Method for processing silver halide color photographic materials

Description

[0001] 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 with sufficient desilvering in a short period of time to obtain a processed material having improved photographic properties.

[0002] The basic procedure for processing a color photographic material includes, in general, a color-development step and a desilvering step. In 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. In the desilvering step, 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 ions (which is generally called a "fixing agent"). After the desilvering step, the thus processed color photographic material may have a color image only.

[0003] 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 a bleaching agent and a fixing agent.

[0004] 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 for improving the storage stability of the images formed. For instance, such auxiliary steps are conducted using a film-hardening bath, a stopping bath, an image-stabilizing bath and a rinsing bath.

[0005] In accordance with the method of the present invention, the term "processing bath having a fixing ability" indicates both the fixing bath and the bleach-fixing bath. As 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.

[0006] On the other hand, in the bleaching step, the use of ferric complexes (for example, aminopolycarboxylic acid iron (III) complexes, especically an (ethylendiaminetetraacetato) iron (III) complex) is essentially in order to achieve rapid and simplified processing and to prevent environmental pollution.

[0007] However, ferric complexes are relatively poor in oxidizability and 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. However, when they are used for processing a high-sensitivity silver halide color photographic material, which essentially contains a silver chlorobromide emulsion or a silver iodobromide emulsion and which has been color-sensitized, especially a picture-taking color reversal photographic material or picture-taking color negative photographic material which contains a silver-rich emulsion, the bleaching capacity is not satisfactory; desilvering is insufficient and a long time is required for bleaching.

[0008] As a means of avoiding these deficiences, a method of using a bleaching agent combination of a (1, 3-diaminopropanetetraacetato) iron (III) complex and an (ethylenediaminetetraacetato) iron (III) complex 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").

[0009] However, it has been found that when a color photographic material is processed with a processing solution having a fixing ability and containing a thiosulfate, immediately after being processed with a bleaching solution containing the (1, 3-diaminopropanetetraacetato) iron (III) complex, the fixation is retarded and cannot be completed within a determined period of time. Such retardation of the fixation is a "fixation insufficiency", which is undesirable.

[0010] When aminopolycarboxylic acid which produces a compound, such as (1,3-diaminopropanetetracetato)iron (III) complex, having a low stability constant in binding to iron (III) is used, the compound causes a remarkable bleaching fog on a photosensitive material and insufficiency of recoloration of cyan dye, although it has a high bleaching ability.

[0011] In addition to such retardation of fixation, another serious problem is that the surface of the processed photographic material is stained.

[0012] In order to overcome such problems, Fuji Film Processing Manual, CN-16 Processing (October, 1985) has proposed a method wherein after processing a photographic material is fully rinsed or washed with water to remove the components of the bleaching solution from the processed photographic material. Although this method is effective to some degree, it interferes with rapid processing and additionally the number of the necessary processing baths 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.

[0013] It is the object of the present invention to provide a rapid desilvering method for processing color photographic materials wherein the material is not stained, has no bleaching fog and a high sufficiency in recoloration.

[0014] According to the present invention this object is attained with a method of processing a silver halide colour photographic material comprising the steps of:

(a) colour-developing an imagewise exposed silver halide colour photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer;

(b) bleaching said colour-developed colour photographic material with a bleaching solution containing (1,3-diamino-propanetetraacetato)iron(III) complex and having a pH of from 5.5 to 2.0 by contacting the emulsion surface of said material with a jet stream of said bleaching solution within 10 s arter introduction or said material into the bleaching solution; and

(c) immersing said material from step (b) in a solution having a fixing ability and contacting the emulsion surface of said material from step (b) with a jet stream of a solution having a fixing ability within 15 s after introduction into said solution having a fixing ability.

[0015] Preferred embodiments of the present invention are set forth in the dependent claims.

[0016] Fig. 1 shows a partial sectional view of one embodiment of an automatic developing apparatus for the method of the present invention.

[0017] The reason for the retardation of fixation in processing of a color photographic material with a processing solution having a fixing ability, after the material is bleached with a bleaching solution containing (1,3-diaminopropanetetraacetato) iron (III) complex, as well as the reason for staining of the surface of the photographic material thus processed is not completely known, but is considered to be as follows. Specifically, when a photographic material containing 1,3-diaminopropanetetraacetato) iron (III) complex (hereinafter referred to as "1,3-DPTA·Fe (III)) having a high oxidizing power in the emulsion layer is introduced into the processing solution having a fixing ability and containing a thiosulfate, 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. Further, the sulfur compound, penetrated into the gelatin layer or adhered to the surface near the layer, causes the stains in the material.

