EP0821271A1 - Produit photothermographique sensible à l'infra-rouge comprenant un sensibilisateur spectral et un supersensibilisateur à base de stilbene - Google Patents

Produit photothermographique sensible à l'infra-rouge comprenant un sensibilisateur spectral et un supersensibilisateur à base de stilbene Download PDF

Info

Publication number
EP0821271A1
EP0821271A1 EP97201904A EP97201904A EP0821271A1 EP 0821271 A1 EP0821271 A1 EP 0821271A1 EP 97201904 A EP97201904 A EP 97201904A EP 97201904 A EP97201904 A EP 97201904A EP 0821271 A1 EP0821271 A1 EP 0821271A1
Authority
EP
European Patent Office
Prior art keywords
recording material
dye
substituted
silver salt
sensi
Prior art date
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.)
Granted
Application number
EP97201904A
Other languages
German (de)
English (en)
Other versions
EP0821271B1 (fr
Inventor
Herman Uytterhoeven
Johan Loccufier
Geert Deroover
Paul Callant
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP19970201904 priority Critical patent/EP0821271B1/fr
Publication of EP0821271A1 publication Critical patent/EP0821271A1/fr
Application granted granted Critical
Publication of EP0821271B1 publication Critical patent/EP0821271B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/164—Infra-red processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • G03C1/49854—Dyes or precursors of dyes

