EP0836116B1 - Empfindlichkeitssteigerndes Aufzeichnungsverfahren für ein lichtempfindliches, wärmeentwickelbares, photographisches Material - Google Patents

Empfindlichkeitssteigerndes Aufzeichnungsverfahren für ein lichtempfindliches, wärmeentwickelbares, photographisches Material Download PDF

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Publication number
EP0836116B1
EP0836116B1 EP97202521A EP97202521A EP0836116B1 EP 0836116 B1 EP0836116 B1 EP 0836116B1 EP 97202521 A EP97202521 A EP 97202521A EP 97202521 A EP97202521 A EP 97202521A EP 0836116 B1 EP0836116 B1 EP 0836116B1
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EP
European Patent Office
Prior art keywords
thermally developable
photographic material
developable photographic
photosensitive
photosensitive thermally
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.)
Expired - Lifetime
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EP97202521A
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English (en)
French (fr)
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EP0836116A1 (de
Inventor
Luc Leenders
Jacobus Bosschaerts
Robert Overmeer
Eddie Daems
Leo Oelbrandt
Hans Strijckers
Thomas Zehetmaier
Jürgen Müller
Friedrich Stumpf
Gerald Halbedl
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority claimed from DE19636235A external-priority patent/DE19636235A1/de
Priority claimed from US08/812,450 external-priority patent/US5804355A/en
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Publication of EP0836116A1 publication Critical patent/EP0836116A1/de
Application granted granted Critical
Publication of EP0836116B1 publication Critical patent/EP0836116B1/de
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49881—Photothermographic systems, e.g. dry silver characterised by the process or the apparatus
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
    • G03D13/00—Processing apparatus or accessories therefor, not covered by groups G11B3/00 - G11B11/00
    • G03D13/002—Heat development apparatus, e.g. Kalvar
    • 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
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser

Definitions

  • the present invention relates to a sensitivity-increasing recording process for photographic materials in which information-wise exposure is carried out during heating.
  • 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 3 become photothermographic if 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”photothermographic 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.
  • DOS 2 248 545 discloses a copying process characterized in that the whole surface of a thermally developable photosensitive silver material is subjected before the complete execution of the exposure to a uniform auxiliary thermal treatment at a temperature, that is within the suitable development temperature range for the photosensitive material, and to thermal development after exposure; and that, in a subclaim, the photosensitive material can also be subjected to auxiliary heating during the exposure thereof.
  • the specification and invention examples give no indication of the efficacity of auxiliary heating during exposure.
  • JP-A-61 196243 discloses a scan type exposure and development installation having as distinctive feature that it has a rotation drum which has a thermal development photosensitive material wound around it and uses the axis center as rotation axis, an exposure head which is positioned opposite the circumference face of the rotation drum and moves in the axis direction of the rotation drum in response to the rotation of the rotation drum, and a heating head which is positioned opposite the circumference face of the rotation drum and moves in the axis direction of the rotation drum in response to the rotation of the rotation drum.
  • the thermal heating head can be a laser heating head and heating development may be carried out while scanning the thermal development photosensitive material and as a result development and exposure may be carried out with the same installation at almost the same time thereby shortening the total treatment time of exposure and development.
  • a recording process comprising the steps of: information-wise exposing to radiation a photosensitive thermally developable photographic material, thereby producing a latent image; and heating the photosensitive thermally developable photographic material, characterized in that the photosensitive thermally developable photographic material is on one and the same holding or guiding means during both the information-wise exposure step and the heating step; the information-wise exposure step is carried out pixelwise during the heating step; the exposure step begins after the start of the heating step; and the duration of the exposure step is less than one tenth of the duration of the heating step.
  • a method of increasing the photosensitivity of a photosensitive thermally developable photographic material characterized in that the photosensitive thermally developable photographic material is on one and the same holding or guiding means during both the information-wise exposure step and the heating step; the information-wise exposure step is carried out pixelwise during said heating step; the exposure step begins after the start of the heating step; and the duration of said exposure step is less than one tenth of the duration of the heating step.
