EP0329051A2 - Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent - Google Patents

Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent Download PDF

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Publication number
EP0329051A2
EP0329051A2 EP89102437A EP89102437A EP0329051A2 EP 0329051 A2 EP0329051 A2 EP 0329051A2 EP 89102437 A EP89102437 A EP 89102437A EP 89102437 A EP89102437 A EP 89102437A EP 0329051 A2 EP0329051 A2 EP 0329051A2
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Prior art keywords
solution
bleaching
processing
photographic material
color
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EP89102437A
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German (de)
English (en)
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EP0329051B1 (fr
EP0329051A3 (en
Inventor
Yoshihiro Fujita
Shinji Ueda
Akira Abe
Shigeru Nakamura
Takatoshi Ishikawa
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP63031120A external-priority patent/JPH07120000B2/ja
Priority claimed from JP63151796A external-priority patent/JP2657268B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0329051A2 publication Critical patent/EP0329051A2/fr
Publication of EP0329051A3 publication Critical patent/EP0329051A3/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
    • 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
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • the present invention relates to a method for processing an exposed silver halide color photographic material (the term "silver halide color photographic material” is hereinafter abbreviated to "color photographic material”) and, in particular, it relates to a method for processing an exposed color photographic material where sufficient desilvering can be effected in a short period of time to give improved photographic properties to the processed material.
  • the basic procedure for processing color photographic material includes, in general, a color-­development step and a desilvering step.
  • the color-­development step the exposed silver halide in a color photographic material is reduced with a color-developing agent to yield silver, while the oxidized color-developing agent is reacted with a coupler to give a color image.
  • the silver formed in the previous color-developing step is oxidized by the action of an oxidizing agent (which is generally called a "bleaching agent”) and then dissolved by the action of a complexing agent for silver irons (which is generally called a "fixing agent").
  • an oxidizing agent which is generally called a "bleaching agent”
  • a complexing agent for silver irons which is generally called a "fixing agent”
  • the desilvering step is conducted either in a two-­bath system using a bleaching agent-containing bleaching bath and a fixing agent-containing fixing bath or in a one-bath system using a bleach-fixing bath containing both bleaching agent and fixing agent.
  • a practical development procedure includes various auxiliary steps, in addition to the above-mentioned basic steps, for the purpose of maintaining the photographic and physical quality of the images formed and of improving the storage stability of the images formed.
  • auxiliary steps are conducted using a film-hardening bath, a stopping bath, an image-stabilizing bath and a rinsing bath.
  • processing bath having a fixing ability indicates both the fixing bath and bleach-fixing bath.
  • the fixing agent for the bath having a fixing ability thiosulfates which are excellent in fixing capacity and are advantageous in view of their cost are generally used.
  • ferric complexes for example, aminopolycarboxylic acid iron (III) complexes, especically (ethylenediaminetetraacetato) iron (III) complex
  • ferric complexes for example, aminopolycarboxylic acid iron (III) complexes, especically (ethylenediaminetetraacetato) iron (III) complex
  • ferric complexes are relatively poor in oxidizability and are insufficient in bleaching power. Accordingly, when they are used for bleaching or bleach-­fixing a low-sensitivity silver halide color photographic material containing essentially a silver chlorobromide emulsion, the intended object can generally be attained.
  • JP-A-62-222252 a method of using a bleaching agent combination of (1, 3-­diaminopropanetetraacetato) iron (III) complex and (ethylenediaminetetraacetato) iron (III) complex and having an excellent bleaching power is known, as described in JP-A-62-222252 (the term "JP-A” as used herein means an "unexamined published Japanese patent application”).
  • aminopolycarboxylic acid which produces a comopound such as (1,3-diaminopropane­tetracetato)iron (III) complex, having a low stability constant in binding to iron (III)
  • the compound causes a remarkable bleaching fog on a photosensitive material and in sufficiency in recoloration of cyan dye, although it has a high bleaching ability.
  • Fuji Film Processing Manual, CN-16 Processing (October, 1985) has proposed a method where a photographic material is, after processing, fully rinsed or washed with water to remove the components of the bleaching solution from the photographic material processed. Although this method is effective to some degree, this interferes with rapid processing and additionally the number of the necessary processing bath must be increased. Accordingly, such a method is not suitable for use in a mini-laboratory system where rapid processability, small installation space and low processing cost are required.
  • a first object of the present invention is to provide a rapid desilvering method for processing color photographic materials.
  • a second object of the present invention is to provide an excellent and rapid desilvering method for processing color photographic materials where the material processed is not stained.
  • the third object of the present invention is to provide a rapid desilvering method for processing color photographic materials where the material processed has no bleaching fog and high sufficiency in recoloration.
  • a method for processing a silver halide color photographic material by the steps of (a) developing an imagewise exposed silver halide color photographic material composed of a support having thereon at least one light-sensitige silver halide emulsion layer; (b) processing the developed color photographic material with a bleaching solution containing (1,3-­diaminopropanetetraacetato)iron (III) complex and (c) containing the emulsion surface of the material from step (b) with a jet stream of a solution having a fixing ability.
  • 1,3-DPTA ⁇ Fe (III) 1,3-­diaminopropanetetraacetato iron (III) complex
  • the 1,3-DPTA ⁇ Fe(III) oxidizes the thiosulfate iron in the emulsion layer or near the surface thereof to give a sulfur compound, and the thus-­formed sulfur compound strongly adheres to the silver halide in the material to retard the fixation procedure.
  • the sulfur compound penetrated into the gelatin layer or adhered to the surface near the layer, causes the stains in the material.
  • a jet stream of a processing solution having a fixing ability is directed against the photographic material containing 1,3-DPTA ⁇ Fe(III), when the photographic material being processed is dipped in the processing solution having a fixing ability, whereby the diffusing of the 1,3-DPTA ⁇ Fe(III) from the emulsion layer of the material is noticeably accelerated, to thereby prevent the formation of the sulfur compound in the layer.
  • the application of the jet stream of the processing solution having a fixing ability to the emulsion layer of the photographic material being processed is preferably conducted as soon as possible after the material has been dipped in the processing solution having a fixing ability.
  • the photographic material color-developed is processed in a processing solution having a fixing ability, while a jet stream of the processing solution having a fixing ability is directed against the emulsion surface of the material being processed.
  • the jet steam of the processing solution having a fixing ability may be provided by pumping the solution having a fixing ability onto the emulsion surface of the photographic material being processed from nozzles provided in a position facing the emulsion surface of the material, a distance between the nozzle and the emulsion surface being preferably short, more preferably from 0.2 cm to 1.5 cm.
  • the device providing the jet stream may have from 10 to 200 nozzles, and the device having more nozzles are better.
