Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/305—Additives other than developers
  • G03C5/3056—Macromolecular additives
• • 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
• • 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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/407—Development processes or agents therefor

Definitions

• the present invention relates to a solution for sludge formation and "pi-line” artefact, while processing silver halide photographic materials.
• dissolution regulators inhibitors
• Typical examples of those dissolution inhibitors are the small heterocyclic thiols without solubilizing groups.
• the selected polymeric compounds preventing sludge formation particularly suitable for use in processing solutions according to the present invention therefore comprise at least one monomer unit having a silver ion complexing moiety and at least one monomer unit having a solubilising group.
• the group complexing silver ions and the solubilising group are, in a particular embodiment, comprised in the same monomer unit.
• the processing solution comprises as an additive a polymeric compound having a thiol or a salt thereof as a group complexing silver ions, a group capable of generating a thiol by hydrolysis or a disulfide.
• the solubilising group is selected from the group consisting of a carboxylic acid or salt thereof, a sulfonic acid or salt thereof, a phosphonic acid or salt thereof, a phosphate and a sulfate.
• non-ionic groups like in (meth)acrylamides and hydrofunctional polymers are very useful additives.
• Polymeric compounds suitable for use as "anti-sludging" additives in the processing solution according to the present invention can be prepared according to any known polymerisation technique, such as radical polymerisation of ethylenically unsatured monomers, polycondensates for the preparations of e.g. polyesters, polyurethanes and polycarbonates and polymers obtained by anionic or cationic ringopening polymerisations.
• any known polymerisation technique such as radical polymerisation of ethylenically unsatured monomers, polycondensates for the preparations of e.g. polyesters, polyurethanes and polycarbonates and polymers obtained by anionic or cationic ringopening polymerisations.
• the polymeric compound comprises at least one ethylenically unsatured monomer according to formula I. wherein:
• the ethylenically unsatured monomer according to the formula I is selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, vinylethers and styrenes.
• the polymeric compound comprises at least one ethylenically unsatured monomer according to formula II : wherein :
• the monomers according to the general formulae I and II are preferably copolymerised with a monomer comprising at least one solubilising group, wherein said solubilising group is more preferably selected from the group consisting of a carboxylic acid or salt thereof, a sulfonic acid or salt thereof, a phosphonic acid or salt thereof, a phosphate or a sulfate in order to provide a polymeric compound suitable for use as an additive in the processing solution according to the present invention.
• Typical monomers having a solubilising group are acrylic acid, methacrylic acid, styrene-4-sulfonic acid, 4-carboxymethyl-styrene, itaconic acid maleic acid, fumaric acid, 2-acrylamino-2-methylpropane-sulfonic acid, without however being limited thereto.
• the molar ratio of the monomer unit comprising a moiety having silver ion complexing ability to the monomer comprising a solubilising group is preferably between 1 to 100 and 100 to 1, more preferably between 1 to 100 and 1 to 1 and still more preferably between 1 to 25 and 5 to 1.
• the polymeric compound preventing sludge formation may further comprise other monomers besides the monomer unit comprising a silver ion complexing moiety and the monomer unit comprising a solubilising group.
• the processing solution is a photographic developing solution.
• the polymeric compound as a coating agent in the protective antistress layers of silver halide materials to be processed.
• silver halide photographic materials especially envisaged within the context of non-destructive testing applications reference is made to the materials having been coated with cubic silver halide grains as described in EP-A's 0 538 947, 0 622 668, 0 620 483, 0 620 484, 0 621 506, 0 698 817, 0 754 971 and 0 754 972 and with tabular silver halide grains as disclosed in EP-A's 0 678 772, 0 890 875, 1 195 642 and 1 197 797.
• the halide composition of the cubic or tabular silver halide grains coated in the radiation sensitive emulsion layers is not restricted to grains rich in silver bromide, like the silver bromoiodide grains normally used, but is also related with grains rich in silver chloride.
• reaction mixture was refluxed for an additional 2 hours. After cooling down to room temperature, the reaction mixture was concentrated to 500 ml and 500 ml of ethylacetate was further added.
• Monomer I.1 precipitated from the medium as a white crystalline solid.
• the compound was isolated by filtration, was washed twice with 500 ml ethylacetate/ethanol 3/1 and dried. 170 grams of monomer I.1 were isolated.
