EP0709730B1 - Method of processing a silver halide photographic material - Google Patents

Method of processing a silver halide photographic material Download PDF

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Publication number
EP0709730B1
EP0709730B1 EP94203085A EP94203085A EP0709730B1 EP 0709730 B1 EP0709730 B1 EP 0709730B1 EP 94203085 A EP94203085 A EP 94203085A EP 94203085 A EP94203085 A EP 94203085A EP 0709730 B1 EP0709730 B1 EP 0709730B1
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EP
European Patent Office
Prior art keywords
silver
silver halide
amount
processing
gelatin
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP94203085A
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German (de)
English (en)
French (fr)
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EP0709730A1 (en
Inventor
Peter Willems
Ann Verbeeck
Freddy Hendrickx
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to DE69422625T priority Critical patent/DE69422625T2/de
Priority to EP94203085A priority patent/EP0709730B1/en
Priority to JP7297359A priority patent/JPH09138486A/ja
Publication of EP0709730A1 publication Critical patent/EP0709730A1/en
Priority to US08/752,521 priority patent/US5795704A/en
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Publication of EP0709730B1 publication Critical patent/EP0709730B1/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G03C5/383—Developing-fixing, i.e. mono-baths
    • 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
    • G03C1/30—Hardeners
    • 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
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
    • 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
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • 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
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with 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
    • G03C1/005—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
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03511—Bromide content
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03517—Chloride content
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03541—Cubic grains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/0357—Monodisperse emulsion
    • 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
    • G03C2005/168—X-ray material or process
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/42—Mixtures in general

Definitions

  • the present invention relates to photographic materials comprising silver halide emulsion grains rich in chloride and the processing thereof.
  • the commonly used silver halides e.g. in medical X-ray applications, micrography etc., are silver bromoiodide grains, wherein said bromoiodide grains are especially preferred for attainable speed.
  • a normal processing cycle is characterised by the following steps: developing at 26°C to 42°C and fixing, rinsing and drying.
  • the developer is normally composed of three concentrates that should be diluted in the right order: alkaline solution A contains hydroquinone, acidic solution B contains 1-phenyl-3-pyrazolidinone and acidic solution C contains glutaric dialdehyd as a hardening agent.
  • alkaline solution A contains hydroquinone
  • acidic solution B contains 1-phenyl-3-pyrazolidinone
  • acidic solution C contains glutaric dialdehyd as a hardening agent.
  • the need for the complex three-part packaged developer concentrates has been dictated by the fact that glutaric aldehyd tends to react with 1-phenyl-3-pyrazolidinone, that this pyrazolidinone is unstable in alkaline medium and that glutaric aldehyd tends to polymerise in alkaline medium.
  • the fixer is composed of 2 concentrated solutions: solution A contains the commonly used highly active ammonium thiosulphate as a fixing agent and solution B aluminum sulphate as a hardening agent. Hardening agents are necessary to lead the film through the processor without damages, to reduce the amount of water absorption and, as a consequence, the drying time and further the total processing time.
  • tabular grains are preferred in rapid processing applications with one-part package chemistry.
  • the main photographic advantages of tabular grains compared to, e.g., cubic grains (crystals) are a high covering power at high forehardening levels, a high developability and higher sharpness (low cross-over) especially in double side coated spectrally sensitized materials.
  • amounts of silver used are high (from 5-15 g of silver, corresponding with equivalent amounts of silver nitrate from 8-24 g), although in that case there is no problem of getting the desired blackening in the high densities, opposite to materials coated from lower amounts of silver.
  • a first object of the present invention is to provide a method of processing a silver halide photographic material, said silver halide substantially consisting of silver chloride, which has a satisfactory photographic performance, i.e., that even with comparable coating amounts of silver as for tabular silver bromoiodide emulsions, being favourable with respect to ecology, no loss in sensitivity and covering power occurs, and that after processing an image is obtained with a black image tone, showing no pressure marks.