  • the inventors of the present invention surprisingly have found that the preheating of materials resulted in thermally developable photographic materials requiring shorter exposure times than with prior art processes in which unheated materials are exposed to recording radiation. This showed that materials upon heating are more sensitive to recording radiation and enables the apparatus to be simplified.
  • the duration of the exposure step be less than one hundredth of the duration of the heating step.
  • thermal development of the photosensitive thermally developable photographic material is carried out during the heating step, during which a visible image is produced from the latent image resulting from the exposure step.
  • the heating step begins before the start of the exposure step and ends after thermal development to produce a visible image is complete.
  • Photographic materials and photosensitive thermally developable photographic materials may, according to the present invention, be exposed with radiation of wavelength between an X-ray wavelength and a 5 microns wavelength with the image being obtained by pixel-wise exposure with a finely focused light source, such as a CRT light source; a UV, visible or IR wavelength laser, such as a He/Ne-laser or an IR-laser diode, e.g. emitting at 780nm, 830nm or 850nm; or a light emitting diode, for example one emitting at 659nm. Exposure with infra-red light or visible light is preferred, visible light in the wavelength range 600nm to 700nm being particularly preferred. Exposure with an infra-red emitting laser diode is preferred, according to the present invention.
  • a finely focused light source such as a CRT light source
  • a UV, visible or IR wavelength laser such as a He/Ne-laser or an IR-la
  • the photosensitive thermally developable photographic material may be heated during the exposure and the heating subsequent to the exposure by the same heating means. Furthermore, the photosensitive thermally developable photographic material may be heated prior to the exposure, during the exposure and during the heating subsequent to the exposure by the same heating means.
  • a heated drum is a preferred common heating means.
  • any sort of heat source can be used that enables the recording materials to be uniformly heated to the development temperature in a time acceptable for the application concerned e.g. contact heating with for example a heated roller, a heated drum, a thermal head, radiative heating, microwave heating etc.
  • the preferred temperature of the photosensitive thermally developable photographic material during thermal development is between 110°C and 130°C.
  • At least two radiation beams move simultaneously over the photosensitive thermally developable photographic material the first of the radiation beams carrying out the information-wise exposing of the photosensitive thermally developable photographic material and the second of which heats the information-wise exposed photosensitive thermally developable photographic material to a uniform development temperature.
  • the photosensitive thermally developable photographic material preferably contains an infrared sensitizer or a visible light sensitizer and particularly preferably further contains photosensitive silver halide, an organic reducing agent and a binder.
  • the use in the present invention of a photosensitive thermally developable photographic material including a gelatinous silver halide emulsion layer is preferred.
  • the use in the present invention of a photosensitive thermally developable photographic material further containing a substantially light-insensitive organic silver salt with which the photosensitive silver halide in catalytic association and an organic reducing agent for the substantially light-insensitive organic silver salt in thermal working relationship therewith is particularly preferred.
  • the photosensitive thermally developable photographic material may have a layer system in which the ingredients are dispersed in different layers, with the proviso that the image-forming process can take place.
  • the photosensitive silver halide or substantially light-insensitive organic silver salt in the case of photosensitive thermally developable photographic materials containing photosensitive silver halide and an organic reducing agent optionally further containing a substantially light-insensitive organic silver salt, the photosensitive silver halide or substantially light-insensitive organic silver salt, if present, must be in thermal working relationship with the organic reducing agent i.e. during the thermal development process the reducing agent must be present in such a way that it is able to diffuse to the photosensitive silver halide or the substantially light-insensitive organic silver salt particles so that reduction of the silver halide or organic silver salt can take place; and the photosensitive silver halide is in catalytic association with the substantially light-insensitive organic silver salt, if present.
  • the photosensitive silver halide used in the present invention may be employed in a range of 0.1 to 100 mol percent; preferably, from 0.2 to 80 mol percent; particularly preferably from 0.3 to 50 mol percent; especially preferably from 0.5 to 35 mol %; and especially from 1 to 12 mol % of substantially light-insensitive organic silver salt.
  • the silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide etc.
  • the silver halide may be in any form which is photosensitive including, but not limited to, cubic, orthorhombic, tabular, tetrahedral, octagonal etc. and may have epitaxial growth of crystals thereon.
