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
  • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
  • G03C5/39—Stabilising, i.e. fixing without washing out

Definitions

• the present invention relates to a process for the production of silver images including a stabilisation-fixing treatment.
• Stabilising baths for exposed and developed photographic silver halide emulsion layers which contain a large variety of organic mercapto compounds are state of the art and particulars concerning such baths are described in, e.g. the book "Modern Photographic Processing” Vol. 2 of Grant Haist - A Wiley Interscience Publication - (1979) New York - p. 210-227.
• the stabilising agent forms an insoluble non-lightsensitive silver compound while the fixing agent forms a soluble silver complex.
• solubility of said compounds in a given medium varies with the pH-value of the medium.
• one compound may be effective as stabilising agent as well as a fixing agent; it depends inter alia on the pH-value of the processing bath.
• a process for the production of a silver image including a stabilisation-fixing treatment of said image formed by development of an imagewise exposed photographic silver halide emulsion material is provided, wherein the imagewise exposed and developed silver halide emulsion material is treated with an aqueous solution containing an alkali metal thiosulphate and a mercapto-triazole compound corresponding to the following general formula (A) : wherein :
• the specified mercapto compounds are simply dissolved in water together with the other ingredients.
• the pH of the treating liquid is in the acidic range, e.g. in the range of 6 to 4.
• Small amounts of water-soluble solvents, e.g. acetic acid and water-miscible alcohols may be added to improve the dissolution of the mercapto-compound.
• the treating liquids used according to the present invention contain an anti-oxidizing agent to shield the mercapto-triazole compound from aerial oxidation.
• Suitable anti-oxidizing agents are ascorbic acid and compounds yielding sulphite ions, e.g. sodium sulphite and potassium metabisulphite.
• the present image-stabilising process makes it possible to eliminate the customary washing procedure and yet to obtain a satisfactory stable print.
• the treatment of the developed silver image with the above aqueous solution containing an alkali metal thiosulphate and a mercapto-triazole compound corresponding to the general formula (A) may be preceded by a rinsing treatment but such is not strictly necessary.
• the image-stabilising liquids used according to the present invention do not alter the binding properties of gelatin, so that no sticky gelatin silver halide emulsion layers are obtained as is the case when using stabilising liquids based on thiocyanates. Further no particular odour is produced and toxicity and corrosivity are very low.
• the fixing-stabilisation treatment according to the present invention is particularly effective for the stabilisation of silver images obtained by means of silver halide emulsion layers wherein the silver halide is for at least 50 mole % silver chloride.
• the present fixing-stabilisation processing is very effective when used in conjunction with silver halide emulsion layers having a silver halide coverage, the silver halide being expressed in an equivalent amount of silver nitrate, not higher than 4 g per sq.m.
• the treatment according to the present invention provides image stabilisation in a short time.
• Fixing-stabilisation treatment according to the present invention may be terminated in 30 s at room temperature (20°C) and may be terminated in 15 s at 35 °C.
• the fixing-stabilisation treatment can be used for photographic black-and-white papers and films, e.g. graphic art film materials, but is likewise applicable for the image stabilisation of photographic colour materials wherein residual silver halide may not remain.
• the photographic materials may contain already before the exposure some or all of the developing agent(s) used in the development step.
• the developing agents When the developing agents are present already in the photographic material during the exposure the development may be carried out with a so-called activator bath which is an alkaline aqueous liquid being free from developing agents and activates these agents already present in the photographic material.
• the silver images stabilised according to the present invention show a very low darkening in the non-image area under circumstances of heat, humidity and/or light-exposure. Such is demonstrated furtheron in comparative tests including the use of stabilising liquids comprising ammonium thiosulphate.
• alkali metal thiosulphate fixing agent in a common fixing bath, e.g. containing 0.1 mole to 1.5 mole per liter of sodium thiosulphate, is counteracted by using therein said mercapto-triazole, e.g. in a concentration up to 1x10 -1 mole per liter. It has been found advantageous to include a washing step to have the still residual amounts of thiosulphate and of complexed silver halide eliminated.
• the washing liquid likewise incoporates the mercapto-triazole compound, e.g. in an amount up to 1x10 mole per liter.
• the application of the treating liquids used in the processing of photographic silver halide emulsion materials may proceed by immersion but more advantageously proceeds by meniscus coating using a lick-roller, sponge or resilient roller to limit the volume of applied liquid .
• an image-wise exposed silver halide emulsion material according to the present invention it is in favour of effective stabilisation to keep the pH of the liquid(s) containing said mercapto-triazole compound in the acidic range and therefore to eliminate as much as possible of the alkaline developing or development activating liquid from the material before applying the stabilising liquid.
• Such may proceed by squeegee, e.g. with rollers or by applying an intermediate rinsing step.
• Said photographic material was treated in unexposed state for 10 s at 20°C with an alkaline aqueous activator liquid having the following composition :
• the developed material was led between squeegee rollers to remove the major part of adhering alkaline liquid and was then dipped for 5 s at 20 °C into a fixing or stabilising-fixing liquid as defined in the following Table.
• Liquid no. 1 contained per liter 198.5 g (0.8 mole) of sodium thiosulphate.5 water and 10 g of sodium sulphite.
• Liquid no. 2 had the same composition as liquid no. 1 but included in addition thereto per liter 1 g of 3-mercapto-4-amino-1,2,4-triazole.
• Liquid no. 3 had the same composition as liquid no. 1 but included per liter 3 g of 3-mercapto-4-amino-5-methyl-1,2,4-triazole.
• Liquid no. 4 contained per liter 118.5 g (0.8 mole) of ammonium thiosulphate and 10 g of sodium sulphite.
• Liquid no. 5 had the same composition as liquid no. 4 but included in addition thereto per liter 1 g of 3-mercapto-4-amino-1,2,4-triazole.
• the efficiency of the stabilisation was determined by measuring the change in optical density ( ⁇ D) obtained after keeping one strip (i) of the processed material for 3 days in the dark at 35 °C at 80 % relative humidity and another strip (ii) for 4 h in a XENOTEST (trade name) exposure apparatus wherein the strip was subjected to a white light illumination of 180,000 lux.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (7)

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Citations (2)

• 1985
  • 1985-01-29 EP EP85200095A patent/EP0189603A1/fr not_active Withdrawn
• 1986
  • 1986-01-24 JP JP1462186A patent/JPS61182037A/ja active Pending

Patent Citations (2)

Non-Patent Citations (1)

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