[0018] In accordance with the method of the present invention, 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.

[0019] Accordingly, 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 conducted within 15 s after the material has been dipped in the processing solution having a fixing ability.

[0020] In accordance with the method of the present invention, the color-developed photographic material 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, the 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 a device having a large number of nozzles is better. Each nozzle has a diameter of from 1mm to 10mm, and preferably from 1mm to 5mm and, e.g., a square, round or hexagonal shape.

[0021] 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"), 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 0.3 m/s to 3 m/s , and more preferred from 2 m/s to 3 m/s .

[0022] In one apparatus useful in the method of the invention, illustrated in Fig. 1, the arrows from the jet stream pipe (17) indicate the jet stream of a bleaching solution or a fixing solution to be jetted from the nozzles provided in the jet stream pipe. The bleaching solution (15) or the fixing solution (16) is introduced into the jet steam pipe (17) via the circulation pipe (19) under suction by the pump (18) At the position (4), the emulsion surface of the photographic material being processed faces downwards. In the bleaching bath (15) and the fixing bath (16), the emulsion surface faces the jet stream pipe.

[0023] In accordance with the method of the present invention, it is preferred that 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 s, after its introduction into the bath.

[0024] 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.

[0025] The acceleration of the fixation by the application of the jet stream of the processing solution having a fixing ability, in accordance with the method of the present invention, prevents the retardation of fixation due to 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 a conventional (ethylenediaminetetraacetato) iron (III) complex only. In addition, in accordance with the method of the present invention, another surprising effect of preventing stains in the processed photographic material can be attained.

[0026] The present invention is now explained in greater detail.

[0027] In the bath having a fixing ability for use in the present invention, a thiosulfate is generally used as the fixing agent. For instance, this includes sodium thiosulfate, ammonium thiosulfate and potassium thiosulfate, and the 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.

[0028] In addition, the bath may further contain thiocyanates, thioureas or thioethers, if desired.

[0029] The fixing solution for use in the present invention preferably contains an organic phosphonic acid type chelating agent for the purpose of improving the stability of the solution.

[0030] Most preferably, 1-hydroxyethylidene-1, 1-diphosphonic acid or N,N,N′,N′-ethylenediaminetetraphosphonic acid is used for the purpose.

[0031] 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.

[0032] 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.

[0033] When 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 :
   (1, 2-Propylenediaminetetraacetato) iron (III) complex,
   (1, 3-Propylenediaminetetraacetato) iron (III) complex,
   (Ethylenediaminetetraacetato) iron (III) complex, (Cyclohexanediaminetetraacetato) iron (III) complex and
   (Diethylenetriaminepentaacetato) iron (III) complex

[0034] The amount of the bleaching agent is preferably from 0.1 mol/l to 0.5 mol/l. 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.

[0035] 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.

[0036] 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 min to 4 min, preferably from 1 min and 30 s to 3 min. The processing temperature is from 25°C to 50°C, preferably from 35°C to 40°C.

[0037] Next, the bleaching solution for use in the present invention will be explained in greater detail.

[0038] 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 processed photographic material. The amount of the 1,3-DPTA·Fe (III) is preferably from 0.05 mol to 1 mol, more preferably from 0.1 mol to 0.5 mol, per liter of the bleaching solution.

[0039] In the method of the present invention, any other (aminopolycarboxylato) iron (III) complexe can be incorporated into the bleaching solution together with the 1,3-DPTA·Fe (III), if desired. Especially preferred are ferric complexes of the following compound group (A):

Compound Group (A):

[0040]    (A-1) Ethylenediaminetetraacetic acid
   (A-2) Diethylenetriaminepentaacetic acid
   (A-3) Cyclohexanediaminetetraacetic acid
   (A-4) 1,2-Propylenediaminetetraacetic acid

[0041] When these additional complexes are added to the solution, the molar proportion of the additional complex is 3 mol or less inclusive of 0 mol) per 1 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 mol, especially preferably from 0.1 to 1.5 mol, per mol of 1,3-DPTA·Fe (III).

[0042] Also in the step of processing the photographic material with the bleaching solution, it is preferred that a jet stream of the bleaching solution is directed against the photographic material being processed within 15 s 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. In particular, the time is especially preferably within 10 s.

[0043] The bleaching solution for use in the method of the present invention 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 bleaching fog. When the pH value of the bleaching solution is 5.5 to 2.0, the bleaching rate is extremely improved and the bleaching fog may be noticeably prevented. However, if the pH value is lower than that, the ferric complex in the bleaching solution precipitates.