  • Each nozzle has a size of from 1 mm to 10 mm, and preferably from 1 mm to 5 mm in a diameter and a shape of square, round, hexagon, etc., with no limitation as to the shape of nozzles. More specifically, the method described in JP-­A-62-183460, from page 3, right-lower column to page 4, right-lower column (example of the invention) may be employed, in which a solution as transferred under pressure by the action of a pump is jetted out from slits or nozzles provided facing the emulsion surface of the photographic material being processed.
  • the speed of the jet stream (flow velocity)
  • flow velocity when it is directed against the emulsion surface, is preferred to be as high as possible within the range where the jet stream does not interfere with the conveyance of the photographic material, being processed in an automatic developing machine, and specifically, the flow velocity at the nozzle is preferred to fall within the range of from about 0.3 m/sec. to about 3 m/sec, and more preferred from about 2 m/sec. to about 3 m/sec.
  • the arrows from the jet stream pipe (13) indicate the jet stream of a fixing solution to be jetted from the nozzles provided in the jet stream pipe.
  • the fixing solution (12) is introduced into the jet stream pipe (13) via the circulation pipe (15) under suction by the pump (14).
  • the emulsion surface of the photographic material being processed faces downwards.
  • the emulsion surface faces the jet stream pipe.
  • the photographic material being processed is introduced into a bath of the solution having a fixing ability and the jet stream of the solution having a fixing ability is directed against the emulsion surface of the material within 15 seconds, more preferably within 10 seconds, after its introduction into the bath.
  • This time is the time from the contact of a certain point of the photographic material being processed with the processing solution having a fixing ability to the contact of the same point with a vertical jet stream of the processing solution.
  • the acceleration of the fixation by the application of the jet stream of the processing solution having a fixing ability prevents the retardation of fixation because of the 1, 3-DPTA ⁇ Fe(III) contained in the emulsion layer of the material being processed, and is basically different from the effect which would be attained in a different system using a bleaching agent of conventional (ethylenediaminetetraacetato) iron (III) complex only.
  • a bleaching agent of conventional (ethylenediaminetetraacetato) iron (III) complex in accordance with the method of the present invention, another surprising effect of preventing stains in the photographic material processed can be attained.
  • a thiosulfate is generally used as the fixing agent.
  • these include sodium thiosulfate, ammonium thiosulfate and potassium thiosulfate, and use of ammonium thiosulfate is most preferred.
  • the amount of the fixing agent to be added to the bath is preferably from 50 g to 500 g, more preferably from 100 g to 300 g, per liter of the solution having a fixing ability.
  • the bath may further contain thiocyanates, thioureas or thioethers, if desired.
  • the fixing solution for using in the present invention preferably contains an organic phosphonic acid type chelating agent for the purpose of improving the stability of the solution.
  • 1-hydroxyethylidene-1, 1-­diphosphonic acid or N,N,N′,N′-ethylenediamine­tetraphosphonic acid is used for the purpose.
  • the amount of the organic phosphonic acid type chelating agent is preferably from 0.005 to 0.5 mol, more preferably from 0.05 to 0.10 mol, per liter of the solution having a fixing ability.
  • the processing solution having a fixing ability for use in the present invention can contain, as a preservative, sulfites such as sodium sulfite, potassium sulfite or ammonium sulfite, as well as sulfinic acids, hydroxylamine, hydrazines or aldehyde compound-bisulfite adducts such as acetaldehyde-sodium bisulfite. Further, it may also contain various brightening agents, de-foaming agents, and surfactants as well as organic solvents such as polyvinyl pyrrolidone or methanol.
  • the bath having a fixing ability for use in the present invention is a bleach-fixing solution
  • the bath preferably contains the various (amino­polycarboxylato) iron (III) complexes described above as a bleaching agent.
  • the following compounds are most preferred, but the present invention is not to be construed as being limited thereto: (1, 2-Propylenediaminetetraacetato) iron (III) complex (1, 3-Propylenediaminetetraacetato) iron (III) complex (Ethylenediaminetetraacetato) iron (III) complex (Cyclohexanediaminetetraacetato) iron (III) complex (Diethylenetriaminepentaacetato) iron (III) complex
  • the amount of the bleaching agent is preferably from 0.1 mol/liter to 0.5 mol/liter.
  • the bleaching agent may be introduced into the bleach-fixing solution as a result of the introduction of the overflow solution from the previous bleaching bath.
  • the bath having a fixing ability for use in the present invention has a pH of from 4.0 to 9.0, preferably from 5.0 to 8.0.
  • the amount of the replenisher for the bath is from 300 ml to 3000 ml, preferably from 300 ml to 1000 ml, per m2 of the photographic material being processed.
  • the combined processing time of the photographic material in the bleaching bath and the bath having a fixing ability, in accordance with the method of the present invention, is from 1 minute to 4 minutes, preferably from 1 minute and 30 seconds to 3 minutes.
  • the processing temperature is from 25°C to 50°C, preferably from 35°C to 40°C.
  • the bleaching solution for use in the present invention contains (1, 3-diaminopropanetetraacetato) ⁇ iron (III) complex.
  • This complex may be in the form of an alkali metal salt such as a sodium or potassium salt, but the complex is preferably in the form of an ammonium salt, since the bleaching rate of the salt is excellent and it prevents the increase of the yellow density in the non-­exposed areas of the photographic material processed.
  • the amount of the 1,3-DPTA ⁇ Fe (III) is from 0.05 mol to one mol, preferably from 0.1 mol to 0.5 mol, per liter of the bleaching solution.
  • any other (aminopolycarboxylato) iron (III) complexes can be incorporated into the bleaching solution together with the 1,3-DPTA ⁇ Fe (III), if desired.
  • ferric complexes of the following compound group (A) although the present invention is not to be construed as being limited thereto:
  • the molar proportion of the additional complex is 3 mols or less inclusive of 0 mol) per one mol of 1,3-­DPTA ⁇ Fe (III), in view of the high bleaching power and the small bleaching fog, and more preferably from 0.1 to 3 mols, especially preferably from 0.1 to 1.5 mols, per mol of 1,3-DPTA ⁇ Fe (III).
  • a jet stream of the bleaching solution is directed against the photographic material being processed within 15 seconds after introduction of the material into the bleaching solution, in the same manner as in the processing step with the processing solution having a fixing ability, to promote acceleration of bleaching, prevention of bleaching fog, prevention of insufficiency in recoloration of cyan dye and acceleration of fixation.
  • the time is especially preferably within 10 seconds. The effect is especially remarkable when the pH value of the bleaching solution is 5.5 or less.
  • the bleaching solution for use in the method of the present invention preferably has a pH value of from 5.5 to 2.0, more preferably from 5.0 to 3.0, most preferably from 4.5 to 3.5, for the purpose of attaining sufficient desilvering and of preventing bleached fog.
  • a pH value of the bleaching solution is 5.5 or less, the bleaching rate is extremely improved and the bleaching fog may noticeably be prevented.
