EP0821272B1 - Procédé de préparation d'un produit d'enregistrement, photothermographique comprenant des colorants sensibilisateurs de l'infra-rouge - Google Patents

Procédé de préparation d'un produit d'enregistrement, photothermographique comprenant des colorants sensibilisateurs de l'infra-rouge Download PDF

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Publication number
EP0821272B1
EP0821272B1 EP97201905A EP97201905A EP0821272B1 EP 0821272 B1 EP0821272 B1 EP 0821272B1 EP 97201905 A EP97201905 A EP 97201905A EP 97201905 A EP97201905 A EP 97201905A EP 0821272 B1 EP0821272 B1 EP 0821272B1
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EP
European Patent Office
Prior art keywords
recording material
sensi
photothermographic recording
water
group
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EP97201905A
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German (de)
English (en)
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EP0821272A1 (fr
Inventor
Geert Deroover
Paul Callant
Herman Uytterhoeven
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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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
    • G03C1/005—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
    • 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
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/20—Methine and polymethine dyes with an odd number of CH groups with more than three CH groups
    • 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—Infrared processes

Definitions

  • the present invention relates to a process for producing a photothermographic recording material comprising photosensitive silver halide spectrally sensitized with specific dyes and a recording process therefor.
  • Thermal imaging or thermography is a recording process wherein images are generated by the use of imagewise modulated 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-P 4,835,096 discloses a photothermographic element characterised in that it contains as a sensitizer a dye of the general formula: wherein R 1 represents a lower alkyl group of from 1 to 5 carbon atoms and X - represents an anion;
  • US-P 5,441,866 discloses a heat-developable photothermographic element comprising
  • a process for producing a photothermographic recording material comprising a support and a photo-addressable thermally developable element exclusive of a supersensitizer and containing a substantially light-insensitive organic silver salt, a reducing agent therefor in thermal working relationship therewith, photosensitive silver halide spectrally sensitized to wavelengths > 700nm with a dye and in catalytic association with the substantially light-insensitive organic silver salt and a water-soluble binder, a water-dispersible binder or a mixture of a water-soluble and a water-dispersible binder, comprising the steps of: (i) producing an aqueous dispersion or aqueous dispersions containing the substantially light-insensitive organic silver salt, the photosensitive silver halide spectrally sensitized to infra-red light with the dye, the reducing agent and the water-soluble binder, water-dispersible binder or mixture of a water-soluble and a water-dispersible
  • infra-red light for the purposes of the present invention means light with a wavelength in the range from 700nm to 1000 ⁇ m.
  • 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.
  • the photo-addressable thermally developable element comprises a dye satisfying the following test: an exposure required by a photothermographic recording material A, consisting of a polyester 100 ⁇ m thick support provided with a photo-addressable thermally developable element produced as described in the description and comprising the dye and a compound corresponding to the formula is > 90% of an exposure required by a photothermographic recording material B produced as described for the photothermographic recording material A except that the compound is omitted, the exposure of the materials A and B being that required to obtain an optical density in an exposed part thereof 0.5 higher than in an non-exposed part thereof when exposed to infra-red light to which it is sensitive and heating with a heat source at 105°C for 15s with the polyester support thereof in contact with the heat source.
  • the dilithium salt of 2,2'-disulfo-4,4'-bis[2- ⁇ 4,6-bis(2-oxynaphtho) ⁇ -triazino]-aminostilbene was chosen as the supersensitizer for the above-mentioned test because it had been found to be an efficient supersensitizer for photothermographic recording materials comprising a photo-addressable thermally developable element coated from aqueous media as is disclosed by the inventors in a copending European Patent Application and can be seen from the comparative examples.
  • the photothermographic recording material has an infra-red sensitivity of less than 8J/m 2 .
  • Suitable IR-sensitizing dyes used according to the present invention are:
  • SENSI 01 was synthesized as described in INVENTION EXAMPLE 1. Similar synthetic techniques to those described in INVENTION EXAMPLE 1 and those described in F.M. Hamer, "The Cyanine Dyes and Related Compounds", Interscience Publishers, New York (1964) can be used to synthesize other IR-sensitizing dyes used according to the present invention.
  • the sensitivity of the photothermographic recording materials comprising IR-sensitizing dyes used according to the present invention will depend upon the choice of IR-sensitizing dye, the concentration thereof, the way in which the IR-sensitizing dye is incorporated and the exact composition of the photothermographic recording material.
  • the photo-addressable thermally developable element used according to the present invention, 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 comprise 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 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 used according to the present invention are silver salts of organic carboxylic acids in particular aliphatic carboxylic acids known as fatty acids, wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, which silver salts are also called "silver soaps"; silver dodecyl sulphonate described in US-P 4,504,575; and silver di-(2-ethylhexyl)-sulfosuccinate described in EP-A 227 141.
  • organic carboxylic acids in particular aliphatic carboxylic acids known as fatty acids, wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, which silver salt