[0044] 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 a low pH condition.

[0045] In accordance with the present invention, when the color photographic material is, after color-development, processed with the bleaching solution, it is particularly preferred that 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.

[0046] 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 s or less, preferably 5 s or less, especially preferably 3 s or less, whereby the processed photographic material may be effectively prevented.

[0047] When a photographic material film is processed with an automatic developing machine in accordance with the method of the present invention, various methods may be used to shorten the crossover time. For instance, 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 cm from the liquid surface of this tank, whereupon it is preferable to provide a dead space between the tanks for the purpose of intermixing of the processing solutions of the respective tanks. Any of these methods can be employed in the practice of the present invention.

[0048] In the case of a small-sized automatic developing machine (a "mini-laboratory"), 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 to 10 s or less, for example 3 s or less.

[0049] In the case where the crossover time is not extremely shortened, for example, from 5 to 10 s, the bromide ion concentration in the bleaching solution is preferably from 1.2 mol/l (or 118 g/l as NH₄Br) to 3.0 mol/l, more preferably 1.5 to 2.8 mol/l and most preferably 1.7 to 2.5 mol/l whereby the yellow density increase is substantially reduced to 0.

[0050] In addition, the other problem of staining of the processed film may also be prevented by elevation of the bromide ion concentration in the bleaching solution. For instance, the bromide ion concentration is preferably from 1.2 mol/l (or 118 g/l as NH₄Br) to 3.0 mol/l, more preferably 1.5 (147 g/l as NH₄Br)to 2.8 mol/l and most preferably 1.7 to 2.5 mol/l. When the said concentration is 1.7 mol/l (or 167 g/l as NH₄Br) or more, staining of the processed film may be completly prevented.

[0051] In accordance with the method of the present invention, shortening of the crossover time from the bleaching solution to the processing solution having a fixing ability to 10 s 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 s or less, especially to 3 s 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.

[0052] 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 US-A-3,893,858, GB-B-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.

[0053] In addition, the compounds of formulae (I), (II), (III), (IV), (V), (VI), (VII) and (VIII) disclosed in JP-A-62-222252, pages 4 to 11 are especially preferred for their excellent bleaching capacity. The effect of these compounds is particularly noticeable when they are used in combination with the jet stream of the bleaching solution applied to the photographic material being processed.

[0054] The amount of the comopounds of formulae (I) to (VIII) to be added is preferably from 1 x 10⁻⁴ to 1 x 10⁻¹ mol/ℓ, more preferably from 3 x 10⁻⁴ to 1 x 10⁻² mol/ℓ and most preferably from 1 x 10⁻³ to 8 x 10⁻³ mol/ℓ.

[0055] The following compounds are preferred.

[0056] 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.

[0057] In the method of the present invention, the replenishing amount of the fixing solution preferably is from 50 ml to 2000 ml, more preferably from 100 ml to 1000 ml, per m² of the photographic material being processed.

[0058] The method of the present invention can be carried out in an automatic developing machine, which will be explained in detail hereunder. In the automatic developing machine to be used for the method of the present invention, 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.

[0059] The stirring acclerating means is more effective when a bleaching accelerator is used, whereby the bleaching accelerating effect can be noticeably enhanced and the fixation retardation or insufficiency may be eliminated because of the bleaching accelerator.

[0060] 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. As described in JP-A-60-191257, 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.

[0061] 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.

D- 1:

N,N-diethyl-p-phenylenediamine

D- 2:

2-Amino-5-diethylaminotoluene

D- 3:

2-Amino-t-(N-ethyl-N-laurylamino)toluene

D- 4:

4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline

D- 5:

2-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline

D- 6:

4-Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)-ethyl]aniline

D- 7:

N-(2-amino-5-diethylaminophenylethyl) methanesulfonamide

D- 8:

N,N-dimethyl-p-phenylenediamine

D- 9:

4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline

D-10:

4-Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline

D-11:

4-Amino-3-methyl-n-ethyl-n-β-butoxyethylaniline

[0062] Among these p-phenylenediamine derivatives, (D-5) is especially preferred.

[0063] 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 0.1 g to 20 g, more preferably from 0.5 g to 10 g per liter of the developer.

[0064] 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.

[0065] 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.

[0066] 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 α-hydoroxyketones and α-aminoketones described in JP-A-63-44656 and/or various saccharides described in JP-A-63-36244 are preferably added to the color developer. Further, in combination with these compounds, 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.