  • the pH value is too low, the ferric complex in the bleaching solution precipitates.
  • the pH value of conventional bleaching solutions is 5.5 or more, since a lower pH value of the solution would generally cause insufficiency in recoloration of cyan dye. Surprisingly, no insufficiency in recoloration of cyan dye occurrs in the method of the present invention, even when the pH value of the bleaching solution used is lowered, but rapid bleaching can be effected under such low pH condition.
  • the material to be processed is directly introduced into the bleaching solution, without the material being processed with any other intermediate processing solutions (such as a rinsing solution), from the viewpoint of acceleration of the processing.
  • the crossover time from the color-developer to the bleaching solution i.e., the time from removing the photographic material being processed from the color-­developer to its introduction into the bleaching solution, is desirably 10 seconds or less, preferably 5 seconds or less, especially preferably 3 seconds or less, whereby the bleaching fog or staining of the surface of the photographic material processed may effectively be prevented.
  • the transfer speed of the film between the processing tanks can be elevated (in general, the linear velocity is elevated), or the conveyance of the film between the processing solution tanks is effected at a position lower than the liquid level of the first tank or at the position falling within the range of from 0 to several centimeters from the liquid surface of this tank, whereupon a dead space is preferred to be provided between the tanks for the purpose of intermixing of the processing solutions of the respective tanks. Any of these methods can be employed in practice of the present invention.
  • the linear velocity in the processing procedure is generally lower than that for a large-sized machine, and the apparatus is required to be small and inexpensive, but it is difficult to shorten the crossover time within 10 seconds, for example 3 seconds or less.
  • the bromide ion concentration in the bleaching solution is preferably from 1.2 mols/liter (or 118 g/liter as NH4Br) to 3.0 mols/liter, more preferably 1.5 to 2.8 mols/liter and most preferably 1.7 to 2.5 mols/liter whereby the yellow density increase is substantially reduced to zero (0).
  • the other problem of staining of the film processed may also be prevented by elevation of the bromide ion concentration in the bleaching solution.
  • the bromide ion concentration is preferably from 1.2 mols/liter (or 118 g/liter as NH4Br) to 3.0 mols/liter, more preferably 1.5 (147 g/liter as NH4Br)to 2.8 mols/liter and most preferably 1.7 to 2.5 mols/liter.
  • the said concentration is 1.7 mols/liter or 167 g/liter as NH4Br) or more, staining of the film processed may completely be prevented.
  • shortening of the crossover time from the bleaching solution to the processing solution having a fixing ability to 10 seconds or less is preferred, since insufficiency in recoloration of cyan dye can be prevented under such conditions. It is more preferred that the crossover time is shortened as much as possible (i.e., to 5 seconds or less, especially to 3 seconds or less) from the viewpoint of the rapid processing of the method of the invention. Under such conditions of shortened crossover time, the effect of the present invention is remarkable.
  • the above method may be used as the present crossover procedure.
  • the bleaching solution for use in the method of the present invention may additionally contain various kinds of bleaching accelerators.
  • Preferred bleaching accelerators include various mercapto compounds as described in U.S. Patent 3,893, 858, British Patent 1,138, 842 and JP-A-53-141623; disulfido bond-containing compounds as described in JP-A-53-95630; thiazolidine derivatives as described in JP-B-53-9854 (the term "JP-B” as used herein means an "examined Japanese patent publication”); isothiourea derivatives as described in JP-­A-53-94927; thiourea derivatives as described in JP-B-45-­8506 and 49-26586; thioamide compounds as described in JP-­A-49-42349; and dithiocarbamic acid salts as described in JP-A-55-26506.
  • the amount of the comopounds of formulae (I) to (VIII) to be added is preferably from about 1 x 10 ⁇ 4 to about 1 x 10 ⁇ 1 mol/l, more preferably from about 3 x 10 ⁇ 4 to about 1 x 10 ⁇ 2 mol/l and most preferably from about 1 x 10 ⁇ 3 to about 8 x 10 ⁇ 3 mol/l
  • the bleaching solution for use in the method of the present invention may further contain, in addition to the bleaching agent and the above compounds, any conventional additives which are generally known to be incorporated into conventional bleaching solutions, for example, one or more inorganic acids, organic acids and salts thereof having a pH buffering capacity, such as nitrates (e.g., sodium nitrate, ammonium nitrate), boric acid, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate or tartaric acid.
  • nitrates e.g., sodium nitrate, ammonium nitrate
  • boric acid sodium metaborate
  • acetic acid sodium acetate
  • sodium carbonate potassium carbonate
  • phosphorous acid phosphoric acid
  • sodium phosphate citric acid
  • citric acid sodium citrate or tartaric acid
  • the replenishing amount of the fixing solution is from 50 ml to 2000 ml, preferably from 100 ml to 1000 ml, per m2 of the photographic material being processed.
  • the method of the present invention can be carried out in an automatic developing machine, which will be explained in detail hereunder.
  • stirring of the processing solution having a fixing ability is preferably increased as much as possible, whereby the time required for desilvering may be shortened.
  • Specific ways of increasing stirring in the step include a method of applying a jet stream of a processing solution to the emulsion surface of the photographic material being processed, as described in JP-­A-62-183460 mentioned before; a method of using a rotating means to elevate the stirring effect in a processing solution, as described in JP-A-62-183461; a method of moving the photographic material being processed while the emulsion surface of the material is contacted with a wiper blade provided in the inside of the processing bath so that the processing solution near the the emulsion surface is made turbulent to thereby elevate the stirring of the bath; and a method of increasing the circulating flow of the total processing solution.
  • Such means are preferably used for increasing the stirring of the fixing solution and bleach-fixing solution as well as bleaching solution.
  • the increase of the stirring of the processing solution is considered to accelerate the introduction of the bleaching agent and the fixing agent into the emulsion layer of the photographic material being processed, and as a result, to elevate the desilvering rate in the processing step.
  • the stirring acclerating means is more effective when a bleaching accelerator is used, whereby the bleaching accelerating effect can noticeably be enhanced and the fixation retardation or insufficiency may be eliminated because of the bleaching accelerator.
  • the automatic developing machine to be used for the method of the present invention is preferred to have a means of conveying the photographic material being processed, as described in JP-A-60-191257, 60-191248 and 60-191259.
  • the conveyance means is effective for noticeably reducing the carryover of the processing solution from the prior bath to the later bath and therefore is also effective for preventing deterioration of the processing solution used. This is especially meaningful for shortening the processing time in the respective processing steps and for reducing the amount of the replenisher for the respective processing steps.
  • the color developer for use in the method of the present invention contains known aromatic primary amine color developing agents.
  • Preferred examples of the color developing agents for use in the present invention are p-­phenylenediamine derivatives. Specific examples of such derivatives are mentioned below, which, however, are not to be construed as limiting the scope of the present invention.
  • (D-5) is especially preferred.