• the intermediate ethyl-bromomethacrylate was prepared by dissolving 130 g (1 mole) of ethyl-hydroxymethacrylate in 1100 ml of diethyl ether. 133 g (0.49 mole) PBr 3 were added dropwise, while the reaction mixture was kept below 0°C. The reaction was allowed to continue for 4 hours at 0°C. After 4 hours, 1100 ml of water were added slowly, while keeping the temperature below 10°C. The organic layer was isolated and the aqueous phase was extracted three times with 250 ml hexane. The pooled organic fractions were dried over Na 2 SO 4 . 200 mg 2,6-di-tert.-butyl-4-methylphenol were added in order to avoid spontaneous polymerisation and the solvents were removed under reduced pressure. The crude product was used without further purification.
• Monomer 1.15 precipitated from the medium as a white crystalline compound.
• Monomer 1.15 was redissolved in 200 ml of ethanol and NaHCO 3 was removed by filtration.
• the ethanol was evaporated under reduced pressure to 35 ml and 75 ml of ethyl acetate were added.
• the precipitated monomer was isolated by filtration, washed with ethyl acetate and dried.
• a gelatino silver iodobromide X-ray emulsion comprising 99 mole % of silver bromide and 1 mole % of silver iodide was prepared in the following way.
• An aqueous solution containing 3 grams of ammonia was added to the reaction vessel containing 1550 ml of a 3% by weight aqueous solution of gelatin at 45°C.
• a solution of 2000 ml of an aqueous 1.5 molar solution of potassium bromide and a solution of 2000 ml of an aqueous 1.5 molar solution of silver nitrate were introduced at constant rate of 86 ml/min under vigorously stirring conditions.
• the pAg value was adjusted to and maintained at a value corresponding to an E.M.F. of +20 mV with reference to a silver/saturated calomel electrode. In this way homogeneous and regular silver halide grains having a crystal diameter of 0.54 ⁇ m were obtained.
• the emulsion was coagulated by adding polystyrene sulphonic acid acting as a flocculating agent after adjustment of the pH value of the emulsion in the reaction vessel to 3.5 with sulphuric acid. After rapid sedimentation of said silver halide emulsion the supernatant liquid was decanted.
• demineralised water of 11°C. was added under controlled stirring conditions followed by a further sedimentation and decantation. This washing procedure was repeated until the emulsion was sufficiently desalted. Thereafter the coagulum was redispersed at 45°C in water after the addition of a sufficient amount of gelatin to obtain a ratio of gelatin to silver halide expressed as silver nitrate of 0.4.
• the pH-value was adjusted to 6.5 and pAg to a value of +70 mV with reference to the silver/saturated calomel electrode.
• Chemical sensitisation of said emulsion was performed by the addition of a sulphur and gold sensitiser and digestion at 50°C to the point where the highest sensitivity was reached for a still acceptable fog level.
• This emulsion was coated at both sides of a blue polyethylene terephthalate support having a thickness of 175 ⁇ m, so that per sq. m. an amount of silver halide corresponding to 14.5 g of silver nitrate and 12.3 g of gelatin were present.
• stabilisers such as 5-methyl-7-hydroxy-5-triazolo-[1,5-a]-pyrimidin and 1-phenyl-5-mercaptotetrazol were added to the emulsion.
• the emulsion layers were covered at both sides with a protective layer of 1.5 grams of gelatin per square meter, which were hardened with 0.093 g of di-(vinyl-sulphonyl)-methane (DVS) per square meter.
• a protective layer 1.5 grams of gelatin per square meter, which were hardened with 0.093 g of di-(vinyl-sulphonyl)-methane (DVS) per square meter.
• the protective layers of material were in addition coated with a polyoxyalkylene compound in an amount of 0.042 g/m 2 at both sides of the film.
• the coated and dried films were exposed according to ISO 7004 with a 235 kV radiation source with a copper filter of 8 mm thickness.
• the exposed radiographic films were developed, fixed, rinsed and dried in an NDT M ECO (trade name product from Agfa-Gevaert, Mortsel, Belgium) automatic machine processing cycle of 5 minutes. Development was run, at 29°C, in the reference developer G135® , in the comparative developer (CD) and in the inventive developer (ID).
• NDT M ECO trade name product from Agfa-Gevaert, Mortsel, Belgium
• fixer G335® (trade name) marketed by Agfa-Gevaert, at 29°C, which comprises aluminum sulphate, sodium sulphite, boric acid and sodium acetate.
• Figures ranging from 0 to 6 were given with the following significance for the appearance of the "pi-line" defect, in order to make a visually acceptable ranking: 6: inadmissable; 4 or 5: admissable for non-critical users who are not informed about the appearance of the defect; 2 or 3: acceptable for users who have already been confronted with the failure; 1: acceptable for critical customers; 0: no visibly detectable pi-line defect.
• the inventive developer having been provided with the "polymeric antisludge” and anti-"pi-line” compound indicated above provides a figure, after evaluation of "sludging" of the developer in the processing machine and "pi-line” occurring on the processed film material, that is clearly more stable and more acceptable than the best known developer G135® , even after quite a high number of square meters of that film material have been run through that processor over a time period of several days.
• Controll was performed for the film material after having been run in G135® and ID respectively.

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Citations (5)

• 2003
  • 2003-07-09 EP EP20030102056 patent/EP1388755B1/fr not_active Expired - Lifetime

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