  • Modified aliphatic carboxylic acids with thioether group as described e.g. in GB-P 1.111.492 and other organic silver salts as described in GB-P 1,439,478, e.g. silver benzoate and silver phthalazinone, may be used likewise to produce a thermally developable silver image.
  • the photosensitive silver halide used in the present invention may be employed in a range of from 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.
  • 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.
  • a production process for the photothermographic recording material further comprising the step of forming particles of the photosensitive silver halide by reacting an aqueous emulsion of particles of the substantially light-insensitive organic silver salt with at least one onium salt with halide or polyhalide anion(s).
  • 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, used 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 used 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.
  • Organic reducing agent for photo-addressable thermally developable elements coated from aqueous media Organic reducing agent for photo-addressable thermally developable elements coated from aqueous media
  • Suitable organic reducing agents for the reduction of the substantially light-insensitive organic heavy metal salts in photo-addressable thermally developable coated from aqueous media are organic compounds containing at least one active hydrogen atom linked to 0, N or C.
  • Particularly suitable organic reducing agents for the reduction of the substantially light-insensitive organic silver salt in such photo-addressable thermally developable elements 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-ary
  • 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 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.
  • the photo-addressable thermally developable element comprises a binder comprising a water-soluble binder, a water-dispersible binder or a mixture of a water soluble binder and a water-dispersible binder.
  • 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 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.
  • water-insoluble polymer e.g. water-insoluble cellulose derivatives, poly
  • a particularly suitable polyvinyl butyral containing a minor amount of vinyl alcohol units is marketed under the trade name BUTVAR B79 of Monsanto USA and provides a good adhesion to paper and properly subbed polyester supports. It should be noted that there is no clear cut transition between a polymer dispersion and a polymer solution in the case of very small polymer particles resulting in the smallest particles of the polymer being dissolved and those slightly larger being in dispersion.
  • 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 binder to organic silver salt weight ratio is preferably in the range of 0.2 to 6. and the thickness of the photo-addressable thermally developable element is preferably in the range of 1 to 50 ⁇ m.
  • binders or mixtures thereof may be used in conjunction with waxes or "heat solvents” also called “thermal solvents” or “thermosolvents” improving the reaction speed of the redox-reaction at elevated temperature.
  • heat solvent in this invention is meant a non-hydrolyzable organic material which is in solid state in the recording layer at temperatures below 50°C but becomes a plasticizer for the recording layer in the heated region and/or liquid solvent for at least one of the redox-reactants, e.g. the reducing agent for the organic silver salt, at a temperature above 60°C.
  • the photo-addressable thermally developable element contains preferably in admixture with the organic silver salts and reducing agents a so-called toning agent known from thermography or photothermography.
  • Suitable toning agents are succinimide and the phthalimides and phthalazinones within the scope of the general formulae described in US-P 4,082,901. Further reference is made to the toning agents described in US-P 3,074,809, 3,446,648 and 3,844,797.
  • Other particularly useful toning agents are the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione as described in GB-P 1,439,478 and US-P 3,951,660.
  • a toner compound particularly suited for use in combination with polyhydroxy benzene reducing agents is 3,4-dihydro-2,4-dioxo-1,3,2H-benzoxazine described in 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 photo-addressable thermally developable element may contain other additives such as free fatty acids, surface-active agents, antistatic agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H, silicone oil, e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY), ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, silica, colloidal silica, fine polymeric particles [e.g. of poly(methylmethacrylate)] and/or optical brightening agents.
  • antistatic agents e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
  • silicone oil e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY)
  • the photothermographic recording 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 used 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 need be to improve the adherence to the thereon coated thermosensitive recording layer.
  • the support may be made of an opacified resin composition, e.g. polyethylene terephthalate opacified by means of pigments and/or micro-voids and/or coated with an opaque pigment-binder layer, and may be called synthetic paper, or paperlike film; information about such supports can be found in EP's 194 106 and 234 563 and US-P's 3,944,699, 4,187,113, 4,780,402 and 5,059,579. Should a transparent base be used, the base may be colourless or coloured, e.g. having a blue colour.
  • One or more backing layers may be provided to control physical properties such as curl or static.
  • the 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 cellulose acetate butyrate, polymethylmethacrylate and polycarbonates, for example 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 polyvinylalcohol being particularly preferred.
  • a protective layer of the photothermographic recording material, used according to the present invention may be crosslinked.
