluble dans l'eau et d'un liant apte à être dispersé dans l'eau ; (ii) couler ladite dispersion aqueuse ou lesdites dispersions aqueuses sur un support pour ainsi obtenir un élément photo-adressable et développable par voie thermique sur ledit support, caractérisé en ce qu'au moins 80 moles % dudit halogénure d'argent photosensible est de l'iodure d'argent et ladite dispersion aqueuse contient en outre ou lesdites dispersions aqueuses contiennent en outre un composé de diazine.
  2. Procédé pour préparer un matériau d'enregistrement photothermographique selon la revendication 1, dans lequel ledit composé de diazine est un composé de 1,2-diazine ou un composé de 1,2-diazine substitué.
  3. Procédé pour préparer un matériau d'enregistrement photothermographique selon la revendication 1 ou 2, dans lequel ledit composé de diazine est une phtalazine ou une phtalazine substituée.
  4. Procédé pour préparer un matériau d'enregistrement photothermographique selon l'une quelconque des revendications précédentes, dans lequel au moins 90 moles % dudit halogénure d'argent photosensible est de l'iodure d'argent.
  5. Procédé pour préparer un matériau d'enregistrement photothermographique selon l'une quelconque des revendications précédentes, dans lequel ledit élément photo-adressable et développable par voie thermique est muni d'une couche de protection.
  6. Procédé pour préparer un matériau d'enregistrement photothermographique selon l'une quelconque des revendications précédentes, dans lequel ledit élément photo-adressable et développable par voie thermique comprend en outre un colorant dont le pouvoir absorbant maximal se situe dans la plage de longueurs d'ondes de 600 à 1100 nm.
  7. Procédé pour préparer un matériau d'enregistrement photothermographique selon l'une quelconque des revendications précédentes, dans lequel ladite dispersion aqueuse ou lesdites dispersions aqueuses englobent une suspension aqueuse de particules d'un sel d'argent essentiellement non photosensible d'un acide gras, que l'on obtient par addition dosée simultanée d'une solution ou d'une suspension aqueuse d'un acide gras ou de son sel et d'une solution aqueuse d'un sel d'argent à un liquide aqueux, et dans lequel ladite addition dosée de ladite solution aqueuse ou de ladite suspension aqueuse dudit acide gras ou de son sel et/ou ladite solution aqueuse dudit sel d'argent est réglée par la concentration des ions argent ou par la concentration des anions dudit sel d'argent dans ledit liquide aqueux.
  8. Matériau d'enregistrement photothermographique comprenant un support et un élément photo-adressable développable par voie thermique contenant un halogénure d'argent photosensible en association catalytique avec un sel d'argent essentiellement non photosensible d'un acide gras, un agent de réduction organique pour ledit sel d'argent essentiellement non photosensible d'un acide gras en relation opératoire thermique avec ledit sel et un liant englobant un liant soluble dans l'eau, un liant apte à être dispersé dans l'eau ou un mélange d'un liant soluble dans l'eau et d'un liant apte à être dispersé dans l'eau, caractérisé en ce qu'au moins 80 moles % dudit halogénure d'argent photosensible est de l'iodure d'argent et ledit élément photo-adressable et développable par voie thermique contient en outre un agent tensioactif et une phtalazine ou un composé de phtalazine substituée.
  9. Matériau d'enregistrement photothermographique selon la revendication 8, dans lequel au moins 90 moles % dudit halogénure d'argent photosensible est de l'iodure d'argent.
EP19970203816 1996-12-30 1997-12-05 Produit d'enrégistrement pouvant être couché à partir d'un milieu aqueux Expired - Lifetime EP0851284B1 (fr)

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JP4037090B2 (ja) * 2001-07-12 2008-01-23 富士フイルム株式会社 熱現像感光材料への画像形成方法
ATE317135T1 (de) 2001-07-12 2006-02-15 Fuji Photo Film Co Ltd Bilderzeugungsverfahren
US20030232288A1 (en) * 2001-11-05 2003-12-18 Yutaka Oka Photothermographic material and method of thermal development of the same

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JPS5435487B2 (fr) * 1973-06-11 1979-11-02
US4201582A (en) * 1974-05-02 1980-05-06 Eastman Kodak Company Photothermographic and thermographic element, composition and process
US4105451A (en) * 1976-12-22 1978-08-08 Eastman Kodak Company Photothermographic material, composition and process
JPS53137096A (en) * 1977-05-06 1978-11-30 Fuji Photo Film Co Ltd Production of slightly soluble silver salt particles
US4168980A (en) * 1977-08-19 1979-09-25 Eastman Kodak Company Heat developable photographic material and process
JPS55153937A (en) * 1979-04-16 1980-12-01 Asahi Chem Ind Co Ltd Image forming material
JPS5828737A (ja) * 1981-07-21 1983-02-19 Konishiroku Photo Ind Co Ltd 熱現像感光材料
US4743534A (en) * 1983-11-30 1988-05-10 Minnesota Mining And Manufacturing Company Preformed silver halides for photothermographic system
US4585734A (en) * 1985-02-01 1986-04-29 Minnesota Mining And Manufacturing Company Photothermographic toners
US5350669A (en) * 1994-01-19 1994-09-27 Minnesota Mining And Manufacturing Company Silver-carboxylate/1,2-diazine compounds as silver sources in photothermographic and thermographic elements
US5541054B1 (en) * 1995-04-20 1998-11-17 Imation Corp Spectral sensitizing dyes for photothermographic elements

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