  • the silver halide used in the present invention may be employed without modification. However, it may be chemically sensitized with a chemical sensitizing agent such as a compound containing sulphur, selenium, tellurium etc., or a compound containing gold, platinum, palladium, iron, ruthenium, rhodium or iridium etc., a reducing agent such as a tin halide etc., or a combination thereof.
  • a chemical sensitizing agent such as a compound containing sulphur, selenium, tellurium etc., or a compound containing gold, platinum, palladium, iron, ruthenium, rhodium or iridium etc.
  • a reducing agent such as a tin halide etc.
  • the photosensitive thermally developable photographic material may contain an infra-red sensitizer or a visible light sensitizer.
  • Suitable sensitizers include cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes.
  • Useful cyanine dyes include those having a basic nucleus, for example a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus.
  • Preferred merocyanine dyes include those having not only the above described basic nuclei but also acid nuclei, for example a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus.
  • those having imino groups or carboxyl groups are particularly preferred.
  • Suitable infra-red sensitizers include those disclosed in EP-A's 465 078, 559 101, 616 014 and 635 756, JN's 03-080251, 03-163440, 05-019432, 05-072662 and 06-003763 and US-P's 4,515,888, 4,639,414, 4,713,316, 5,258,282 and 5,441,866.
  • IR-sensitizing dyes according to general formula (I) suitable for use according to the present invention are:
  • the photosensitive thermally developable photographic material further includes a supersensitizer.
  • Preferred supersensitzers are selected from the group of compounds consisting of: mercapto-compounds, disulfide-compounds, stilbene compounds, organoborate compounds and styryl compounds.
  • Suitable supersensitizers for use with infra-red spectral sensitizers are disclosed in EP-A 559 228, EP-A 587 338, US-P 3,877,943, US-P 4,873,184 and unpublished European Patent Application EP 96202107.7.
  • Preferred substantially light-insensitive organic silver salts used in the photosensitive thermally developable photographic material used in the present invention are silver salts of 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.
  • 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 thermosensitive silver image.
  • Silver imidazolates and the substantially light-insensitive inorganic or organic silver salt complexes described in US-P 4,260,677 are also suitable.
  • substantially light-insensitive organic silver salt for the purposes of the present invention also includes mixtures of organic silver salts.
  • the silver halide may be added to the photosensitive thermally developable photographic material in any fashion which places it in catalytic proximity to the substantially light-insensitive organic silver salt.
  • Photosensitive silver halide and 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 they may be blended for a long period of time prior to use.
  • a particularly preferred mode of preparing the emulsion of organic silver salt and photosensitive silver halide for coating of the photosensitive thermally developable photographic material from solvent media, according to the present invention is that disclosed in US-P 3,839,049, but other methods such as those described in Research Disclosure, June 1978, item 17029 and US-P 3,700,458 may also be used.
  • Suitable organic reducing agents for use in the photosensitive thermally developable photographic material used in the present invention are organic compounds containing at least one active hydrogen atom linked to 0, N or C, such as is the case with, mono-, bis-, tris- or tetrakis-phenols; mono- or bis-naphthols; di- or polyhydroxy-naphthalenes; di- or polyhydroxybenzenes; hydroxymonoethers such as alkoxynaphthols, e.g. 4-methoxy-1-naphthol described in US-P 3,094,41; pyrazolidin-3-one type reducing agents, e.g.
  • PHENIDONETM pyrazolin-5-ones; indan-1,3-dione derivatives; hydroxytetrone acids; hydroxytetronimides; 3-pyrazolines; pyrazolones; reducing saccharides; aminophenols e.g. METOLTM; p-phenylenediamines, hydroxylamine derivatives such as for example described in US-P 4,082,901; reductones e.g. ascorbic acids; hydroxamic acids; hydrazine derivatives; amidoximes; n-hydroxyureas; and the like, see also US-P 3,074,809, 3,080,254, 3,094,417 and 3,887,378.
  • Particularly preferred catechol-type reducing agents are described in EP-A 692 733 and EP-A 599 369.