[0067] As other preservatives, various metals described in JP-A-57-44148 and 57-53749, the salicylic acids described in JP-A-59-180588, the alkanolamines described in JP-A-54-3532, the polyethyleneimines described in JP-A-56-94349, and the aromatic polyhydroxy compounds described in US-A-3, 746, 544 may optionally be incorporated into the color developer for use in the present invention. In particular, incorporation of aromatic polyhydroxy compounds as a preservative is preferred.

[0068] 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.

[0069] In order to maintain this pH value, the color developer preferably contains various buffers.

[0070] Specific examples of 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 and sodium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

[0071] The amount of the buffer to be added to the color developer is preferably 0.1 mol/l or more, and is especially preferably from 0.1 mol/l to 0.4 mol/l.

[0072] In addition, 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.

[0073] As the chelating agents organic acid compounds are preferred, in particular e.g., aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids. Specific examples of 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)ethylenedimaine-N,N′-diacetic acid. These chelating agents may be used alone or in the form of a mixture of two or more of them, if desired.

[0074] 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. For instance, the amount may be from 0.1 g to 10 g per liter of the developer.

[0075] The color developer may contain any optional development accelerator, if desired. However, it is preferred that 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. The term "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.

[0076] Other 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 US-A-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 US-A-2,494,903, US-A-3,128,182, US-A-4,230,796 and US-A-3,253,919, JP-B-41-11431, US-A-2,482,546, US-A-2,596,926 and US-A-3,582,346, the polyalkyleneoxides described in JP-B-37-16088 and 42-25201, US-A-3,18,183, JP-B-41-11431 and 42-23883 and US-A-3,532,501 as well as other 1-phenyl-3-pyrazolidones and imidazoles.

[0077] In accordance with the present invention, any optional anti-foggant can be added to the color developer, if desired. As the anti-foggant alkali metal halides such as sodium chloride, potasium bromide or potassium idodide can be used, as well as organic anti-foggants. Specific examples of organic anti-foggants which may be used in the present invention, 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.

[0078] The color developer for use in the present invention preferably contains a brightening agent. As the brightening agent 4,4′diamino-2, 2′-disulfostilbene compounds are preferred. The amount of the brightening agent to be added to the color developer is up to 5 g/l, preferably from 0.1 to 4 g/l.

[0079] In addition, 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.

[0080] 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 s to 5 min, preferably from 30 s to 3 min. 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 processed photographic material.

[0081] The color development may be effected in a multi-bath system containing two or more baths, where a replenisher for the 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.

[0082] The processing method of the present invention can be applied to color reversal processing. In such 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.

[0083] 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 methylbenzothiazoie, a water softener such as polyphosphates, and a development accelerator such as a trace amount of iodides or mercapto compounds.

[0084] The processing method of the present invention includes the processing steps of color development, bleaching, bleach-fixation and fixation. After the bleach-fixation or fixation step, the photographic material processed is generally subjected to a processing step of rinsing in water or stabilization. After being processed in the bath having a fixing ability, the material may simply and directly be subjected to stabilization, without substantial rinsing in water.

[0085] Known additives may be added to the rinsing water used in the rinsing step, if desired. For instance, 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. In addition, 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.

[0086] As the stabilizing solution used in the stabilization step, a processing solution for stabilizing the color images formed is used. For instance, 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.

[0087] For the rinsing step or stabilization step, 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.

[0088] As the 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/l or less, and water that has been sterilized by treatment with a halogen or ultraviolet sterilizing lamp is preferred.

[0089] When the method of the present invention is carried out continuously by the use of an automatic developing machine, the processing solution is often concentrated by evaporation during processing. In particular, when the amount of the photographic material to be processed is small or when the open area of the processing solution is large, such concentration of the processing solution is noticeable. In order to compensate the thus-concentrated processing solution, a proper amount of water or replenisher is preferably added to the processing solution.

[0090] 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.

[0091] 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 contains silver iodide in an amount of 30 mol% or less, preferably 1 mol% to 25 mol%. More preferably, the silver halide is silver iodobromide, silver iodochloride or silver iodochlorobromide containing 30 mol% or less silver iodide. Especially preferably, it is silver iodobromide containing silver iodide in an amount of from 1 mol to 25 mol%.

[0092] 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.

[0093] Regarding the grain size of the silver halide grains, the grains may be fine grains having a grain size of 0.2 »m or less or may be large-sized grains having a projected area diameter of up to 10 »m. The emulsion of the grains may be either a polydispersed emulsion or a monodispersed emulsion.