  • the p-phenylenediamine derivatives may also be in the form of salts such as sulfates, hydrochlorides, sulfites or p-toluenesulfonates.
  • the amount of the aromatic primary amine developing agent contained in the color developer is preferably from about 0.1 g to about 20 g, more preferably from about 0.5 g to about 10 g or so, per liter of the developer.
  • the color developer for use in the present invention can further contain, if desired, sulfites, such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite or potassium metasulfite, as well as carbonyl-sulfite adducts, as a preservative.
  • sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite or potassium metasulfite, as well as carbonyl-sulfite adducts, as a preservative.
  • the preferred amount of the preservative to be added to the color developer is from 0.5 g to 10 g, more preferably from 1 g to 5 g, per liter of the developer.
  • various hydroxylamines As compounds capable of directly preserving the color developing agents, various hydroxylamines, the hydroxamic acids described in JP-A-63-43138, the hydrazines and hydrazides described in JP-A-63-146041, the phenols described in JP-A-63-44657 and 63-58443, the ⁇ -­ hydoroxyketones and ⁇ -aminoketones described in JP-A-63-­44656 and/or various saccharides described in JP-A-63-­36244 are preferably added to the color developer.
  • the monoamines described in JP-A-63-4235, 63-24254, 63-21647, 63-146040, 63-27841 and 63-25654, the diamines described in JP-A-63-30845, 63-146040 and 63-43139, the polyamines described in JP-A-63-21647 and 63-26655, the polyamines described in JP-A-63-44655, the nitroxy radicals described in JP-A-63-44655, the nitroxy radicals described in JP-A-­63-53551, the alcohols described in JP-A-63-43140 and 63-­53549, the oximes described in JP-A-63-56654, and the tertiary amines described in EP-248450A may preferably be used.
  • the color developer for use in the present invention preferably has a pH value of from 9 to 12, more preferably from 9 to 11.0, and the color developer can contain various known developer components in addition to the above-mentioned ingredients.
  • the color developer preferably contains various buffers.
  • useful buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxy-benzoate, sodium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
  • these compounds are not intended to restrict the scope of the present invention.
  • the amount of the buffer to be added to the color developer is preferably 0.1 mol/liter or more, and is especially preferably from 0.1 mol/liter to 0.4 mol/liter.
  • the color developer may also contain various chelating agents as an agent for preventing precipitation of calcium or magnesium or for the purpose of improving the stability of the color developer.
  • organic acid compounds are preferred, in particular e.g., aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids.
  • the acid compounds include nitrilotriacetic acid, diethylene-triaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-­trimethylenephosphonic acid, ethylenediamine-N,N,N′ ,N′-­tetramethylenephosphonic acid, transcyclohexanediamine­tetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethylimino-diacetic acid, glycol ether diamine­tetraacetic acid, ethylenediamino-orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-­hydroxyethylidene-1, 1-diphosphonic acid and N,N-bis(2-­hydroxybenzyl
  • the amount of the chelating agent to be added to the color developer is any that is sufficient for sequestering the metal ion in the color developer.
  • the amount may be from 0.1 g to 10 g or so per liter of the developer.
  • the color developer may contain any optional development accelerator, if desired.
  • the color developer for use in the present invention is substantially free from benzyl alcohol, in view of the prevention of environmental pollution, the easiness of the preparation of the developer solution and the prevention of fog.
  • substantially free from benzyl alcohol means that the content of benzyl alcohol in the developer is 2 ml or less per liter of the developer, and preferably the developer contains no benzyl alcohol.
  • development accelerators which can be added to the color developer for use in the present invention, include, for example, the thioether compounds described in JP-B-37-16088, 37-5978, 38-7826, 44-12380 and 45-9019 and U.S. Patent 3,813,247, the p-phenylenediamine compounds described in JP-A-52-49829 and 50-15554, the quaternary ammonium salts described in JP-A-50-137726, JP-B-44-30074 and JP-A-56-156826 and 52-43429, the amine compounds described in U.S. Patents 2,494,903, 3,128,182, 4,230,796 and 3,253,919, JP-B-41-11431, U.S.
  • any optional anti-foggant can be added to the color developer, if desired.
  • the anti-foggant can be used alkali metal halides such as sodium chloride, potasium bromide or potassium idodide, as well as organic anti-foggants.
  • organic anti-foggants which may be used in the present invention, there are nitrogen-­containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzo­triazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-­thiazolyl-benzimidazole, 2-thiozolylmethyl-benzimidazole, indazole, hydroxyazaindolidine and adenine.
  • nitrogen-­containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzo­triazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-­thiazolyl-benzimidazole, 2-thiozolylmethyl-benzimidazole, indazole, hydroxyazaindolidine and adenine.
  • the color developer for use in the present invention preferably contains a brightening agent.
  • a brightening agent are preferred 4,4′-diamino-2, 2′-­disulfostylbene compounds.
  • the amount of the brightening agent to be added to the color developer is up to 5 g/liter, preferably from 0.1 to 4 g/liter.
  • various kinds of surfactants can be added to the color developer, if desired, including alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids.
  • the processing temperature of the color developer of the present invention is from 20 to 50°C, preferably from 30 to 45°C.
  • the processing time is from 20 seconds to 5 minutes, preferably from 30 seconds to 3 minutes.
  • the amount of the replenisher is preferably small and is, for example, from 100 to 1500 ml, preferably from 100 to 800 ml, more preferably from 100 to 400 ml, per m2 of the photographic material processed.
  • the color development may be effected in a multi-­bath system containing two or more baths, where a replenisher for color developer is introduced into the first bath or into the last bath so that the development time may be shortened and the amount of the replenisher may be reduced.
  • the processing method of the present invention can be applied to color reversal processing.
  • a first black-and-white developer which is generally used in conventional reversal processing of general color photographic materials or a common black-and-white developer which is generally used for processing of conventional black-and-white developer can be incorporated into the developer.
  • Examples of typical additives include a developing agent such as 1-phenyl-3-pyrazolidone, Metol or hydroquinone, a preservative such as sulfites, an alkali accelerator such as sodium hydroxide, sodium carbonate or potassium carbonate, an inorganic or organic inhibitor such as potassium bromide, 2-methylbenzimidazole or methylbenzothiazole, a water softener such as polyphosphates, and a development accelerator such as a trace amount of iodides or mercapto compounds.
  • a developing agent such as 1-phenyl-3-pyrazolidone, Metol or hydroquinone
  • a preservative such as sulfites
  • an alkali accelerator such as sodium hydroxide, sodium carbonate or potassium carbonate
  • an inorganic or organic inhibitor such as potassium bromide, 2-methylbenzimidazole or methylbenzothiazole
  • a water softener such as polyphosphates
  • a development accelerator such as a trace amount of i
  • the processing method of the present invention includes the processing steps of color development, bleaching, bleach-fixation and fixation.