Definitions

  • the present invention relates to a photothermographic recording material comprising a photo-addressable thermally developable element comprising a species which increases the infrared sensitivity thereof.
  • Thermal imaging or thermography is a recording process wherein images are generated by the use of thermal energy.
  • thermography three approaches are known:
  • Thermographic materials of type 1 become photothermographic 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.
  • the most widely used radiation-sensitive salt in such materials is silver halide, which must be present in catalytic association with the organic silver salt so that the species formed on exposure can catalyze the thermal image forming process.
  • Silver halide requires spectral sensitization with dyes to extend its sensitivity range into the infra-red region of actinic radiation.
  • US 4,873,184 discloses a spectrally sensitized silver halide photothermographic emulsion layer comprising a reducible silver source material as 20 to 70% by weight of said emulsion layer, photosensitive silver halide, and a reducing agent for silver ion, said photosensitive silver halide having no latent image therein and being present as 1.5 to 7% by weight of said emulsion layer and said emulsion layer having a speed increasing effective amount of a metal complexing agent therein in an amount equal to 0.4 to 40% by weight of total silver in said emulsion.
  • EP-A 559 228 discloses a photothermographic emulsion comprising a binder, a light insensitive silver salt, a reducing agent for silver ion, and silver halide, the silver halide being spectrally sensitized to radiation of from 750 to 1300 nm and the emulsion containing a supersensitizing amount of a compound selected from the group consisting of heteroaromatic mercapto compounds or heteroaromatic disulfide compounds. Furthermore, a comparative example is disclosed demonstrating an absence of supersensitization with a stilbene compound, Leucophor BCF from SANDOZ.
  • the heat developable photosensitive material may contain organic metal salts as oxidising agents in conjunction with the photosensitive silver halide in this invention;
  • the divalent aromatic residue may be a 2,2'-disulfostilbene, a 4,4'-bis(benzoylamino)-2,2'-disulfostilbene residues; and water-soluble and water-dispersible polymers may be used with gelatin, a water-soluble polymer being used in the invention examples.
  • No invention examples are disclosed in which in the compound (A) W 1 and W 2 are both N.
  • a photothermographic recording material comprising a support and a photo-addressable thermally developable element comprising a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association with the substantially light-insensitive organic silver salt and spectrally sensitized to infra-red light with a dye, a supersensitizer for the dye, a reducing agent in thermal working relationship with the substantially light-insensitive organic silver salt and a binder, characterized in that the binder comprises a water soluble polymer, a water-dispersible polymer or a water soluble polymer and a water-dispersible polymer; the dye absorbs electromagnetic radiation in the wavelength range from 700 to 1100nm; and the supersensitizer is a stilbene compound represented by general formula (I): wherein R 1 , R 2 , R 3 and R 4 are independently hydrogen or alkyl, aryl, aralkyl, alkaryl, alkoxy or aryloxy groups
  • a process is also provided producing a photothermographic recording material, as referred to above, comprising the steps of; (i) producing an aqueous dispersion or aqueous dispersions comprising the substantially light-insensitive organic silver salt, the photosensitive silver halide spectrally sensitized to infra-red light with the dye, the supersensitizer for the dye, the reducing agent and the binder; (ii) coating the aqueous dispersion or aqueous dispersions onto a support.
  • a recording process for a photothermographic recording material us further provided comprising the steps of: imagewise exposing to infrared actinic radiation a photothermographic material as referred to above or produced according as referred to above; and overall heating of the photothermographic recording material.
  • 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.
  • a dye which spectrally sensitizes photosensitive silver halide to infra-red light, wherein the dye absorbs electromagnetic radiation in the wavelength range from 700 to 1100nm and preferably in the wavelength range from 750 to 950nm.
  • the dye corresponds to the general formula (II): wherein Z 1 and Z 2 independently represent S, O or Se; R 1 and R 17 are independently each an alkyl or substituted alkyl group; R 2 , R 3 , R 4 , R 5 , R 13 , R 14 , R 15 and R 16 are independently each hydrogen, chlorine, bromine, fluorine or a keto-, sulfo-, carboxy-, ester-, sulfonamide-, amide-, dialkylamino, nitro-, cyano-, alkyl-, alkenyl-, hetero-aromatic, aryl-, alkoxy- or aryloxy- group, which groups may be substituted; or each of R 2 together with R 3 , R 3 together with R 4 , R 4 together with R 5 , R 13 together with R 14 , R 14 together with R 15 and R 15 together with R 16 may independently constitute the atoms necessary to complete a benzene
  • R 1 and R 17 each independently represent an alkyl group consisting of 1 to 6 carbon atoms which may be substituted with a sulfo- or a carboxy-group.
  • Suitable infra-red sensitizing dyes for photosensitive silver halide are the N-alkyl benzothiazole heptamethine cyanine dyes: the N-alkylsulfo benzothiazole heptamethine cyanine dyes: the N-alkylcarboxy benzothiazole heptamethine cyanine dyes:
  • the term carboxy-group represents -COOH and its salts and the term sulfo-group represents -SO 3 H and its salts.
  • the stilbene compound used in the present invention at least two of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 in general formula (I) are sulfo- or carboxy-groups.
  • the compound represented by general formula (I) is a 2,2'-disulfo-4,4'-bis(triazinylamino)stibene compound.
  • Particularly preferred supersensitizers used according to the present invention are:
  • the photo-addressable thermally developable element includes a binder containing a water-soluble binder, a water-dispersible binder or a mixture of a water soluble binder and a water-dispersible binder.
  • a binder containing a water-soluble binder, a water-dispersible binder or a mixture of a water soluble binder and a water-dispersible binder.
  • 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: polyvinyl alcohol, polyacrylamide, polyacrylic acid, polymethacrylic acid, polyethyleneglycol, proteins, such as gelatin and modified gelatins such as phthaloyl gelatin, 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 comprises a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association therewith and an organic reducing agent in thermal working relationship with the substantially light-insensitive organic silver salt and a water soluble or water-dispersible binder.