[0094] As one embodiment of the silver halide emulsion for use in the present invention, 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 EP-B-285,176. Such emulsion is excellent in high sharpness, small color turbidity and broad exposure latitude.

[0095] 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).

[0096] In addition, the monodispersed emulsions described in US-A-3,574,628 and US-A-3,655,394 and GB-B-1,413,748 are also preferably used.

[0097] Further tabular grains having an aspect ratio of 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), US-A-4,434,226, US-A-4,414,310, US-A-4,433,043 and US-A-4,439,520 and GB-B-2,112,157.

[0098] 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 junction structure.

[0099] A mixture of grains of various crystal forms may also be used in the present invention.

[0100] 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.

[0101] Known photographic additives which can be used in the present invention are also described in these two Research Disclosures, and the relevant parts are also summarized in the same Table.

[0102] 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.

[0103] As yellow couplers, for example, the compounds described in US-A-3,933,501, US-A-4,022,620, US-A-4,326,024 and US-A-4,401, 752, JP-B-58-10739, GB-B-1,425,020 and GB-B-1,476,760 are preferred.

[0104] As magenta coulpers, 5-pyrazolone and pyrazoloazole compounds are preferred. For example, the compounds described in US-A-4,310,619 and US-A-4,351,894, EP-B-73,636, US-A-3,061,432, and US-A-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 US-A-4,500,630 and US-A-4,540,654 are especially preferred.

[0105] As cyan couplers, phenol coulpers and naphthol couplers can be used. For example, the compounds described in US-A-4,052,212, US-A-4,146,396, US-A-4,228,233, US-A-4,296,200, US-A-2,369,9292, US-A-2,801,171, US-A-2,772,162, US-A-2,895,826, US-A-3,772,002, US-A-3,758,308, US-A-4,334,011 and US-A-4,327,137, DE-A-3,329,729, EP-A-121,365, US-A-3,446,622, US-A-4,333,999, US-A-4,451,559 and US-A-4,427,767 and EP-A-161, 626 are preferred.

[0106] Especially preferred cyan couplers are 5-amidonaphthol type cyan couplers described in EP-A-161,626, 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.

[0107] Specific examples of such couplers include the following compounds.

[0108] As colored couplers for correcting the unnecessary absorption of the colored dyes, the compounds described in Research Disclosure Item 17643, VII-G, US-A-4,163,670, JP-B-57-39413, US-A-4,004,929 and US-A-4,138,258 and GB-B-1,146,368 are preferred.

[0109] As couplers capable of forming colored dyes having a suitable diffusibility, the compounds described in US-A-4,366,237, GB-B-2,125,570, EP-B-96,570 and DE-A-3,234,533 are preferred.

[0110] Specific examples of polymerized dye-forming couplers which may be used in the present invention are described in US-A-3,451,820, US-A-4,080,211 and US-A-4,367,282 and GB-B-2,102,173.

[0111] Couplers capable of releasing a photographically useful group by coupling may also be preferably used in the present invention. As 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 US-A-4,248,962 are preferred.

[0112] As couplers capable of imagewise releasing a nucleating agent or a development accelerator in development, the compounds described in GB-B-2,097,140 and GB-B-2,131,188 and JP-A-59-157638 and 59-170840 are preferred.

[0113] In addition, couplers which can be used in the photographic material according to the present invention, include the competing couplers described in US-A-4,130,427, the polyequivalent couplers described in US-A-4,130,427, the polyequivalent couplers described in US-A-4,283,472, US-A-4,338,393 and US-A-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 EP-A-173,302.

[0114] The couplers for use in the present invention can be incorporated into the photographic materials by various known dispersing methods.

[0115] For instance, a water-in-oil dispersing method may be employed, and examples of high boiling point solvents to be used in the same method are described in US-A-2,322,027.

[0116] A method of using a polymer as a coupler-dispersing medium may also be employed, which is described in JP-B-48-30494, US-A-3,619,195, DE-B-1,957,467 and JP-B-51-59835.

[0117] 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 US-A-4,199,363, DE-A-2,541,274 and DE-A-2,541,230.

[0118] 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. Examples of the compound of the type are described in EP-B-285,176.