  • Crosslinking can be achieved by using crosslinking agents such as described in WO 95/12495 for protective layers, e.g. tetraalkoxysilanes, polyisocyanates, zirconates, titanates, melamine resins etc., with tetraalkoxysilanes such as tetramethylorthosilicate and tetraethylorthosilicate being preferred.
  • a protective layer used 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 and/or particulate material, e.g. talc particles, optionally protruding from the outermost layer.
  • suitable lubricating materials are surface active agents, liquid lubricants, solid lubricants which do not melt during thermal development of the recording material, solid lubricants which melt (thermomeltable) during thermal development of the recording material or mixtures thereof.
  • the lubricant may be applied with or without a polymeric binder.
  • 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.
  • 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 recording material of the present invention may proceed by any coating technique e.g. such as described in Modern Coating and Drying Technology, edited by Edward D. Cohen and Edgar B. Gutoff, (1992) VCH Publishers Inc. 220 East 23rd Street, Suite 909 New York, NY 10010, U.S.A.
  • Photothermographic materials used according to the present invention, may be exposed with infrared radiation of wavelength > 700 nm 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 appropriate illumination 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 appropriate illumination 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 infrared 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.
  • SENSI 01 The synthesis of SENSI 01 involves the coupling of two intermediates. A and B, which are themselves synthesized from a succession of intermediates in a synthesis ladder.
  • the first step in the synthesis of intermediate A was the synthesis of D.
  • D was prepared according to the following reaction scheme: 10L of butylacetate, 2425g of F en 3038 g of E were added to a flask and the mixture heated to the reflux temperature and then heated for a further 8 hours at the reflux temperature. Upon subsequent cooling to room temperature, the product precipitated out. It was then filtered off and washed with butyl acetate to produce a yield of 74% of intermediate D.
  • Intermediate A was then synthesized according to the following reaction scheme: 294g of intermediate D, 343g of intermediate C and 600mL of sulfolan was added to a flask and heating with stirring on an oil bath for 24 hours at 125°C. The reaction mixture was then cooled to 60°C and 1200mL of acetone added. The resulting suspension was then stirred for 1 hour at room temperature after which it was filtered and thoroughly washed with acetone to produce a 51% yield of intermediate A.
  • the first step in the synthesis of intermediate B was the preparation of intermediate H according to the following synthesis scheme: 2L of ethanol. 5.5g of sodium ethoxide and 759mL diethyl malonate were added to a flask and the mixture cooled to -30°C and the atmosphere above the mixture changed to nitrogen. 758mL of acrolein dissolved in 750mL of ethanol were then added over a period of 60 hours while maintaining the temperature of the reaction mixture between 0 and 5°C. Upon completion of the acrolein addition the temperature was allowed to rise to room temperature and 8g of sodium ethoxide dissolved in 180mL of ethanol was added. After allowing to stand overnight, 19mL of acetic acid was added and the reaction mixture evaporated under reduced pressure. The liquid residue was then distilled under reduced temperature to produce a 26% yield of intermediate H.
  • Intermediate H was then used to prepare intermediate G according to the following synthesis scheme: 162 g of intermediate H, 162mL of ethanol and 0.16g of p-toluenesulfonic acid monohydrate were added to a flask and thoroughly mixed at room temperature. 206mL of intermediate I were then added with stirring and the stirred reaction mixture then heated to 30 to 40°C until the reaction was completed. 0.33mL of a 33% soltion of odium methoxide was then addedand the mixture stirred at 30 to 40°C for a further 15 minutes. Finally the reaction mixture was vacuum distilled to produce a 99% yield of intermediate G.
  • Intermediate G was then used to prepare intermediate B according to the following reaction scheme: 73mL of dimethylformamide in a flask was cooled to 0°C. 59mL of phosphoryl chloride were then added with stirring and the mixture stirred for a further hour at room temperature. 98g of intermediate G were then added with stirring and the mixture stirred for a further 90 minutes at room temperature. 720mL of ethanol and 33mL of deionized water were then added and the mixture stirred for a further 30 minutes at room temperature. 273mL of aniline were then added with stirring and the mixture stirred for a further 30 minutes at room temperature. Finally 3000mL of a 6N solution of hydrochloric acid was added and the mixture stirred for a further 15 minutes at room temperature. The resulting precipitate was filtered off and washed with a warm mixture of methanol and ethyl acetate to produce an 86% yield of intermediate B.
  • SENSI 01 was prepared according to the following reaction scheme: 28g of intermediate B, 180mL of N,N-dimethylacetamide, 11mL of acetic acid anhydride and 37mL of 1-8 diazabicyclo[5.4.0]undec-7ene were added to a flask and mixed at room temperature to produce an orange solution. 39g of intermediate A were then added to the reaction mixture and then stirred for 2.5 hours at room temperature. An extra 9mL of 1-8 diazabicyclo[5,4,0]undec-7ene were then added and the mixture stirred for a further hour at room temperature. Finally 360mL of acetone were added to precipitate the product and filtration, washing and drying produced a 62% yield of SENSI 01.
  • 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 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 INVENTION EXAMPLES 2 to 35 and COMPARATIVE EXAMPLES 1 to 6 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 for 15s with the side of the support not provided with a silver behenate/silver halide emulsion layer with a heated metal block at a temperature of 105°C .
  • the optical densities of the images were measured in transmission with a MacBethTM TR924 densitometer through a visual filter to produce a sensitometric curve for the photographic recording materials from which the exposure required to obtain an optical density of D min + 0.5 was determined.