  • a second object of the invention is to provide a method having an increased efficiency and capacity in the processing, i.a., a shortened developing, fixing and drying time, even in hardener-free processing chemistry as for an X-ray photographic material, wherein more customer-friendly chemicals in lower amounts are consumed thus requiring less regeneration if compared with hardener containing processing chemistry.
  • the present invention also provides a method of processing an exposed high-speed fore-hardened photographic material comprising the steps of development, fixing, rinsing and drying characterised in that the total processing time is less than 45 seconds and in that the processing is preferably substantially free from hardening agents.
  • the silver halide grains rich in chloride used in the method according to this invention provide satisfactory photographic performance, especially high sensitivity, even in rapid processing.
  • a processing sequence free from hardening agents is made possible by reducing the coated amount of gelatin and simultaneously increasing the amount of hardener in the thinner emulsion layer.
  • Lower coating amounts of gelatin are, e.g., 2.5 g/m 2 , but said amounts may be variable as they depend on the total amount of silver halide coated. As a consequence the amount of water being absorbed after rinsing the film with water is reduced, offering the possibility to the film material to be completely dry within the proposed total processing time.
  • the emulsions used in the method according to the present invention are emulsions containing silver chloride crystals or silver chlorobromide crystals containing up to 25 mole% of bromide-ions.
  • gelatino silver chloride or chlorobromide emulsions used in the method according to the present invention conventional lime treated or acid treated gelatin can be used.
  • the preparation of such gelatin types has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 and next pages.
  • the gelatin can also be an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, N° 16, page 30 (1966).
  • the gelatin concentration is kept from about 0.05 % to 5.0 % by weight in the dispersion medium. Additional gelatin can be added in a later stage of the emulsion preparation, e.g. after washing, to establish optimal coating conditions and/or to establish the required thickness of the coated emulsion layer.
  • the gelatin to silver halide ratio then ranges from 0.3 to 0.6.
  • the total silver halide precipitated preferably 0.5 % to 5.0 % is added during said nucleation step which consists preferably of an approximately equimolecular addition of silver and halide salts.
  • the rest of the silver and halide salts is added during one or more consecutive double jet growth steps.
  • the different steps of the precipitation can be alternated by physical ripening steps.
  • an increasing flow rate of silver and halide solutions is preferably established, e.g. a linearly increasing flow rate.
  • the flow rate at the end is about 3 to 10, preferably 3 to 5 times greater then at the start of the growth step.
  • These flow rates can be monitored by e.g. magnetic valves.
  • a crystal growth accelerator can be added, as, e.g., methionin and 1,8-dihydroxy-3,6-dithiooctane.
  • an amount of not more than 25 mole% of bromide ions, and more preferably not more than 10 mole%, may be built into the silver halide crystals, whether it is built in homogeneously or, as is the case for core-shell emulsions, heterogeneously.
  • the pAg is maintained between 140 and 110 mV (measured versus a silver/silver chloride electrode as a reference electrode) during the nucleation step and preferably between 125 and 80 mV during the growth phase and pH is maintained between 5.2 and 5.8, preferably between 5.6 and 5.8.
  • silver halide emulsion grains rich in chloride show a cubic morphology with (100) crystal faces offering better developing characteristics than other crystallographic forms, as, e.g., octahedral, rhombic dodecahedral or tabular silver chloride crystals, which require the use of so-called "growth modifiers” or "crystal habit modifiers".
  • the silver halide grains used in the method in accordance with the present invention preferably have an average grain size from 0.3 to 1.0 ⁇ m and a homogeneous crystal size distribution wherein the ratio between the standard deviation from the average crystal size and said average crystal size is not more than 0.20.
  • cubic crystals having a crystal size smaller than 0.3 ⁇ m are giving a higher covering power, such crystals are useless as the required sensitivity cannot be reached and as image tone is turning from black to reddish brown again.
  • a wash technique in order to remove the excess of soluble salts is applied at a pH value which can vary during washing but remains comprised between 3.7 and 3.3 making use of a flocculating agent like polystyrene sulphonic acid.