[0119] Specifically, such compounds include the following compounds:

D-1

R_a = C₃F₇(n)   R_b = H   R_c = -CH₂CH₂CO₂CH₃

D-2

R_a = C₃F₇(n)   R_b = -C₂H₅   R_c = -CH₂CH₂CO₂CH₃

D-3

R_a = C₃F₇(n)   R_b = H

D-4

R_a = C₃F₇(n)   R_b = -C₂H₅

D-5

R_a = C₃F₇(n)   R_b = H   R_c = -CH₂CO₂CH₃

D-6

R_a = C₃F₇(n)   R_b = -C₄H₉(n)   R_c = -CH₂CO₂CH₃

D-7

R_a = (t)C₄F₉   R_b = H   R_c = -CH₂CH₂CO₂CH₃

D-8

R_d = H

D-9

R_d = COOC₂H₅

[0120] Incorporation of 5-amidohydroquinone derivatives (described in EP-B-284,082) into the photographic materials for use in the present invention is preferred, as these derivatives are excellent in high color reproducibility, small sensitivity fluctuation in running procedure, small insufficiency in recoloration and fine graininess.

[0121] Specific examples of such derivatives include the following compounds:

[0122] 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.

[0123] The following examples are provided to illustrate specific embodiments of the present invention in greater detail. Unless otherwise indicated all parts, ratios and percentages are by weight.

EXAMPLE 1

[0124] 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.

[0125] The 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.

First Layer: Anti-halation Layer

Second Layer: Interlayer

Third Layer: Low-sensitive Red-sensitive Emulsion Layer

Fourth Layer: High-sensitive Red-sensitive Emulsion Layer

Fifth Layer: Interlayer

Sixth layer: Low-sensitive Green-sensitive Emulsion Layer

Seventh Layer: High-sensitive Green-sensitive Emulsion Layer

Eighth Layer: Interlayer

Nineth Layer: Donor Layer for Interlayer Effect to Red-sensitive Layer

Tenth Layer: Yellow Filter Layer

Eleventh Layer: Low-sensitive Green-sensitive Emulsion Layer

Twelfth Layer: High-sensitive Blue-sensitive Emulsion Layer

Thirteenth Layer: First Protective Layer

Fourteenth Layer: Second Protective Layer

[0126] In addition to the above-mentioned components, the respective layers contained a stabilizer Cpd-3 (0.04 g/m²) and a surfactant Cpd-4 (0.02 g/m²) as coating aids.

[0127] The compounds used were as follows:

Solv-1

Tricresyl Phosphate

Solv-2

Dibutyl Phthalate

Solv-3

Solv-4

[0128] 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 macnine shown in Fig. 1 (processing speed of 40 cm/min₁) 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).

[0129] The thus processed sample was dried at 65°C for 45 s. The crossover time between the respective steps was 5 s, and the processing time shown in Table 1 above includes the crossover time.

[0130] The compositions of the processing solutions used in the respective steps were as follows.

Color Developer:

[0131] 

Bleaching Solution:

[0132] 

Fixing Solution:

[0133] 

Stabilizer:

[0134] 

[0135] 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 s after the sample was introduced into the bleaching bath or the fixing bath.

[0136] For the thus processed samples, the residual silver amounts in the 20 CMS-exposed area and the non-exposed area were measured by a fluorescent X-ray method. In addition, the degree of the stain, if any, of the processed sample was visually observed.

[0137] The results of the samples processed by the circulation-stirring system of the bleaching bath are shown in Table 2-1 and those of samples processed by the jet steam-stirring system of the bleaching bath are shown in Table 2-2.

Stirring System:

[0138] 

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

[0139] In Tables 2-1 and 2-2, 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.

[0140] As is clear from the results in Table 2-1, the amount of the silver due to fixation failure was far smaller in the case where the fixing solution was applied to the sample in accordance with a jet stream-stirring system (Examples Nos. 2 to 6 and Nos. 13 to 15 of Table 2-1) than in the case where the fixing solution was applied to the sample by conventional circulation-stirring system (Examples Nos. 8 to 12 and Nos. 16 to 18 of Table 2-1).

[0141] In addition, when the bleaching solution was applied to the sample in accordance with a jet stream-stirring system (see Table 2-2), the amount of the silver due to fixation failure was further reduced when the fixing solution was applied to the sample by a jet stream-stirring system, but this effect could not be obtained when the fixing solution was applied to the sample by a conventional circulation-stirring system.

[0142] Further, as is noted from the results in Table 2-1 and 2-2, the amount of the residual silver in the non-exposed part increased in accordance with the increase of the proportion of 1,3-DPTA·Fe(III) and the photographic material samples processed were noticeably stained, when the fixation was effected by conventional circulation stirring (Comparative Examples Nos. 7 to 12 of Tables 2-1 and 2-2).

[0143] As opposed to this, excellent desilvering which was free from these problems was possible, when the jet stream-stirring of the present invention was employed in the fixation step (Examples Nos. 2 to 6 of Table 2-2).