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Claims (6)

  1. Procédé pour préparer un matériau d'enregistrement photothermographique comprenant un support et un élément photo-adressable et développable par voie thermique, à l'exclusion d'un supersensibilisateur et contenant un sel d'argent organique essentiellement non photosensible, un agent de réduction pour ce dernier en relation de travail thermique avec lui, un halogénure d'argent photosensible sensibilisé par voie spectrale à des longueurs d'ondes > 700 nm avec un colorant et en association catalytique avec ledit sel d'argent organique essentiellement non photosensible, et 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 ledit sel d'argent organique essentiellement non photosensible, ledit halogénure d'argent photosensible sensibilisé par voie spectrale à la lumière infrarouge avec ledit colorant, ledit agent de réduction et ledit liant soluble dans l'eau, ledit liant apte à être dispersé dans l'eau ou ledit 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 ; caractérisé en ce que ledit matériau d'enregistrement photothermographique possède une sensibilité à l'infrarouge qui est inférieure à 20 J/m2 et ledit colorant répond de manière satisfaisante au test suivant : l'exposition requise par un matériau d'enregistrement photothermographique A constitué par un support en polyester possédant une épaisseur de 100 µm muni d'un élément photo-adressable et développable par voie thermique préparé comme décrit dans la description et englobant le colorant et un composé répondant à la formule :
    Figure imgb0038
     représente > 90 % de l'exposition requise par un matériau d'enregistrement photothermographique B préparé comme décrit pour ledit matériau d'enregistrement photothermographique A, avec cette exception que le composé est omis, ladite exposition desdits matériaux A et B étant requise pour obtenir une densité optique dans une partie exposée desdits matériaux supérieure à concurrence d'une valeur de 0,5 à celle régnant dans leur partie non exposée, lorsqu'on les expose à la lumière infrarouge à laquelle ils sont sensibles et lorsqu'on les chauffe avec une source de chaleur à 105°C pendant 15 secondes, en mettant leur support en polyester en contact avec la source de chaleur ; ledit colorant répondant à la formule générale (I) :
    Figure imgb0039
     comprenant un anion si nécessaire pour la compensation des charges, où Z1 et Z2 représentent, indépendamment l'un de l'autre, un atome de soufre, un atome d'oxygène, ou un atome de sélénium ; R1 et R17 représentent, chacun indépendamment l'un de l'autre, un groupe alkyle portant au moins un substituant choisi parmi le groupe comprenant un atome de fluor, un atome de chlore, un atome de brome, un atome d'iode ou encore un groupe aryloxy, un groupe alcoxy, un groupe -(C=O)-R, un groupe -(S=O)-R' ou un groupe -(SO2)-R' où R représente un groupe alcoxy, un groupe aryloxy, un groupe amino ou un groupe amino substitué et R' représente un groupe hydroxyle, un groupe mercapto, un groupe alcoxy, un groupe aryloxy, un groupe amino ou un groupe amino substitué ; R2, R3, R4, R5, R13, R14, R15 et R16 représentent, chacun indépendamment l'un de l'autre, un atome d'hydrogène, un atome de chlore, un atome de brome, un atome de fluor ou encore un groupe céto, un groupe sulfo, un groupe carboxyle, un groupe ester, un groupe sulfonamide, un groupe amide, un groupe dialkylamino, un groupe nitro, un groupe cyano, un groupe alkyle, un groupe alcényle, un groupe hétéroaromatique, un groupe