  • the photographic material processed is generally subjected to a processing step of rinsing in water or stabilization.
  • the material may simply and directly be subjected to stabilization, without substantial rinsing in water.
  • a water softener such as inorganic phosphoric acids, aminopolycarboxylic acids or organic phosphoric acids; a bactericide or fungicide for preventing propagation of various bacteria, fungi and algae (such as isothiazolines, organic chlorine-containing bactericides, benzotriazoles); as well as a surfactant for preventing drying load or unevenness may be added to the rinsing water.
  • a surfactant for preventing drying load or unevenness
  • the compounds described in L.E. West, "Water Quality Criteria" Phot. Sci. and Eng. , Vol. 9, No. 6, pages 34 to 359, (1965) may also be used for the purpose.
  • a processing solution for stabilizing the color images formed is used.
  • a solution having a buffering capacity for a pH value of from 3 to 6, as well as a solution containing an aldehyde (such as formalin) can be used.
  • the stabilizing solution may contain, if desired, an ammonium compound, a metal compound such as Bi or Al compound, a brightening agent, a chelating agent (such as 1-hydroxy-ethylidene-1, 1-­diphosphonic acid), a bactericide, a fungicide, a film hardening agent and a surfactant.
  • a multistage countercurrent system is preferred.
  • the number of the stages is preferably from 2 to 4 stages.
  • the amount of the replenisher to the step is from 1 to 50 times, preferably from 2 to 30 times, more preferably from 2 to 15 times, the carryover amount from the previous bath, per unit area of the photographic material being processed.
  • water used in the rinsing step or stabilization step city water, water deionized by treatment with an an ion-exchange resin to have a Ca or Mg concentration of 5 mg/liter or less, and water as sterilizing by treatment with a halogen or ultraviolet sterilizing lamp is preferred.
  • the processing solution is often concnetrated by evaporation during processing.
  • concentration of the processing solution is noticeable.
  • a proper amount of water or replenisher is preferably added to the processing solution.
  • the overflow from the rinsing bath or stabilization bath may preferably be re-circulated to the previous bath having a fixing ability, whereby the amount of the drainage from the method may advantageously be reduced.
  • the silver halide incorporated into the photographic emulsion layer of the photographic material to be processed by the method of the present invention is silver chloride, silver bromide, silver chlorobromide, silver iodochloride, silver chloroiodobromide or silver iodobromide. It is preferred that the silver halide is that containing silver iodide in an amount of 30 mol% or less, preferably about 1 mol% to about 25 mol%. More preferably, the silver halide is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less silver iodide. Especially preferably, it is silver iodobromide containing silver iodide in an amount of from about 1 mol to about 25 mol%.
  • the silver halide grains in the photographic emulsion may have a regular crystal form such as a cubic, octahedral or tetradecahedral crystal form, or an irregular crystal form such as a spherical or tabular crystal form, or a crystal form having a crystal defect such as a twin plane, or further a composite form of these crystal forms.
  • the grains may be fine grains having a grain size of about 0.2 ⁇ m or less or may be large-sized grains having a projected area diameter of up to about 10 ⁇ m.
  • the emulsion of the grains may be either a polydispersed emulsion or a monodispersed emulsion.
  • an emulsion with a distribution where the maximum grain size of the grains in the grain group of up to 30% by number as counted from the smallest grains in the emulsion is 0.3 ⁇ m or less, especially preferably 0.17 ⁇ m or less, as the sphere-­corresponding diameter may be used, which is illustrated in European Patent 285,176.
  • Such emulsion is excellent in high sharpness, small color turbidity and broad exposure latitude.
  • the silver halide photographic emulsions to be used in the present invention can be prepared, for example, by the methods described in Research Disclosure (RD), Item 17643 (December 1978), pages 22 to 23, "I. Emulsion Preparation and Types"; RD Item 18716 (November 1979), page 648; P. Glafkides, Chemie et Phisique Photographique (Paul Montel, 1967); and G.F. Duffin, Photographic Emulsion Chemistry (Focal Press, 1966); and V.L. Zelikman et al., Making and Coating Photographic Emulsion (Focal Press, 1964).
  • tabular grains having an aspect ratio of about 5 or more may also be used. Such tabular grains may easily be prepared by the methods described, for example, in Gutoff, Photographic Science and Engineering, Vol. 14, pages 278 to 257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,043 and 4,439,520 and british Patent 2,112,157.
  • the crystal structure of the silver halide grains may be uniform throughout the whole grain, or the inside part and the outside part of one grain may have different halogen compositions, or one grain may have a layered structure. Further, silver halides of different compositions may be jointed by epitaxial junction or a silver halide may also be jointed with other compounds than silver halides, such as silver rhodanide or lead oxide, to form silver halide grains with a function struchture.
  • a mixture of grains of various crystal forms may also be used in the present invention.
  • the silver halide emulsion for use in the present invention is, in general, physically ripened, chemically ripened and spectrally sensitized. Additives for the ripening step or sensitizing step are described in Research Disclosure , Items 17643 and 18716, and the relevant parts are summarized in the following Table.
  • Stain Inhibitor p. 25 right column p. 650, from left to right column 8. Color Image Stabilizer p. 25 9. Hardening Agent p. 26 p. 651, left column 10. Binder p. 26 " 11. Plasticizer Lubricant p. 27 p. 650, right column 12. Coating Aid Surfactant pp. 26-27 " 13. Antistatic Agent p. 27 "
  • Various color couplers may be incorporated into the color photographic materials to be processed by the method of the present invention. Specific examples of couplers usable in the materials are described in the patent publications referred to in Research Disclosure (RD) item 17643, VII-C to G.
  • RD Research Disclosure
  • yellow couplers for example, the compounds described in U.S. Patents 3,933,501, 4,022,620, 4,326,024 and 4,401, 752, JP-B-58-10739, British Patents 1,425,020 and 1,476,760 are preferred.
  • 5-pyrazolone and pyrazoloazole compounds are preferred.
  • the compounds described in U.S. Patents 4,310,619 and 4,351,894, European Patent 73,636, U.S. Patents 3,061,432, and 3,725,067, Research Disclosure Item 24,220 (June, 1984), JP-A-60-33552, Research Disclosure Item 24,230 (June, 1984), JP-A 60-43659 and U.S. Patents 4,500,630 and 4,540,654 are especially preferred.
  • cyan couplers phenol coulpers and naphthol couplers
  • phenol coulpers and naphthol couplers can be used.
  • the compounds described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,9292, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,137, West German Patent Application (OLS) No. 3,329,729, European Patent 121,365A, U.S. Patents 3,446,622, 4,333,999, 4,451,559 and 4,427,767 and European Patent 161, 626A are preferred.