[0144] When the pH value of the bleaching solution was lowered, the fixation failure increased in the comparative case where the fixation was effected by conventional circulation stirring, while no fixation was noted in the case of the present invention where the fixation was effected by the jet stream-stirring system of the invention.

[0145] As is clear from the above results, the desilvering was effectively achieved by the method of the present invention and the photographic materials after being desilvered were not stained.

Example 2

[0146] 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.

[0147] The 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. The 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

Second Layer: Interlayer

Third Layer: First Red-sensitive Emulsion Layer

Fourth Layer: Second Red-sensitive Emulsion Layer

Fifth Layer: Third Red-sensitive Emulsion Layer

Sixth Layer: Interlayer

Seventh Layer: First Green-sensitive Emulsion Layer

Eighth Layer: Second Green-sensitive Emulsion Layer

Nineth Layer: Third Green-sensitive Emulsion Layer

Tenth Layer: Yellow Filter Layer

Eleventh Layer: First Blue-sensitive Emulsion Layer

Twelfth Layer: Second Blue-sensitive Emulsion Layer

Thirteenth layer: Third Blue-sensitive Emulsion Layer

Fourteenth Layer: First Protective Layer

Fifteenth Layer: Second Protective Layer

[0148] In addition to the above-mentioned components, a gelatin hardening agent H-1 and a surfactant were added to each of the respective layers.

[0149] The compounds used were as follows.

U-1:

Same as UV-1 in Example 1

U-2:

Same as UV-2 in Example 1

U-3:

Same as UV-3 in Example 1

U-4:

Same as UV-4 in Example 1

U-5:

Same as UV-5 in Example 1

EX-1:

Same as ExM-9 in Example 1

EX-2:

Same as ExC-2 in Example 1

EX-3:

Same as ExC-4 in Example 1

EX-4:

Same as ExC-7 in Example 1

EX-5:

Same as Cpd-1 in Example 1

EX-6:

Same as ExM-8 in Example 1 (mean molecular weight: 30,000)

EX-7:

Same as ExM-12 in Example 1

EX-8:

Same as ExY-13 in Example 1

EX-9:

Same as ExY-15 in Example 1

EX-10:

Same as ExC-16 in Example 1

EX-11:

Same as ExM-9 in Example 1 (R =H)

EX-12:

Same as ExF-1 in Example 1

S-1:

Same as Cpd-5 in Example 1

S-2:

Same as Cpd-6 in Example 1

HBS-1:

Tricresyl Phosphate (same as Solv-1 in Example 1)

HBS-2:

Dibutyl Phthalate( same as Solv-2 in Example 1)

HBS-3:

Bis(2-ethylhexyl) Phthalate

HBS-4:

Same as Solv-4 in Example 1

Sensitizing Dyes:

[0150] The thus prepared Sample (B) was imagewise exposed in the same manner as in Example 1 and then developed in accordance with the development procedure.

[0151] The nozzles used have a round shape, each nozzle having a diameter of 5 mm. 30 nozzles are arranged in such a way that 3 nozzles are horizontally and 10 nozzles are vertically 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.

[0152] After being processed, the sample was dried at 65°C for 45 s.

[0153] In the above procedure, the stabilization was effected by a three-tank countercurrent system from the bath (3) to (2) to (1).

[0154] The crossover time between the respective steps was 5 s, and the processing time shown in the Table 3 above includes the crossover time.

[0155] The color developer and the stabilization used were the same as those used in Example 1, and the bleaching solution and fixing solution used were as follows.

Bleaching Solution:

[0156] 

Fixing Solution:

[0157] 

[0158] The stirring system in the bleaching bath and the fixing bath was the same as that in Example 1. In 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.

[0159] The amount of the residual silver, the minimum yellow density and the maximum cyan density were measured for the thus processed samples, and the results are shown in Table 4 below.

[0160] For determination of the color density, an X-light 310 Photographic Densitometer was used.

[0161] As is noted from the results of Tests Nos. 4 to 7 in Table 4 above, when the time from the introduction of the photographic material sample into the bleaching bath to the application of the jet stream of the bleaching solution to the same sample was more than 10 s, the amount of the residual silver in the sample processed was large and increase of the minimum yellow density (bleaching fog) and depression of the maximum cyan density (insufficiency in recoloration) were noticeable, however, when the said time was 10 s or less, these problems were overcome.

EXAMPLE 3

[0162] The same process as in Example 2 was repeated except that a multilayer color photographic material (Sample C) 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.