  • the element may include a layer system with the silver halide in catalytic association with the substantially light-insensitive organic silver salt, spectral sensitizer optionally together with a supersensitizer in intimate 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, are in thermal working relationship with the substantially light-insensitive organic silver salt i.e. during the thermal development process the reducing agent and the toning agent, if present, are able to diffuse to the substantially light-insensitive organic silver salt.
  • Preferred substantially light-insensitive organic silver salts produced using the process according to the present invention and used in the photothermographic materials, according to the present invention are silver salts of organic carboxylic acids having as their organic group: aryl, aralkyl, alkaryl or alkyl.
  • organic carboxylic acids having as their organic group: aryl, aralkyl, alkaryl or alkyl.
  • aliphatic carboxylic acids known as fatty acids wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, which silver salts are also called "silver soaps”.
  • Silver salts of modified aliphatic carboxylic acids with thioether group as described e.g. in GB-P 1,111,492, may likewise be used to produce a thermally developable silver image.
  • the substantially light-insensitive organic silver salt is a silver salt of a fatty acid.
  • substantially light-insensitive organic silver salt for the purposes of the present invention also includes mixtures of organic silver salts.
  • the binder to organic silver salt weight ratio is preferably in the range of 0.2 to 6, and the thickness of the recording layer is preferably in the range of 1 to 50 ⁇ m.
  • 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 organic silver salt, with the range of 0.5 to 20 mol percent being preferred and the range of 1 to 12 mol percent being particularly preferred.
  • 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.
  • particles of the photosensitive silver halide are non-aggregating in the photo-addressable thermally developable element and are uniformly distributed over and between particles of the substantially light-insensitive organic silver salt, at least 80% by number of the particles having a diameter, determined by transmission electron microscopy, of ⁇ 40nm.
  • the suspension of particles of a substantially light-insensitive organic silver salt may be produced by simultaneous metered addition of an aqueous solution or suspension of an organic carboxylic acid, or its salt, and an aqueous solution of a silver salt to an aqueous liquid and the metered addition of the aqueous solution or suspension of the organic carboxylic 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 as disclosed in EP-A 754 969.
  • 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 organic silver salt.
  • Silver halide and the substantially light-insensitive organic silver salt which are separately formed, i.e. ex-situ or "preformed", in a binder can be mixed prior to use to prepare a coating solution, but it is also effective to blend both of them for a long period of time.
  • it is effective to use a process which comprises adding a halogen-containing compound to the organic silver salt to partially convert the substantially light-insensitive organic silver salt to silver halide as disclosed in US-P 3,457,075.
  • the aqueous emulsion of the organic silver salt optionally including photosensitive silver halide can, according to the present invention, also be produced from particles of the organic silver salt 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 produced by reacting an aqueous dispersion of particles of the substantially light-insensitive organic silver salt with at least one onium salt with halide or polyhalide anions may be present.
  • Onium cations, according to the present invention may be polymeric or non-polymeric.
  • Preferred non-polymeric onium salts for partial conversion of particles of substantially light-insensitive organic silver salt into photosensitive silver halides according to the present invention are:
  • the onium salts are present in quantities of between 0.1 and 35mol % with respect to the quantity of substantially light-insensitive organic silver salt of organic, with quantities between 0.5 and 20mol% being preferred and with quantities between 1 and 12mol % being particularly preferred.
  • Suitable organic reducing agents for the reduction of the substantially light-insensitive organic heavy metal salts are organic compounds containing at least one active hydrogen atom linked to O, N or C.
  • Particularly suitable organic reducing agents for the reduction of the substantially light-insensitive organic silver salt, an organic reducing agent for the substantially light-insensitive organic silver salt 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 annelated 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
  • Particularly preferred reducing agents are substituted catechols or substitued hydroquinones 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 organic silver salt particles so that reduction of the substantially light-insensitive organic silver salt can take place.
  • auxiliary reducing agents may be used in conjunction with so-called auxiliary reducing agents.
  • Auxiliary reducing agents that may be used in conjunction with the above mentioned primary reducing agents are sulfonyl hydrazide reducing agents such as disclosed in US-P 5,464,738, trityl hydrazides and formyl-phenyl-hydrazides such as disclosed in US-P 5,496,695 and organic reducing metal salts, e.g. stannous stearate described in US-P 3,460,946 and 3,547,648.
  • 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 organic silver salt, 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 organic silver salts and reducing agents during thermal processing. Any known toning agent from thermography or photothermography may be used.
  • Suitable toning agents are succinimide and the phthalimides and phthalazinones within the scope of the general formulae described in US-P 4,082,901 and the toning agents described in US-P 3,074,809, US-P 3,446,648 and US-P 3,844,797.
  • Particularly useful toning agents are the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type as described in GB-P 1,439,478 and US-P 3,951,660.
  • 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 the substantially light-insensitive organic silver salt in aqueous media and to disperse water-dispersible binders, such as polymer latexes, in aqueous media.
  • the surfactant is a sulfonate e.g. alkyl, aryl, alkaryl or aralkyl sulfonate, with alkyl and alkaryl sulfonates being particularly preferred e.g.:
  • the photothermographic material may contain other additives such as free organic carboxylic acids, surface-active agents, antistatic agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H, silicone oil, e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY), ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, silica, and/or optical brightening agents.
  • antistatic agents e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
  • silicone oil e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY)
  • ultraviolet light absorbing compounds e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GER
  • the photothermographic recording material further comprises an antihalation or acutance dye which absorbs light which has passed through the photosensitive layer, thereby preventing its reflection.