  • a flocculating agent like polystyrene sulphonic acid.
  • the emulsion is washed by diafiltration by means of a semipermeable membrane, also called ultrafiltration, so that it is not necessary to use polymeric flocculating agents that may disturb the coating composition stability before, during or after the coating procedure.
  • Such procedures are disclosed, e.g., in Research Disclosure Vol. 102, Oct. 1972, Item 10208, Research Disclosure Vol. 131, March, Item 13122 and US-P 4,334,012.
  • pH and pAg are the same as at the end of the preceding precipitation without any adjustment stage.
  • the emulsions present in the radiographic materials used in the method according to the present invention can be chemically sensitized as described, e.g., in "Chimie et Physique Photographique” by P. Glafkides, in “Photographic Emulsion Chemistry” by G.F. Duffin, in “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in “Die Grundlagen der Photographischen Sawe mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur, e.g., thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines and/or the corresponding selenium and/or tellurium compounds.
  • sulphur e.g., thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines and/or the corresponding selenium and/or tellurium compounds.
  • Unstable compounds slowly releasing sulphur, selenium or tellurium can be used.
  • Sulphur compounds of the class which have sulphur covalently bound derived from an ion such as a mercaptide or xanthate or coordinately bound sulphur from a thioether are especially preferred.
  • the emulsions can be sensitized also by means of gold-sulphur, gold-selenium and gold-tellurium ripeners or by means of reductors, e.g., tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine sulphinic acids etc.
  • reductors e.g., tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine sulphinic acids etc.
  • the cubic crystals used in the method according to the present invention are spectrally sensitized; they are preferably sensitized by at least one spectral sensitizer corresponding to the general formula (I) and at least one spectral sensitizer corresponding to the general formula (II) wherein
  • said spectrally sensitised cubic crystals are sensitised by at least one spectral sensitiser corresponding to the general formula (I) and at least one spectral sensitiser corresponding to the general formula (II) in a weight ratio in the range from 3:1 to 10:1 and in amounts for each of them in the range from 1 to 10 mg per gram of silver chloride or silver bromochloride. It has been found that such combination is in the interest of speed and decolourising properties.
  • Silver halide crystals used in the method according to this invention but prepared according to the method described in EP-A 0 682 287 are not excluded.
  • the silver halide emulsion layer(s) or the non-light-sensitive layers of the material used in the method in accordance with the present invention may comprise compounds preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of the photographic elements or during the photographic treatment thereof.
  • Many known compounds can be added as fog-inhibiting agent or stabilizer to the silver halide emulsion at any stage of the emulsion preparation.
  • Suitable examples are, e.g., the heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotriazoles, mercaptotetrazoles, in particular 1-phenyl-5-mercapto-tetrazole, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione, oxazoline-thione, triazaindenes, tetrazaindenes and pentazaindenes, especially those described by Birr in Z.
  • the heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimid
  • the ratio of gelatin to silver halide, expressed as the equivalent amount of silver nitrate, in the silver halide emulsion layers of the photographic material used in the method according to the present invention is comprised between 0.3 and 0.6, preferably from 0.4 to 0.6.
  • Amounts of coated silver, expressed as the equivalent amount of silver nitrate, are in the range from 2.5 to 7.4 g/m 2 .
  • the gelatin binder of the photographic elements used in the method according to the present invention can be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type, e.g., 1,3-vinylsulphonyl-2-propanol, di-(vinyl-sulphonyl)-methane and- ethylene di-(vinyl-sulphone), aldehydes, e.g., formaldehyde, glyoxal, and glutaric aldehyde, N-methylol compounds, e.g., dimethylolurea and methyloldimethylhydantoin, dioxan derivatives, e.g., 2,3-dihydroxy-dioxan, active vinyl compounds, e.g., 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compounds, e.g.,
  • the binder can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US-P 4,063,952 and with the onium compounds as disclosed in EP-A 0 408 143.
  • fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US-P 4,063,952 and with the onium compounds as disclosed in EP-A 0 408 143.
  • Hardening is to such an extent that when the photographic material is immersed in demineralized water of 25°C less than 4 g, and more preferably at most 3 g of water is absorbed per gram of gelatin in 3 minutes.
  • the photographic element used in the method according to the present invention may further comprise various kinds of surface-active agents in the photographic emulsion layer or in at least one other hydrophilic colloid layer.
  • Suitable surface-active agents include non-ionic agents such as saponins, alkylene oxides, e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids
  • Such surface-active agents can be used for various purposes, e.g., as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics, e.g., higher contrast, sensitization, and development acceleration.
  • Preferred surface-active coating agents are compounds containing perfluorinated alkyl groups.
  • Development acceleration can be accomplished by incorporating in the emulsion layer or adjacent layers various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US Patents 3,038,805 - 4,038,075 and 4,292,400.
  • the photographic elements may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents and plasticizers.
  • the photographic material used in the method according to the present invention is not limited to be a material for medical X-rays, but it can also be an industrial X-ray material for non-destructive purposes or for micrography etc.
  • the photographic element may contain one single emulsion layer, as it is the case for many applications, or it can be built up by two or even more emulsion layers.
  • a material with a single or a duplitized emulsion layer coated on one or both sides of the support may contain silver halide emulsions according to the invention.
  • duplitized emulsions differing in photographic speed by at least 0.15 log E a gain in cross-over exposure in double side coated materials can be obtained.
  • the photographic material may contain several light-insensitive layers, e.g. a protective layer, one or more backing layers, one or more subbing layers, one or more intermediate layers e.g. filter layers and even an afterlayer containing e.g. the hardening agent(s), the antistatic agent(s), filter dyes for safety-light purposes etc.
  • the material used in the method according to this invention is a duplitized material having on both sides of the film support emulsion layers, wherein both emulsion layers are overcoated with an antistress outermost layer.
  • the support of the photographic material used in the method according to the present invention may be a transparent resin, preferably a blue coloured polyester support like polyethylene terephtalate.
  • the thickness of such organic resin film is preferably about 175 ⁇ m.
  • the support is provided with a substrate layer at both sides to have good adhesion properties between the emulsion layer said support.
  • the photographic material used in the method according to the present invention can be image-wise exposed by any convenient radiation source in accordance with its specific application.
  • the energy expressed in kV, depends on the specific application.
  • a metal filter usually a lead filter, can be used in combination with the photographic film.
  • an automatically operating apparatus is used provided with a system for automatic replenishment of the processing solutions.
  • Film materials used in the method in accordance with this invention may be processed in developer solutions of different compositions as, e.g., hydroquinone-1-phenyl-3-pyrazolidinone, 1-phenyl-3-pyrazolidinone-ascorbic acid and ascorbic acid itself.
  • an amount of potassium thiocyanate in the range of 10 -3 to 10 -1 mole per litre of the developer solution is present in order to obtain high gradation values and high sensitivity.
  • An amount of 25 to 250 mg of potassium iodide per liter is particularly recommended to obtain a higher speed.
  • the developer solution used in the method according to this invention has to be replenished not only for decrease of the liquid volume due to cross-over into the next processing solution but also for pH-changes due to oxidation of the developer molecules. This can be done on a regular time interval basis or on the basis of the amount of processed film or on a combination of both.
  • the development step can be followed by a washing step, treatment with a fixing solution and another washing or stabilization step.
  • the processing proceeds in a time of less than 90 seconds and more preferably in a time of less than 45 seconds.
  • reaction vessel 41.3 ml of solutions 1 and 2 were introduced into a reaction vessel in 28 seconds using the double jet technique.
  • Said reaction vessel initially contained 2.16 liter of destilled water at 45°C, 12.6 grams of potassium bromide and 12.5 grams of gelatin. After one minute the reaction temperature of this mixture was raised to 70°C in 20 minutes and 47.5 grams of phthalated gelatin in 475 ml destilled water were added. After 10 minutes the neutralization step was started.