  • Polyphenols such as the bisphenols used in the 3M Dry SilverTM materials, sulfonamide phenols such as used in the Kodak DacomaticTM materials, and naphthols are particularly preferred for photosensitive thermally developable photographic materials on the basis of silver halide/organic silver salt/reducing agent.
  • reducing agents being considered as primary or main 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 sulfonamidophenols as described in the periodical Research Disclosure, February 1979, item 17842, in US-P 4,360,581 and 4,782,004, and in EP-A 423 891.
  • auxiliary reducing agents that may be used in conjunction with the above mentioned primary reducing agents are hydrazides such as disclosed in EP-A 762 196, 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; trityl hydrazides and formyl-phenyl-hydrazides with diverse auxiliary reducing agents such as disclosed in US-P 5,545,505, US-P 5.545.507 and US-P 5,558,983; acrylonitrile compounds as disclosed in US-P 5,545,515 and US-P 5,635,339; and organic reducing metal salts, e.g. stannous stearate described in US-P 3,460,946 and 3,547,648.
  • hydrazides such as disclosed in EP-A 762 196, sulfonyl hydrazi
  • the binder for the photosensitive thermally developable photographic material used in the present invention may be coatable from a solvent or aqueous dispersion and must themselves be film-forming or must be used in association with a film-forming binder.
  • Film-forming binders coatable from a solvent dispersion and usable in the present invention may be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously: e.g. polyurethanes, polyesters, polyamides, polycarbonates and polymers derived from ⁇ , ⁇ -ethylenically unsaturated compounds, polyvinyl acetals preferably polyvinylbutyral, and homopolymers and copolymers produced using monomers selected from the group consisting of: acrylonitrile, acrylamides, methacrylamides. methacrylates, acrylates, methacrylic acids, acrylic acids, vinyl esters, styrenes and alkenes; or mixtures thereof.
  • the organic silver salt can be dispersed homogeneously: e.g. polyurethanes, polyesters, polyamides, polycarbonates and polymers derived from ⁇ , ⁇ -ethylenically unsatur
  • the film-forming binder coatable from an aqueous dispersion used in the present invention may be all kinds of transparent or translucent water-dispersible or water soluble natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously for example proteins, such as gelatin and gelatin derivatives ; cellulose derivatives; polysaccharides; galactomannan; polyvinyl alcohol; polyvinylpyrrolidone; polyurethanes; polyesters; polyamides; polycarbonates; polymers derived from ⁇ , ⁇ -ethylenically unsaturated compounds, for example polyvinyl acetals, preferably polyvinylbutyral, and homopolymers and copolymers produced using monomers selected from the group consisting of: acrylonitrile, acrylamides, methacrylamides. methacrylates, acrylates, methacrylic acids, acrylic acids, vinyl esters, styrenes and alkenes; and latexe
  • binders or mixtures thereof may be used in conjunction with waxes or "heat solvents” also called “thermal solvents” or “thermosolvents” improving the reaction speed of the redox-reaction at elevated temperature.
  • the photosensitive thermally developable photographic material used according to the present invention may also contain at least one polycarboxylic acid and/or anhydride thereof in a molar percentage of at least 20 with respect to all the organic silver salt(s) present and in thermal working relationship therewith.
  • Preferred aromatic polycarboxylic acids are ortho-phthalic acid and 3-nitro-phthalic acid, tetrachlorophthalic acid, mellitic acid, pyromellitic acid and trimellitic acid and the anhydrides thereof.
  • the photosensitive thermally developable photographic material preferably contains 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, phthalazine 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, 3,446,648 and 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, US-P 3,951,660 and US-P 5,599,647.
  • the photosensitive thermally developable photographic materials used in the present invention may also contain antihalation or acutance dyes which absorb light which has passed through the photosensitive thermally developable photographic material, thereby preventing its reflection. Such dyes may be incorporated into the photosensitive thermally developable photographic material or in any other layer of the photographic material of the present invention.
  • the photosensitive thermally developable photographic material used in the present invention may also contain additives such as free fatty acids, surface-active agents, silicone oil, e.g. BAYSILONETM ⁇ l A (from BAYER AG, GERMANY) ; ultraviolet light absorbing compounds; silica; colloidal silica; fine polymeric particles, e.g. of poly(methylmethacrylate); and/or optical brightening agents.