  • an antihalation or acutance dye which absorbs 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 antihalation dye may also be bleached either thermally during the thermal development process or photo-bleached after removable after the thermal development process and it may be contained in a layer which can be removed subsequent to the exposure process.
  • 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, e.g. having a white light reflecting aspect and is preferably a thin flexible carrier made e.g. from paper, polyethylene coated paper or transparent resin film, e.g. made of a cellulose ester, e.g. cellulose triacetate, corona and flame treated polypropylene, polystyrene, polymethacrylic acid ester, polycarbonate or polyester, e.g. polyethylene terephthalate or polyethylene naphthalate as disclosed in GB 1,293,676, GB 1,441,304 and GB 1,454,956.
  • a 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.
  • 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 thermosensitive 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 and US-P 4,478,907 which relates to subbing layers applied from aqueous dispersion of sulfonated copolyesters, and further the subbing layers described 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.
  • 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 and polyvinyl alcohol being particularly preferred.
  • a protective layer used in 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 used in the present invention may include 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 and/or particulate material, e.g. talc particles, optionally protruding from the outermost layer.
  • the lubricant may be applied with or without a polymeric binder.
  • Such protective layers may also include particulate material, e.g. talc particles, optionally protruding from the protective outermost layer as described in WO 94/11198.
  • particulate material e.g. talc particles
  • Other additives can also be incorporated in the protective layer e.g. colloidal particles such as colloidal silica.
  • 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 infrared radiation with the image either being obtained by pixel-wise exposure with a finely focussed light source, such as an IR wavelength laser or an IR-laser diode, e.g. emitting at 780nm, 830nm or 850nm; or by direct exposure to the object itself or an image therefrom with IR light.
  • a finely focussed light source such as an IR wavelength laser or an IR-laser diode, e.g. emitting at 780nm, 830nm or 850nm; or by direct exposure to the object itself or an image therefrom with IR light.
  • 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.
  • a photothermographic recording process comprising the steps of: (i) image-wise exposing a photothermographic recording material, as referred to above, with actinic radiation to which the photothermographic recording material is sensitive; and (ii) thermally developing the image-wise exposed photothermographic recording material.
  • 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.
  • Silver behenate was prepared by dissolving 34g (0.1 moles) of behenic acid in 340mL of 2-propanol at 65°C, converting the behenic acid to sodium behenate by adding 400mL of 0.25M aqueous sodium hydroxide to the stirred behenic acid solution and finally adding 250mL of 0.4M aqueous silver nitrate the silver behenate precipitating out. This was filtered off and then washed with a mixture of 10% by volume of 2-propanol and 90% by volume of deionized water to remove residual sodium nitrate.
  • the silver behenate was dispersed in deionized water with the anionic dispersion agents UltravonTM W and MersolatTM H to produce, after rapid mixing using a high speed impingement mill (rotor-stator mixer) to obtain a paste and homogenization with a microfluidizer, a finely divided and stable dispersion containing 20% by weight of silver behenate, 2.1% by weight of UltravonTM W and 0.203% by weight of MersolatTM H. The pH of the resulting dispersion was adjusted to about 6.5.
  • the following ingredients were then added with stirring to 3.0g of the silver behenate dispersion: 2g of a 2.22% by weight aqueous solution of 3-(triphenyl-phosphonium)propionic acid bromide (PC02), corresponding to a concentration of 8 mol% of PC02 with respect to silver behenate, at a pH of 4 to accomplish in situ conversion of part of the silver behenate to silver bromide.
  • PC02 3-(triphenyl-phosphonium)propionic acid bromide
  • the supersensitizer was added with stirring as a solution in water and/or methanol, as specified in table 1, immediately followed by the IR-spectral sensitizer as a solution or dispersion in water and/or methanol as specified in table 1.
  • a subbed polyethylene terephthalate support having a thickness of 100 ⁇ m was doctor blade-coated with the silver behenate/silver bromide dispersion at a blade setting 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 40°C.
  • the photothermographic materials of COMPARATIVE EXAMPLES 1 to 22 were exposed to a beam of a 836nm diode laser type HL 8318G from HITACHI with a nominal power of 12.8mW focussed to give a spot diameter (1/e 2 ) of 115 ⁇ m, scanned at a speed of 5m/s with a pitch of 63 ⁇ m and an overlap of 30% through a wedge filter with optical density varying between 0 and 3.3 in optical density steps of 0.15.
  • the maximum exposure (filter optical density 0) was about 50J/m 2 .
  • Thermal processing was carried out on a heated metal block for 5 to 30s at 105 to 115°C, as specified in table 2.
  • the maximum and minimum optical densities, D max and D min , of the images were measured in transmission with a MacBethTM TR924 densitometer through a visible filter.
  • Photothermographic recording materials comprising photo-addressable thermally developable elements with IR-sensitizers and stilbene supersensitizers coated from aqueous media:
  • the photothermographic emulsions of INVENTION EXAMPLES 1 to 12 and COMPARATIVE EXAMPLES 23 to 25 were prepared as described for COMPARATIVE EXAMPLES 1 to 22 except that the IR-sensitizer, IR-sensitizer solution or dispersion, weight of IR-sensitizer solution or dispersion, supersensitizer, supersensitizer solution and weight of supersensitizer solution used for each photothermographic emulsion is as given in table 3.
EP19970201904 1996-07-24 1997-06-21 Procédé pour la production d'un produit photothermographique sensible à l'infra-rouge comprenant un sensibilisateur spectral et un supersensibilisateur à base de stilbene et procédé d'enregistrement. Expired - Lifetime EP0821271B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19970201904 EP0821271B1 (fr) 1996-07-24 1997-06-21 Procédé pour la production d'un produit photothermographique sensible à l'infra-rouge comprenant un sensibilisateur spectral et un supersensibilisateur à base de stilbene et procédé d'enregistrement.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP96202107 1996-07-24
EP96202107 1996-07-24
EP19970201904 EP0821271B1 (fr) 1996-07-24 1997-06-21 Procédé pour la production d'un produit photothermographique sensible à l'infra-rouge comprenant un sensibilisateur spectral et un supersensibilisateur à base de stilbene et procédé d'enregistrement.