  • a double jet precipitation was started using solutions 1 and 2 which continued for 40 minutes 51 seconds. During this precipitation, the pBr value was kept constant at 1.63. The flowing rate of solution 1 was 7.5 ml per minute at the start, linearly increas2ing to 26.7 ml per minute at the end of the precipitation. Thereafter the second neutralisation phaze was started.
  • Second growth step (during which 47.0 % of the total amount of AgNO 3 was used):
  • solution 1 704 ml of solution 1 was injected in the reaction vessel at a rate of 7.5 ml per minute at the start linearly increasing to 37.5 ml per minute at the end of the precipitation.
  • the pBr was kept constant at 2.77 using solution 2 for the first 8 minutes and 51 seconds, followed by the replacement of solution 2 by solution 3 for the rest of the precipitation.
  • a silver chloride emulsion was prepared by a double jet technique.
  • the silver halide composition was 100 mole % of chloride and the average grain size was 0.55 ⁇ m. Therefor an amount of 615 ml of demineralized water was used as starting volume in the vessel, containing further 46 g of inert gelatin and 10.3 mmoles of sodium chloride at 60°C.
  • the flocculation procedure could begin: pH was adjusted at a value of 3.3 with sulphuric acid, 3 M, and 4.5 g of polystyrene sulphonic acid was added slowly in 2 minutes. The washing procedure was performed in a discontinous way, adding 3 l of demineralised water, containing up to 8 mmole of sodium chloride pro liter, until pAg was reaching a value of about 100 mV.
  • the emulsion was peptised and was chemically ripened to an optimal fog-sensitivity relationship at 52°C, pAg having a value of about 125 mV.
  • Chemical ripening agents besides gold (in an amount of 0.019 mmole) and sulphur (tetramethyl thiodithiocarboxylic acid diamide in an amount of 0.061 mmole), were toluene thiosulphonic acid and iodide ions, both being predigestion agents in amounts of 4 mg and 8.6 mmoles respectively.
  • a photographic material was prepared having on a subbed polyester base a gelatinous silver halide emulsion of which the silver halide consists for 100 % of silver chloride having an average grain size of 0.55 ⁇ m the preparation of which has been described above.
  • the emulsion was further stabilised with 0.22 mmole of compound (V) and 0.68 mmole of compound (VI) per mole of silver nitrate.
  • the sodium salts of 7-sulpho-naphto-[2,3-D]-oxazoline-2-thion and 1-phenyl-5-mercaptotetrazole were added as stabilizers in amounts of 40, respectively 30 mg pro 100 g AgNO 3 .
  • a coated amount of silver expressed as the equivalent amount of silver nitrate of 4.0 g per square meter and a gelatin to silver chloride (expressed in equivalent amount of silver nitrate) ratio of 0.35 was provided with a gelatin covering layer (anti-stress layer) of 1.30 g of gelatin per m2.
  • Said comparative emulsion was stabilized with 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and after addition of the normal coating additives the solutions were coated simultaneously together with a protective layer containing 1.1 g gelatine per m 2 per side on both sides of a polyethylene terephthalate film support having a thickness of 175 ⁇ m.
  • the resulting photographic material contained per side an amount of silver halide corresponding to 3.5 grams of AgNO 3 per m 2 .
  • GXXX G138 hydroquinone 20 g 30 g 1-phenyl-3-pyrazolidinone 4.6 mmole 9.3 mmole potassium bromide 2.5 g 4.0 g potassium iodide 0.1 g --- potassium thiocyanate 1.0 g --- polyglycol (M.W. 400) 20 ml --- polyglycol (M.W.
  • Turpinal 2NZ (trade name for 1-hydroxy-ethyldiphosphonic acid disodium salt from HENKEL) 1 g 1 g methyl benztriazole ---- 0.09 g E.D.T.A.Na4 2.1 g 2.1 g diethylene glycol ---- 15 ml 5-nitroindazole ---- 0.25 g glutardialdehyde ---- 4.75 ml Water to make 1 liter. pH 10.5 10.1 (pH values were adjusted with acetic acid after the developer has been made ready for use: no dilution for GXXX, 1+3 for G138).