  • silicone oil e.g. BAYSILONETM ⁇ l A (from BAYER AG, GERMANY)
  • ultraviolet light absorbing compounds e.g. BAYSILONETM ⁇ l A (from BAYER AG, GERMANY)
  • silica colloidal silica
  • fine polymeric particles e.g. of poly(methylmethacrylate)
  • optical brightening agents e.g., optical brightening agents.
  • the support for the photosensitive thermally developable photographic material used in 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, polyethene coated paper or transparent resin material, 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 thin flexible carrier made e.g. from paper, polyethene coated paper or transparent resin material, e.g. made of a cellulose ester, e.g. cellulose triacetate, corona and flame treated polypropylene, polystyrene, polymethacrylic acid ester, polycarbonate or
  • 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.
  • One or more backing layers may be provided to control physical properties such as curl or static.
  • the outermost layer of the side of the photosensitive thermally developable photographic material which is photosensitive may be a protective layer to avoid local deformation of the photosensitive thermally developable photographic material and to improve resistance against abrasion.
  • the protective layer preferably comprises a binder, which may be hydrophobic (solvent soluble) or hydrophilic (water soluble) e.g. as described in EP-A 614 769.
  • Hydrophilic binders are, however, preferred for the protective layer, as coating can be performed from an aqueous composition and mixing of the hydrophilic protective layer with the immediate underlayer can be avoided by using a hydrophobic binder in the immediate underlayer.
  • a protective layer used in the present invention may also contain at least one solid lubricant having a melting point below 150°C and at least one liquid lubricant at least one of these lubricants being a phosphoric acid derivative; and additional 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 contain 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 therein e.g. colloidal particles such as colloidal silica.
  • the photosensitive thermally developable photographic materials used in the present invention may further include an antistatic layer.
  • Suitable antistatic layers 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.
  • Particularly preferred antistatic layers are those based on polythiophene as disclosed in EP-A 628 560, US-P 5,354,613, US-P 5,372,924, US-P 5,370,981 and US-P 5,391,472.
  • any layer of the photosensitive thermally developable photographic materials used in the present invention may proceed by any thin-film coating technique known in the art.
  • any thin-film coating technique known in the art.
  • slide hopper coating is preferred, but other coating techniques such as dip coating and air knife coating may also be used. Details about such coating techniques can be found in "Modern Coating and Drying Technology" by Edward D. Cohen and Edgar B. Gutoff, published by VCH Publishers, Inc. 220 East 23rd Street, Suite 909 New York, NY 10010.
  • the photosensitive thermally developable photographic materials used in 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.
  • a polyethylene terephthalate (PET) foil pigmented with a blue pigment was first coated on both sides with a subbing layer consisting of a terpolymer latex of vinylidene chloride-methyl acrylate-itaconic acid (88/10/2) in admixture with colloidal silica (surface area 100m 2 /g). After stretching the foil in the transverse direction the foil had a thickness of 175 ⁇ m with coverages of the terpolymer and of the silica in the subbing layers of 170mg/m 2 and 40mg/m 2 respectively on each side of the PET-foil.
  • PET polyethylene terephthalate
  • the antihalation/antistatic layer was prepared by first adsorbing antihalation dye D01 onto the polymethyl methacrylate particles of LATEX01 by adding 55mg of D01 dissolved in ethyl acetate/g polymethyl methacrylate and then evaporating off the ethyl acetate.
  • a silver halide emulsion consisting of 3.11% by weight of silver halide particles consisting of 97mol% silver bromide and 3mol% silver iodide with a weight average particle size of 50nm, 0.47% by weight of GEL as dispersing agent in deionized water was prepared using conventional silver halide preparation techniques such as described, for example, in T.H. James, "The Theory of the Photographic Process", Fourth Edition, Macmillan Publishing Co. Inc., New York (1977), Chapter 3, pages 88-104.