  • cyan couplers are 5-­amidonaphthol type cyan couplers described in European Patent 161,626A, JP-A-60-237448, 61-143640 and 61-145557, JP-A-62-123157, 62-123158, 62-269958 and 63-258446 and Japanese Patent Application No. 63-36542.
  • couplers include the following compounds but the present invention is not to be construed as being limited thereto.
  • polymerized dye-forming couplers which may be used in the present invention are described in U.S. Patents 3,451,820, 4,080,211 and 4,367,282 and British Patent 2,102,173.
  • Couplers capable of releasing a photographically useful group by coupling may also be preferably used in the present invention.
  • DIR couplers capable of releasing a development inhibitor the compounds described in the patent publications referred to in the RD Item 17,643, VII-F as well as those described in JP-A-57-­151944, 57-154234 and 60-184248 and U.S. Patent 4,248,962 are preferred.
  • couplers capable of imagewise releasing a nucleating agent or a development accelerator in development the compounds described in British Patents 2,097,140 and 2,131,188 and JP-A-59-157638 and 59-170840 are preferred.
  • couplers which can be used in the photographic material for the present invention include the competing couplers described in U.S. Patent 4,130,427, the polyequivalent couplers described in U.S. Patent 4,130,427, the polyequivalent couplers described in U.S. Patent 4,283,472, 4,338,393 and 4,310,618, the DIR redox compound-releasing couplers described in JP-A-60-185950, and the couplers capable of releasing a dye, which may be recolored after release, described in European Patent 173,302A.
  • the couplers for use in the present invention can be incorporated into the photographic materials by various known dispersing methods.
  • a water-in-oil dispersing method may be employed, and examples of high boiling point solvent to be used in the same method are described in U.S. Patent 2,322,027.
  • a method of using a polymer as a coupler-­dispersing medium may be also be employed, which is described in JP-B-48-30494, U.S. Patent 3,619,195, West German Patent 1,957,467 and JP-B-51-59835.
  • a latex-dispersing method may further be employed, and the steps of the method, the effect of the method and examples of dipping latexes to be used in the method are described in U.S. Patent 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
  • the photographic materials to be processed by the method of the present invention may contain a compound which may release a compound by reaction with the oxidation product of a developing agent, whereupon the thus-released compound further reacts with the oxidation product of another molecule of the developing agent to thereby release a development inhibitor.
  • a compound which may release a compound by reaction with the oxidation product of a developing agent whereupon the thus-released compound further reacts with the oxidation product of another molecule of the developing agent to thereby release a development inhibitor.
  • Examples of the compound of the type are described in European Patent 285,176.
  • such compounds include the following compounds, but the present invention is not to be construed as being limited thereto:
  • Supports which may suitably be used for the photographic materials to be processed by the method of the present invention may be those described, for example, in the RD Item 17643, page 28 and Item 18716, from page 647, right-hand column to page 648, left-hand column.
  • a multilayer color photographic material (Sample A) was prepared by forming the layers having the compositions shown below on a subbed cellulose triacetate film support.
  • compositions of the layers were as follows.
  • the amount coated was represented by the unit of g/m2 as silver, for silver halide and colloidal silver. It was represented by the unit of g/m2 for couplers, additives and gelatin. It was represented by the number of mols per mol of the silver halide in the same layer, for sensitizing dyes.
  • the respective layers contained a stabilizer Cpd-3 (0.04 g/m2) and a surfactant Cpd-4 (0.02 g/m2) as coating aids.
  • the thus-prepared multilayer color photographic material sample was exposed to light at 10 CMS at a color temperature of 4800°K and then processed in an automatic developing machine shown in Fig. 1 (processing speed is 40 cm/min.) in accordance with the procedure mentioned below (Table 1), whereupon the (aminopolycarboxylato)iron(III) complex (compounds (1) and (2)) in the bleaching solution and the pH value of the solution were varied as indicated below (Tables 2-1, 2-2).
  • the thus processed sample was dried at 65°C for 45 seconds.
  • the crossover time between the respective steps was 5 seconds, and the processing time shown in Table 1 above includes the crossover time.
  • compositions of the processing solutions used in the respective steps were as follows.
  • Diethylenetriaminepentaacetic Acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic Acid 2.0 g Sodium Sulfite 4.0 g Potassium Carbonate 30.0 g Potassium Bromide 1.4 g Potassium Iodide 1.3 mg Hydroxylamine Sulfate 2.4 g 4-(N-ethyl-N- ⁇ -hydroxyethylamino)-2-methylaniline Sulfate 4.5 g Water to make 1 liter pH 10.0
  • 1-Hydroxyethylidene-1,1-diphosphonic Acid 5.0 g Disodium Ethylenediaminetetraacetic Acid 5.0 g Sodium Sulfite 4.0 g Aqueous Ammonium Thiosulfate (70 wt.%/volume) 240 ml Sodium Bisulfite 4.6 g Water to make 1.0 liter pH 6.6
  • Formalin (40 wt.%) 1.0 ml Polyoxyethylene-p-monononylphenyl Ether (mean polymerization degree; about 10) 0.3 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.03 g Water to make 1.0 liter
  • Stirring of the bleaching bath and the fixing bath was effected in accordance with two different systems: (1) a jet stream-stirring system and (2) a circulation-­stirring system, which were applied to the bleach-fixing bath in Example 1 of JP-A-62-183460.
  • the former system is an embodiment of the present invention, while the latter system is a comparative conventional embodiment.
  • the jet stream of the processing solution was applied to the sample in 10 seconds after the sample was introduced into the bleaching bath or the fixing bath.
  • the residual silver amounts in the 20 CMS-exposed area and the non-­exposed area were measured by a fluorescent X-ray method.
  • the degree of the stain, if any, of the processed sample was visually observed.
  • J Jet stream-stirring system, described in Example 1 of JP-A-62-183460 N : Normal circulation-stirring system, described in Example 1 of JP-A-62-183460
  • the amount of the residual silver in the 20 CMS-exposed area contains both the non-­bleached silver and the non-fixed silver halide; while the amount of the residual silver in the non-exposed area corresponds to the non-fixed silver halide only and is the value of the silver due to fixation failure.
  • a multilayer color photographic material (Sample B) was prepared by forming the layers having the compositions shown below on a subbed cellulose triacetate film support.
  • compositions of the layers were as follows, where values are the amount coated (g/m2), and amount of the silver halide emulsion coated is the amount of silver therein.
  • amount of the sensitizing dye coated is represented by the molar unit to mol of the silver halide in the same layer.