  • FXXX G334 ammonium thiosulphate (60%) 710 ml 850 ml boric acid 20.8 g 25 g sodium sulphite 45 g 54 g sodium acetate.3 aq. 58 g 70 g acetic acid 48.5 ml 39 ml sulphuric acid 20 ml -- demineralised water to make 1 liter.
  • G334 opposite to FXXX which is a one-part fixer, comprises a part B: demineralised water 610 ml acetic acid 40 ml sulphuric acid 30 ml aluminum sulphate (27 wt%) 320 ml
  • Fixer FXXX can be applied as such, while fixer G334, trade name product from Agfa-Gevaert, has to be diluted: part A 1+4; part B 1+19.
  • the amount of water absorption per square meter has been determined by making the difference by weight of the material after dipping it in demineralised water of 25°C during 3 minutes, squeezing the material and calculating the difference between said weight and the dry weight of said material before inserting it into the automatic developer.
  • the water absorption itself is expressed per gram of gelatin coated.
  • Coating amounts of silver halide are expressed in grams of equivalent amounts of silver nitrate per square meter.
  • the scratch resistance values correspond to the pressure (in g) that can be applied to the exposed unprocessed film, before pressure marks are visible after processing: the higher said value, the lower the pressure sensitivity of the coated crystals.
  • Covering power is expressed as the ratio between the measured maximum density obtained and the amount in grams of developed silver present in the area of maximum density.
  • Fig. 1A illustrates the shape of the developed silver, from the crystals rich in chloride developed in G138 and fixed in G334.
  • Fig. 1B illustrates the clearly different shape obtained in GXXX/FXXX processing, resulting in an enhanced covering power, according to one of the objects of this invention as set forth hereinbefore.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP94203085A 1994-10-24 1994-10-24 Method of processing a silver halide photographic material Expired - Lifetime EP0709730B1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE69422625T DE69422625T2 (de) 1994-10-24 1994-10-24 Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials
EP94203085A EP0709730B1 (en) 1994-10-24 1994-10-24 Method of processing a silver halide photographic material
JP7297359A JPH09138486A (ja) 1994-10-24 1995-10-19 ハロゲン化銀写真材料の処理方法
US08/752,521 US5795704A (en) 1994-10-24 1996-11-20 Method of hardener-free processing of a forehardened silver halide photographic material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP94203085A EP0709730B1 (en) 1994-10-24 1994-10-24 Method of processing a silver halide photographic material

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EP0709730A1 EP0709730A1 (en) 1996-05-01
EP0709730B1 true EP0709730B1 (en) 2000-01-12

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US5667957A (en) * 1996-05-23 1997-09-16 Eastman Kodak Company Xanthate salts as chemical sensitizers for silver halides

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GB1565503A (en) * 1976-09-10 1980-04-23 Minnesota Mining & Mfg Photographic materials
US4414304A (en) * 1981-11-12 1983-11-08 Eastman Kodak Company Forehardened high aspect ratio silver halide photographic elements and processes for their use
EP0527521B1 (en) * 1991-08-13 1996-05-22 Agfa-Gevaert N.V. A silver halide photographic material
JP2670921B2 (ja) * 1991-08-19 1997-10-29 富士写真フイルム株式会社 Ｘ線画像の形成方法
JPH0594019A (ja) * 1991-10-02 1993-04-16 Fuji Photo Film Co Ltd 平版印刷版の製版方法およびこれに用いる拡散転写処理液
EP0538947B1 (en) * 1991-10-24 1997-04-09 Agfa-Gevaert N.V. X-ray silver halide photographic material suitable for rapid processing systems

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EP0709730A1 (en) 1996-05-01
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DE69422625T2 (de) 2000-07-13

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