  • the silver behenate/silver halide emulsion was prepared by adding a solution of 6.8kg of behenic acid in 67L of 2-propanol at 65°C to a 400L vessel heated to maintain the temperature of the contents at 65°C, converting 96% of the behenic acid to sodium behenate by adding with stirring 76.8L of 0.25M sodium hydroxide in deionized water, then adding with stirring 10.5kg of the above-described silver halide emulsion at 40°C and finally adding with stirring 48L of a 0.4M solution of silver nitrate in deionized water. Upon completion of the addition of silver nitrate the contents of the vessel were allowed to cool and the precipitate filtered off, washed, slurried with water, filtered again and finally dried at 40°C for 72 hours.
  • the emulsion layer coating composition for the photosensitive thermally developable photographic material was prepared by adding the following solutions or liquids to 40.86g of the above-mentioned silver behenate/silver halide emulsion in the following sequence with stirring: 10.87g of 2-butanone, 0.75g of a 9% solution of TMABP in methanol followed by 2 hours stirring, 1.3g of 2-butanone, 0.2g of a 11% solution of calcium bromide in methanol and 1.3g of 2-butanone followed by 30 minutes stirring, a solution consisting of 0.21g of LOWINOXTM 22IB46, 0.5g of TMPS and 9.24g of 2-butanone followed by 10 minutes stirring, 1.84g of a 0.11% methanol solution of SENSI followed by 30 minutes stirring and finally 4.35g of ButvarTM B76 were added followed by 45 minutes of stirring and then 4.79g of 2-butanone.
  • the PET-support subbed and coated with an antihalation/antistatic layer as described above was then doctor blade-coated at a blade setting of 150 ⁇ m on the side of the support not coated with a backside layer with the coating composition to a wet layer thickness of 80 ⁇ m followed by drying for 5 minutes at 80°C on an aluminium plate in a drying cupboard.
  • a protective layer coating composition for the photosensitive thermally developable photographic material was prepared by dissolving 4.08g of CAB and 0.16g of PMMA in 36.3g of 2-butanone and 4.16g of methanol adding the following solids or solution with stirring in the following sequence: 0.5g of phthalazine, 0.2g of 4-methylphthalic acid, 0.1g of tetrachlorophthalic acid, 0.2g of tetrachlorophthalic acid anhydride and a solution consisting of 2.55g of LOWINOXTM 22IB46 and 5.95g 2-butanone.
  • the emulsion layer was then doctor blade-coated at a blade setting of 100 ⁇ m with the protective layer coating composition to a wet layer thickness of 57 ⁇ m, which after drying for 8 minutes at 80°C on an aluminium plate in a drying cupboard produced a layer with the following composition: CAB 4.08g/m 2 PMMA 0.16g/m 2 Phthalazine 0.50g/m 2 4-methylphthalic acid 0.20g/m 2 tetrachlorophthalic acid 0.10g/m 2 tetrachlorophthalic acid anhydride 0.20g/m 2 LOWINOXTM 22IB46 2.55g/m 2
  • Sheets of the photosensitive thermally developable photographic material were information-wise exposed and thermally developed in an apparatus in which information-wise exposure and thermal development took place on the same heatable drum 198 mm in diameter and the photosensitive thermally developable photographic material was transported at a speed of 20.73 mm/s with its antistatic/antihalation-layer in contact with the drum i.e. with the protective layer for the silver behenate/silver halide emulsion layer outermost.
  • the optical densities of the resulting images were measured in transmission with a MacBethTM TR924 densitometer through a visible filter to produce a sensitometric curve for the photosensitive thermally developable photographic materials from which the maximum and minimum optical densities, D max and D min , and the relative photosensitivities for D min + 1.0 determined.
  • DRYVIEWTM photosensitive thermally developable photographic material from IMATION was used instead of the photosensitive thermally developable photographic material of COMPARATIVE EXAMPLE 1 and INVENTION EXAMPLES 1 to 4.
  • the DRYVIEWTM material is based on a conventional silver halide/silver behenate/reducing agent concept and is spectrally sensitized to infra-red radiation. Information-wise exposure and thermal processing were carried out using the apparatus used for COMPARATIVE EXAMPLE 1 and INVENTION EXAMPLES 1 to 4 with thermal development carried out at 123.9°C for 17.5 s instead of for 15 s at 121°C.