  • First Layer Anti-halation Layer Black Colloidal Silver 0.18 as Ag Gelatin 0.40
  • Second Layer Interlayer 2,5-Di-t-pentadecylhydroquinone 0.18 Ex-1 0.07 Ex-3 0.02 Ex-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04
  • Third Layer First Red-sensitive Emulsion Layer Monodispersed Silver Iodobromide Emulsion (AgI 6 mol%; mean grain size 0.6 ⁇ m; variation coefficient of grain size 0.15) 0.55 as Ag Sensitizing Dye I 6.9 x 10 ⁇ 5 Sensitizing Dye II 1.8 x 10 ⁇ 5 Sensitizing Dye III 3.1 x 10 ⁇ 4 Sensitizing Dye IV 4.0 x 10 ⁇ 5 EX-2 0.350 HBS-1 0.005 EX-10 0.020 Gelatin 1.20
  • Fourth Layer Second Red-sensitive Emulsion Layer Tabular Silver Iodobromide Grain Emulsion (AgI 10 mol
  • a gelatin hardening agent H-1 and a surfactant were added to each of the respective layers.
  • the nozzles used have a round shape, each nozzle has 5 mm in diameter. 30 nozzles are arranged in a way to have 3 nozzles horizontally and 10 nozzles vertically and those are placed at the same intervals. The distance from the nozzle to the emulsion surface of the photographic material is about 1 cm, and the liquid is circulated at 15 l/min of jet stream speed.
  • Table 3 Processing Steps (temperature 38°C) Steps Processing Time Tank Capacity Color Development 3 min 00 sec 8 liters Bleaching 1 min 30 sec 8 liters Fixation 1 min 30 sec 8 liters Stabilization (1) 15 sec 4 liters Stabilization (2) 15 sec 4 liters Stabilization (3) 15 sec 4 liters
  • the stabilization was effected by a three-tank countercurrent system from the bath (3) to (2) to (1).
  • the crossover time between the respective steps was 5 seconds, and the processing time shown in the Table 3 above includes the crossover time.
  • the color developer and the stabilization used were same as those used in Example 1, and the bleaching solution and fixing solution used were as follows.
  • Compound (A) (indicated in Table 4) See Table 4 Bleaching Accelerator (indicated in Table 4) 7 x 10 ⁇ 3 mol Compound (B) (indicated in Table 4) See Table 4 Disodium Ethylenediaminetetraacetate 10.0 g Ammonium Bromide 150.0 g Ammonium Nitrate 10.0 g pH See Table 4 Water to make 1.0 liter
  • Example 2 The stirring system in the bleaching bath and the fixing bath was same as that in Example 1.
  • Example 2 the position of the first nozzle from which the jet stream of the bleaching solution was jetted was varied to thereby vary the time from the introduction of the sample being processed into the bleaching bath to the first application of the jet stream of the bleaching solution to the same sample. Accordingly, the time-dependent effect of the jet stream of the bleaching solution applied to the sample was clarified.
  • Example C a multilayer color photographic material prepared as mentioned below was used in place of Sample (B) used in Example 2.
  • the results obtained were the same as those in Table 4 of Example 2, and demonstrate that the method of the present invention is extremely excellent in desilvering capacity and is effective for prevention of bleaching fog and for prevention of insufficiency in recoloration of cyan dye.
  • the images formed were stored under the condition of 60°C and relative humidity of 70 % for 2 weeks, and the variation of the minimum magenta density after and before storage was determined.
  • Sample (C) was prepared by forming the layers having the compositions shown below on a subbed cellulose triacetate film support.
  • compositions of the layers were as follows.
  • the amount coated is in units of g/m2, calculated as silver for silver halide and colloidal silver, and in units of g/m2 for couplers, additives and gelatin.
  • the coated amount of sensitizing dye (ExS) is represented in molar amounts per mol of silver halide incorporated in the same layer.
  • the method of the present invention is effective for improving the image storability of the sample processed.
  • Example 2 The same samples as those in Example 2 were, after being imagewise exposed in the same manner as in Example 2, processed in accordance with the procedure described below.
  • Table 6 Steps Processing/time Tank Capacity l Amount of Replenisher (*) ml Color Development 3 min 15 sec 8 38 Bleaching 30 sec 8 8 Bleach-fixation 1 min 45 sec 8 33 Rinsing (1) 20 sec 4 - Rinsing (2) 20 sec 4 33 Stabilization 20 sec 4 33 (*)
  • the amount of the replenisher is that per 1 m of the photographic material sample (35 m/m width) processed.
  • the rinsing was effected by a two-tank countercurrent system from the rinsing tank 2) to the rinsing tank (1).
  • the overflow from the bleaching bath was introduced into the bleach-fixing bath.
  • compositions of the respective processing solutions used were as follows. Each replenisher used was the same as that of tank solution therefor.
  • Compound (A) (indicated in Table 7) See Table 7
  • Compound (B) (indicated in Table 7) See Table 7 Disodium Ethylenediamine tetraacetate 10.0 g Ammonium Nitrate 10.0 g Ammonium Bromide 150 g Bleaching Accelerator (Compound indicated in Table 7) 5 x 10 ⁇ 3 mol Water to make 1.0 l
  • Compound (A) (indicated in Table 7) See Table 7
  • Compound (B) (indicated in Table 7) See Table 7 Disodium Ethylenediamine tetraacetate 5.0 g Sodium Sulfite 12.0 g Aqueous Ammonium Thiosulfate (70 wt%) 240 ml Aqueous Ammonium to make pH of 7.3 Water to make 1.0 l
  • Fuji Color Super HR 100 (Emulsion No. 6266689) Fuji Color Super HR 200 (Emulsion No. 523009) Fuji Color Super HR 400 (Emulsion No. 315059) Fuji Color Super HR 1600 (Emulsion No. 723005)
  • Konica Color GX 100 (Emulsion No. 106)
  • Konica Color GX 400 (Emulsion No. 861)
  • Konica Color GX 3200 (Emulsion No. 751)
  • Kadacolor VRG 100 (Emulsion No. 5095 104) Kadacolor VRG 200 (Emulsion No. 5096 034) Kadacolor VRG 400 (Emulsion No. 5097 123) Kadacolor VRG 1000 (Emulsion No. 5090 254)
  • Sample (B) of Example 2 was exposed to light at 20 CMS at 4800°K and then processed.
  • the cyan dye density of the image formed was measured (first measurement).
  • the thus processed sample was dipped in the recloloring solution described below and then rinsed with water and dried.
  • the cyan dye density was again measured (second measurement).
  • the difference between the two values measured indicates the degree of insufficiency in recoloration of cyan dye. The larger the value, the greater the insufficiency in recoloration.
  • FIG. 1 show a partial sectional view of one embodiment of an automatic developing apparatus for the method of the present invention
  • (1) is a processing solution level
  • (2) is a means for liquid sealing and liquid squeezing
  • (3) is a receiver of liquid drops
  • (4) is a following lid
  • (5) is a conveyance roller
  • (6) is a conveyance roller
  • (7) is a pair of facing rollers
  • (8) is photographic material being processed
  • (9) is a processing liquid tank
  • (10) is a conveyance level
  • (11) is a bleaching solution
  • (12) is a fixing solution
  • (13) is a jet stream pipe
  • (14) is a circulation pump
  • (15) is a circulation pipe.