aryle, un groupe alcoxy ou un groupe aryloxy, les groupes que l'on vient de citer pouvant être substitués ; ou bien chacun des radicaux R2 ensemble avec R3, R3 ensemble avec R4, R4 ensemble avec R5, R13 ensemble avec R14, R14 ensemble avec R15 et R15 ensemble avec R16 peuvent constituer de manière indépendante les atomes nécessaires pour compléter un noyau benzénique qui peut être substitué ; R6, R7, R8, R9, R10, R11 et R12 représentent, chacun indépendamment l'un de l'autre, un atome d'hydrogène, un groupe alkyle, un groupe alkyle substitué, un groupe alcoxy, un groupe aryloxy, un groupe thioalkyle, un groupe thioaryle, un atome de chlore, un atome de fluor, un atome de brome, un atome d'iode, un groupe amino disubstitué, les substituants pouvant constituer les atomes nécessaires pour compléter un noyau hétérocyclique contenant 5 atomes nucléaires ou 6 atomes nucléaires, ou bien chacun des radicaux R6 ensemble avec R8, R8 ensemble avec R10, R10 ensemble avec R12, R7 ensemble avec R9 et R9 ensemble avec R11 peuvent constituer de manière indépendante les atomes nécessaires pour compléter un noyau hétérocyclique ou carbocyclique pentagonal ou hexagonal qui peut être substitué ; et chacun des radicaux R1 ensemble avec R6 et R12 ensemble avec R17 peuvent constituer de manière indépendante les atomes nécessaires pour compléter un noyau hétérocyclique pentagonal ou hexagonal qui peut être substitué.
  2. Procédé selon la revendication 1, dans lequel ledit matériau d'enregistrement photothermographique possède une sensibilité à l'infrarouge inférieure à 8 J/m2.
  3. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit colorant répond à la formule :
    Figure imgb0040
  4. Procédé selon l'une quelconque des revendications 1 à 2, dans lequel ledit colorant répond à la formule :
    Figure imgb0041
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit colorant répond à la formule :
    Figure imgb0042
  6. Procédé d'enregistrement photothermographique comprenant les étapes consistant à : (i) exposer en forme d'image un matériau d'enregistrement photothermographique préparé conformément à l'une quelconque des revendications précédentes à un rayonnement infrarouge auquel ledit matériau d'enregistrement photothermographique est sensible ; et (ii) développer par voie thermique ledit matériau d'enregistrement photothermographique exposé en forme d'image.
EP97201905A 1996-07-24 1997-06-21 Procédé de préparation d'un produit d'enregistrement, photothermographique comprenant des colorants sensibilisateurs de l'infra-rouge Expired - Lifetime EP0821272B1 (fr)

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EP97201905A EP0821272B1 (fr) 1996-07-24 1997-06-21 Procédé de préparation d'un produit d'enregistrement, photothermographique comprenant des colorants sensibilisateurs de l'infra-rouge

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* 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
JPH07119952B2 (ja) * 1986-03-11 1995-12-20 富士写真フイルム株式会社 熱現像感光材料
US4873184A (en) * 1988-02-05 1989-10-10 Minnesota Mining And Manufacturing Company Supersensitization of silver halide photothermographic emulsions
EP0486246A1 (fr) * 1990-11-14 1992-05-20 Canon Kabushiki Kaisha Matériel photosensible développable à chaud
CA2087480A1 (fr) * 1992-03-06 1993-09-07 James B. Philip, Jr. Elements photothermographiques
GB9218599D0 (en) * 1992-09-02 1992-10-14 Minnesota Mining & Mfg Silver halide imaging materials
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

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