Claims (10)

  1. Ein durch die nachstehenden Schritte gekennzeichnetes Aufzeichnungsverfahren :
    informationsmäßige Strahlungsbelichtung von einem strahlungsempfindlichen wärmeentwickelbaren fotografischen Material, wodurch ein latentes Bild erhalten wird, und
    Erhitzung des strahlungsempfindlichen wärmeentwickelbaren fotografischen Materials,
    dadurch gekennzeichnet, daß das strahlungsempfindliche wärmeentwickelbare fotografische Material sowohl während der informationsmäßigen Belichtungsstufe als der Erhitzungsstufe auf ein und demselben Halte- oder Führungsmittel vorliegt, die informationsmäßige Belichtungsstufe pixelweise während der Erhitzungsstufe erfolgt, die Belichtungsstufe nach dem Beginn der Erhitzungsstufe anfängt und die Dauer der Belichtungsstufe weniger als ein Zehntel der Dauer der Erhitzungsstufe beträgt.
  2. Aufzeichnungsverfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Wärmeentwicklung des strahlungsempfindlichen wärmeentwickelbaren fotografischen Materials während der Erhitzungsstufe vorgenommen wird.
  3. Aufzeichnungsverfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Dauer der Belichtungsstufe unter einem Hundertstel der Dauer der Erhitzungsstufe eingestellt wird.
  4. Aufzeichnungsverfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das strahlungsempfindliche wärmeentwickelbare fotografische Material einen Infrarotsensibilisator enthält.
  5. Aufzeichnungsverfahren nach Anspruch 4, dadurch gekennzeichnet, daß der Infrarotsensibilisator der allgemeinen Formel (I) entspricht :
    Figure 00340001
    mit nötigenfalls einem Anion für den Ladungsausgleich,
    in der bedeuten :
    Z1 und Z2 unabhängig voneinander S, O oder Se,
    R1 und R13 unabhängig voneinander eine Alkylengruppe,
    X1 und X2 unabhängig voneinander eine -(C=O)-R18-, -(SO2)-R19-oder -(S=O)-R20-Gruppe, wobei R18, R19 und R20 unabhängig voneinander eine Alkoxy-, Aryloxy-, Amino- oder substituierte Aminogruppe bedeuten,
    R2, R3, R4, R5, R14, R15, R16 und R17 unabhängig voneinander ein Wasserstoffatom, ein Chloratom, ein Bromatom, ein Fluoratom, ein Iodatom oder eine gegebenenfalls substituierte Keto-, Sulfo-, Carboxyl-, Ester-, Sulfonamido-, Amido-, Dialkylamino-, Nitro-, Cyan-, Alkyl-, Alkenyl-, eine heteroaromatische, Aryl-, Alkoxy- oder Aryloxygruppe, oder wobei R2 zusammen mit R3, R3 zusammen mit R4, R4 zusammen mit R5, R14 zusammen mit R15, R15 zusammen mit R16 und R16 zusammen mit R17 unabhängig voneinander die zum Vervollständigen eines gegebenenfalls substituierten Benzolringes benötigten Atome bedeuten können,
    R6, R7, R8, R9, R10, R11 und R12 unabhängig voneinander ein Wasserstoffatom, ein Chloratom, ein Bromatom, ein Fluoratom, ein Iodatom, eine Alkylgruppe, eine substituierte Alkylgruppe, eine Alkoxygruppe, eine Aryloxygruppe, eine Thioalkylgruppe, eine disubstituierte Aminogruppe, wobei die Substituenten die zum Vervollständigen eines 5-atomigen oder 6-atomigen heterocyclischen Ringes benötigten Atome bedeuten können, R6 zusammen mit R8, R8 zusammen mit R10, R10 zusammen mit R12, R7 zusammen mit R9 und R9 zusammen mit R11 unabhängig voneinander die zum Vervollständigen eines gegebenenfalls substituierten 5-atomigen oder 6-atomigen carbocyclischen oder heterocyclischen Ringes benötigten Atome bedeuten können, und R1 zusammen mit R6 und R13 zusammen mit R12 unabhängig voneinander die zum Vervollständigen eines gegebenenfalls substituierten 5-atomigen oder 6-atomigen heterocyclischen Ringes benötigten Atome bedeuten können.