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP05108808 Division 1997-06-21

Publications (2)

Publication Number Publication Date
EP0821271A1 true EP0821271A1 (fr) 1998-01-28
EP0821271B1 EP0821271B1 (fr) 2006-04-19

Family

ID=26143036

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19970201904 Expired - Lifetime EP0821271B1 (fr) 1996-07-24 1997-06-21 Procédé pour la production d'un produit photothermographique sensible à l'infra-rouge comprenant un sensibilisateur spectral et un supersensibilisateur à base de stilbene et procédé d'enregistrement.

Country Status (1)

Country Link
EP (1) EP0821271B1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017123444A1 (fr) 2016-01-15 2017-07-20 Carestream Health, Inc. Procédé de préparation de savons de carboxylate d'argent
US10473658B2 (en) 2013-03-15 2019-11-12 Visen Medical, Inc. 4,4-disubstituted cyclohexyl bridged heptamethine cyanine dyes and uses thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5828737A (ja) * 1981-07-21 1983-02-19 Konishiroku Photo Ind Co Ltd 熱現像感光材料
JPS61193142A (ja) * 1985-02-04 1986-08-27 Konishiroku Photo Ind Co Ltd 熱現像感光材料
JPS6323145A (ja) * 1986-03-11 1988-01-30 Fuji Photo Film Co Ltd 熱現像感光材料
EP0559228A1 (fr) * 1992-03-06 1993-09-08 Minnesota Mining And Manufacturing Company Eléments photothermographiques
EP0609571A1 (fr) * 1993-02-01 1994-08-10 Agfa-Gevaert N.V. Composés stilbèniques utilisés comme supersensibilisateurs dans des matériaux photographiques sensibles à l'IR

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5828737A (ja) * 1981-07-21 1983-02-19 Konishiroku Photo Ind Co Ltd 熱現像感光材料
JPS61193142A (ja) * 1985-02-04 1986-08-27 Konishiroku Photo Ind Co Ltd 熱現像感光材料
JPS6323145A (ja) * 1986-03-11 1988-01-30 Fuji Photo Film Co Ltd 熱現像感光材料
EP0559228A1 (fr) * 1992-03-06 1993-09-08 Minnesota Mining And Manufacturing Company Eléments photothermographiques
EP0609571A1 (fr) * 1993-02-01 1994-08-10 Agfa-Gevaert N.V. Composés stilbèniques utilisés comme supersensibilisateurs dans des matériaux photographiques sensibles à l'IR