  • the arrows from the jet stream pipe (13) indicate the jet stream of a fixing solution to be jetted from the nozzles as provided in the jet stream pipe.
  • the fixing solution (12) is introduced into the jet stream pipe (13) via the circulation pipe (15) under section by the pump (14).
  • the emulsion surface of the photographic material being processed faces downwards.
  • the emulsion surface faces the jet stream pipe.
  • the crossover time between the bleaching solution and the fixing solution was varied, by changing the distance between the two tanks, as indicated in Table 8 below (Tests Nos. 1-1 to 9-2 ⁇ .
  • the processing procedure included the following Steps Processing/time Tank Capacity °C Amount of Replenisher (per m of 35 mm wide sample) ml Color Development 3 min 15 sec 38 20 Bleaching 40 sec 38 4 Fixation 1 min 15 sec 38 30 Rinsing (1) 20 sec 38 - Rinsing (2) 20 sec 38 20 Stabilization 20 sec 38 35 Drying 1 min 15 sec 50 to 70 -
  • the rinsing was carried out by a two-tank countercurrent system from the rinsing tank (2) to the rinsing tank (1).
  • the processing time for all the steps (except the bleaching step) contained a 5 second-crossover time.
  • the bleaching step included no crossover time
  • compositions of the processing solutions used were as follows.
  • City water was passed through a mixed bed column filled with an H-type strong acidic cation-exchange resin (Amberlite 1R-120B, product by Rhom and Haas Co.) and an OH-type anion-exchange resin (Amberlite IR-400, product by Rhom and Haas Co.) thereby to reduce the calcium ion concentration and the magnesium ion concentration to 3 mg/liter or less.
  • H-type strong acidic cation-exchange resin Amberlite 1R-120B, product by Rhom and Haas Co.
  • an OH-type anion-exchange resin Amberlite IR-400, product by Rhom and Haas Co.
  • Table 8 No. Crossover Time Jet Stream of Bleaching Solution Jet Stream of Fixing Solution Time Required until Arraival at Jet Stream of Fixing Solution Amount of Residual Silver ( ⁇ g/cm2) Degree of Recoloration Insufficiency Remarks 1-1 20 sec No No - 23 0.03 Comparative Example 1-2 Yes 23 0.03 " 2-1 10 No No - 21 0.10 " 2-2 Yes 21 0.09 " 3-1 10 No Yes 20 sec 9 0.10
  • the automatic developing machine used in Example 8 was a belt conveyance type machine described in JP-A-60-­191257, and the respective processing baths were stirred by the jet stream-stirring system described in JP-A-62-­183460.
  • the processing steps were as follows. Steps Processing/time Temperature °C Amount of Replenisher (per m of 35 mm wide sample) ml Color Development 3 min 15 sec 38 38 Bleaching 1 min 38 4 Fixation 1 min 38 30 Stabilization(1) 20 sec 38 - Stabilization(2) 20 sec 38 20 Stabilization(3) 20 sec 38 35 ml (*) Drying 1 min 15 sec 50 to 70 - (*)
  • the stabilization was carried out by a three-tank countercurrent system from the stabilization tank (3) to (2) to (1).
  • the crossover time in the respective steps was 5 seconds, and the above processing times include the crossover time.
  • compositions of the processing solutions used were as follows.
  • Tank Solution Replenisher 1-Hydroxyethylidene-1,1-diphosphonic Acid 5.0 g 6.0 g Sodium Sulfite 7.0 g 8.0 g Sodium Bisulfite 5.0 g 5.5 g
  • Aqueous Ammonium Thiosulfate Solution (700 g/l) 170.0 ml 200.0 ml Water to make 1.0 l 1.0 l pH 6.7 6.6
  • the sample processed with the bleaching solution (A) had the largest residual silver amount and that processed with the bleaching solution (B) had the second largest residual silver amount, while the samples processed with bleaching solutions (D), (E) and (H) had the smallest residual silver amount. It is noted from the results, that the ratio of EDTA ⁇ Fe/1,3-EDTA ⁇ Fe in the bleaching solution is preferably 3 to less.

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EP89102437A 1988-02-13 1989-02-13 Procédé de traitement de matériaux photographiques couleur à l'halogénure d'argent Expired - Lifetime EP0329051B1 (fr)

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JP63031120A JPH07120000B2 (ja) 1988-02-13 1988-02-13 ハロゲン化銀カラー写真感光材料の処理方法
JP3654988 1988-02-19
JP36549/88 1988-02-19
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064750A (en) * 1988-08-05 1991-11-12 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
EP0430018B1 (fr) * 1989-11-20 1997-01-22 Konica Corporation Procédé de traitement des matériaux photographiques à l'halogénure d'argent

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US3678842A (en) * 1969-06-06 1972-07-25 Norman C Reid Method and apparatus for processing photographic prints

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2719982A1 (de) * 1976-05-04 1977-11-10 Konishiroku Photo Ind Verfahren zum behandeln eines lichtempfindlichen photographischen silberhalogenidmaterials
JPS62183460A (ja) * 1986-02-07 1987-08-11 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
JPS62222252A (ja) * 1986-03-24 1987-09-30 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4601975A (en) * 1983-12-23 1986-07-22 Konishiroku Photo Industry Co., Ltd. Method for processing light-sensitive silver halide color photographic material
JPS64558A (en) * 1987-03-04 1989-01-05 Konica Corp Processing solution for silver halide color photographic sensitive material with improved faulty recoloring
EP0330043B1 (fr) * 1988-02-13 1996-01-17 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2719982A1 (de) * 1976-05-04 1977-11-10 Konishiroku Photo Ind Verfahren zum behandeln eines lichtempfindlichen photographischen silberhalogenidmaterials
JPS62183460A (ja) * 1986-02-07 1987-08-11 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
JPS62222252A (ja) * 1986-03-24 1987-09-30 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
62 183460 (FUJI PHOTO FILM) 11 August 1987, *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 32 (P-661)(2879) 30 January 1988, & JP-A-62 183460 (FUJI PHOTO FILM) 11 August 1987, *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 88 (P-678)(2935) 23 March 1988, & JP-A-62 222252 (FUJI PHOTO FILM) 30 September 1987, *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064750A (en) * 1988-08-05 1991-11-12 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material
EP0430018B1 (fr) * 1989-11-20 1997-01-22 Konica Corporation Procédé de traitement des matériaux photographiques à l'halogénure d'argent

Also Published As

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EP0329051B1 (fr) 1995-08-02
AU2989789A (en) 1989-08-17
AU614332B2 (en) 1991-08-29
DE68923630T2 (de) 1996-03-07
EP0329051A3 (en) 1990-06-13
DE68923630D1 (de) 1995-09-07

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