  6. Aufzeichnungsverfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das strahlungsempfindliche wärmeentwickelbare fotografische Material einen Sensibilisator für sichtbares Licht enthält.
  7. Aufzeichnungsverfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das strahlungsempfindliche wärmeentwickelbare fotografische Material weiterhin strahlungsempfindliches Silberhalogenid, ein organisches Reduktionsmittel und ein Bindemittel enthält.
  8. Aufzeichnungsverfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das strahlungsempfindliche wärmeentwickelbare fotografische Material weiterhin ein wesentlich lichtunempfindliches organisches Silbersalz enthält.
  9. Aufzeichnungsverfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß zumindest zwei Strahlenbündel gleichzeitig das strahlungsempfindliche wärmeentwickelbare fotografische Material abtasten, wobei das erste Strahlenbündel das strahlungsempfindliche wärmeentwickelbare fotografische Material informationsmäßig belichtet und das zweite Strahlenbündel das informationsmäßig belichtete strahlungsempfindliche wärmeentwickelbare fotografische Material auf eine gleichmäßige Entwicklungstemperatur erhitzt.
  10. Verfahren zur Steigerung der Fotoempfindlichkeit eines strahlungsempfindlichen wärmeentwickelbaren fotografischen Materials, dadurch gekennzeichnet, daß das strahlungsempfindliche wärmeentwickelbare fotografische Material sowohl während der informationsmäßigen Belichtungsstufe als der Erhitzungsstufe auf ein und demselben Halte- oder Führungsmittel vorliegt, die informationsmäßige Belichtungsstufe pixelweise während der Erhitzungsstufe erfolgt, die Belichtungsstufe nach dem Beginn der Erhitzungsstufe anfängt und die Dauer der Belichtungsstufe weniger als ein Zehntel der Dauer der Erhitzungsstufe beträgt.
EP97202521A 1996-09-06 1997-08-14 Empfindlichkeitssteigerndes Aufzeichnungsverfahren für ein lichtempfindliches, wärmeentwickelbares, photographisches Material Expired - Lifetime EP0836116B1 (de)

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US812450 1985-12-23
DE19636235 1996-09-06
DE19636235A DE19636235A1 (de) 1996-09-06 1996-09-06 Verfahren und Vorrichtung zum Aufzeichnen von Informationen auf thermisch entwickelbarem fotografischen Material
US08/812,450 US5804355A (en) 1996-03-14 1997-03-06 Producing a contone image by sequentially exposing a thermo-sensitive imaging material by means of a set of radiation beams

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DE19747302A1 (de) 1997-10-25 1999-05-06 Agfa Gevaert Ag Vorrichtung zum Beschreiben von thermografischem Material
US20020099119A1 (en) * 1999-05-27 2002-07-25 Bradley D. Craig Water-borne ceramer compositions and antistatic abrasion resistant ceramers made therefrom

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JPS61196243A (ja) * 1985-02-26 1986-08-30 Fuji Photo Film Co Ltd 走査型露光現像装置

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JPS5292608A (en) * 1976-01-26 1977-08-04 Canon Kk Electrostatic printing master
JPS5681843A (en) * 1979-12-07 1981-07-04 Asahi Chem Ind Co Ltd Image formation and its device
JPS6214650A (ja) * 1985-07-12 1987-01-23 Fuji Photo Film Co Ltd 画像記録装置
US5038166A (en) * 1987-12-29 1991-08-06 Canon Kabushiki Kaisha Optical image recording apparatus
DE68926587T2 (de) * 1988-03-11 1996-10-17 Canon Kk Photoempfindliches Material und Verfahren zur Bildherstellung
EP0582144B1 (de) * 1992-08-03 1997-04-23 Minnesota Mining And Manufacturing Company Laseradressierbares wärmeempfindliches Aufzeichnungsmaterial
US5541054B1 (en) * 1995-04-20 1998-11-17 Imation Corp Spectral sensitizing dyes for photothermographic elements

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