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section PQ Week 8641, Derwent World Patents Index; Class P83, AN 86-267419, XP002024492 *
DATABASE WPI Section PQ Week 8810, Derwent World Patents Index; Class P83, AN 88-068085, XP002043732 *
J.A. VERDONE ET AL: "POLYMERIC BINDERS FOR PHOTOTHERMOGRAPHIC MATERIALS", RESEARCH DISCLOSURE, no. 186, October 1979 (1979-10-01), HAVANT GB, pages 573, XP002024491 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10473658B2 (en) 2013-03-15 2019-11-12 Visen Medical, Inc. 4,4-disubstituted cyclohexyl bridged heptamethine cyanine dyes and uses thereof
US11193932B2 (en) 2013-03-15 2021-12-07 Visen Medical, Inc. 4,4-disubstituted cyclohexyl bridged heptamethine cyanine dyes and uses thereof
WO2017123444A1 (fr) 2016-01-15 2017-07-20 Carestream Health, Inc. Procédé de préparation de savons de carboxylate d'argent

Also Published As

Publication number Publication date
EP0821271B1 (fr) 2006-04-19

Similar Documents

Publication Publication Date Title
EP0839337B1 (fr) Materiau d'enregistrement photothermographique
US6143488A (en) Photothermographic recording material coatable from an aqueous medium
EP0904565B1 (fr) Materiau d'enregistrement photothermographique
US6274297B1 (en) Photothermographic recording material with in-situ and ex-situ photosensitive silver halide and a substantially light-insensitive organic salt
US5876915A (en) Photothermographic recording material comprising sensitizing dyes and a recording process therefor
EP0904564B1 (fr) Procede de production d'un materiau photothermographique et procede d'enregistrement correspondant
US6074814A (en) Photothermographic material comprising an infra-red sensitizer
US5851755A (en) Photothermographic material comprising at least one dye absorbing electromagnetic radiation in the wavelength range 700 to 1100NM
US5958667A (en) Photothermographic recording material comprising IR-sensitizing dyes
EP0821271B1 (fr) Procédé pour la production d'un produit photothermographique sensible à l'infra-rouge comprenant un sensibilisateur spectral et un supersensibilisateur à base de stilbene et procédé d'enregistrement.
EP0922995B1 (fr) Matériau d'enregistrement photothermographique avec halogénure d'argent in situ et ex situ et avec un sel organique d'argent substantiellement insensible à la lumière
US6383725B2 (en) Emulsion for a photothermographic material, a production process for the thermographic material and a recording process therefor
EP0851284B1 (fr) Produit d'enrégistrement pouvant être couché à partir d'un milieu aqueux
JPH10111543A (ja) ７００〜１１００ｎｍの波長領域における電磁線を吸収する少なくとも１種の色素を含むフオトサーモグラフイ材料
EP0821270A1 (fr) Produit photothermographique comprenant un sensibilateur pour l'infra-rouge
EP0821272B1 (fr) Procédé de préparation d'un produit d'enregistrement, photothermographique comprenant des colorants sensibilisateurs de l'infra-rouge
JP3794793B2 (ja) 増感色素を含むフオトサーモグラフイ記録材料及びそのための記録法
EP0821266A1 (fr) Produit d'enregistrement photothermographique comprenant des colorants sensibilisateurs et procédé d'enregistrement l'utilisant
EP0821268B1 (fr) Emulsion pour un produit photothermographique, procédé pour la production dudit produit photothermographique et procédé de reproduction l'utilisant
US6010843A (en) Photothermographic recording material comprising a hydrazine compound and a recording process therefor
EP0959383A1 (fr) Matériau d'enregistrement photothermographique contenant des grains tabulaires et un composé d'hydrazine
EP0810468A1 (fr) Colorants anti-halo pour un matériau d'enregistrement photothermographique et procédé d'enregistrement utilisant ce matériau
JPH1010672A (ja) 熱現像感光材料
EP0821269A1 (fr) Matériau d'enregistrement photothermographique comprenant un composé d'hydrazine et procédé d'enregistrement associé
JPH1073901A (ja) 赤外増感染料を含んでなるフオトサーモグラフイ記録材料

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17P Request for examination filed

Effective date: 19980728

RBV Designated contracting states (corrected)

Designated state(s): BE DE FR GB

17Q First examination report despatched

Effective date: 19990106

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: AGFA-GEVAERT

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: PROCESS FOR PREPARING AN INFRA-RED PHOTOTHERMOGRAPHIC MATERIAL COMPRISING A SPECTRAL SENSITIZER AND A STILBENE DERIVATIVE

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060419

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69735697

Country of ref document: DE

Date of ref document: 20060524

Kind code of ref document: P

ET Fr: translation filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

Effective date: 20070213

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20070122

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070529

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070608

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070525

Year of fee payment: 11

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080621

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20090228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080630