[0163] In addition, it was also demonstrated that the method of the present invention is effective to improve image storability, which is often problematic in rapid photographic processing, as shown by the experimental data in Table 5 below.

[0164] For evaluation of image stability, 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.

[0165] Sample (C) was prepared by forming the layers having the compositions shown below on a subbed cellulose triacetate film support.

[0166] The 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.

First Layer: Anti-halation Layer

Second Layer: Interlayer

Third Layer: First Red-sensitive Emulsion Layer

Fourth Layer: Second Red-sensitive Emulsion Layer

Fifth Layer: Third Red-sensitive Emulsion Layer

Sixth Layer: Interlayer

Seventh Layer: First Green-sensitive Emulsion Layer

Eighth Layer: Second Green-sensitive Emulsion Layer

Nineth Layer: Interlayer

Tenth Layer: Third Green-sensitive Emulsion Layer

Eleventh Layer: Yellow Filter Layer

Twelfth Layer: Interlayer

Thirteenth Layer: First Blue-sensitive Emulsion Layer

Fourteenth Layer: Second Blue-sensitive Emulsion Layer

Fifteenth Layer: Interlayer

Sixteenth Layer: Third Blue-sensitive Emulsion Layer

Seventeenth Layer: First Protective Layer

Eighteenth Layer: Second Protective Layer

[0167] The compounds used were as follows













:

[0168] As is clear from the data in Table 5, the method of the present invention is effective for improving the image storability of the sample processed.

EXAMPLE 4

[0169] 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.

[0170] After being thus processed, the sample was dried at 65°C for 1 min.

[0171] In the above procedure, 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.

[0172] The compositions of the respective processing solutions used were as follows. Each replenisher used was the same as that of tank solution therefor.

Color Developer:

[0173] Same as that used in Example 1

Bleaching Solution:

[0174] 

Bleach-fixing Solution:

[0175] 

[0176] 

Rinsing Solution:

[0177] 20 mg/ℓ of sodium chloroisocyanurate were added to deionized water having an electroconductivity of 5 »s/cm.

Stabilizing Solution:

[0178] 

[0179] As is clear from the data in Table 7, the method of the present invention proved effective in the procedure where the photographic material sample was bleached and then bleach-fixed.

Example 5

[0180] The processes of Tests Nos. 2 to 6, Nos. 13 to 15 in Example 1 and Tests Nos. 3 to 16 in Example 2 were carried out, using color negative films mentioned below, and the same good results as those attained in Examples 1 (Tables 2-1 and 2-2) and 2 were also attained.
Color Negative Films Used:
   Products by Fuji Photo Film Co.
   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)
   Products by Konica Co.
   Konica Color GX 100 (Emulsion No. 106)
   Konica Color GX 400 (Emulsion No. 861)
   Konica Color GX 3200 (Emulsion No. 751)
   Products by Eastman Kodak Co.
   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)

EXAMPLE 6

[0181] 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). Next, the thus processed sample was dipped in the recloloring solution described below and then rinsed with water and dried. Then the cyan dye density was again measured (second measurement). The difference between the two values measured (Value of the second measurement minus value of the first measurement) indicates the degree of insufficiency in recoloration of cyan dye. The larger the value, the greater the insufficiency in recoloration.

[0182] The procedure of processing the exposed sample was as follows.

[0183] An automatic developing machine shown in Fig. 1, which was equipped with a conveyance mechanism, was used for processing the exposed sample. With reference to Fig. 1, which shows 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; (15) is a bleaching solution; (16) is a fixing solution; (17) is a jet stream pipe; (18) is a circulation pump; and (19) is a circulation pipe. The arrows from the jet stream pipe (17) indicate the jet stream of a fixing solution to be jetted from the nozzles as provided in the jet stream pipe. The fixing solution (16) is introduced into the jet stream pipe (17) via the circulation pipe (19) under section by the pump (18) At the position (18), the emulsion surface of the photographic material being processed faces downwards. In the fixing bath (16), the emulsion surface faces the jet stream pipe.

[0184] 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).

[0185] The processing procedure included the following

[0186] 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 s-crossover time. The bleaching step included no crossover time

[0187] The compositions of the processing solutions used were as follows.

Color Developer:

[0188] 

Bleaching Solution:

[0189] 

Fixing Solution:

[0190] 

Stabilizing solution: Tank Solution and replanisher were same.

[0191] 

Rinsing Solution

[0192] City water was passed through a mixed bed column filled with a commercially available H-type strong acidic cation-exchange resin and an OH-type anion-exchange resin of the commercial type to thereby reduce the calcium ion concentration and the magnesium ion concentration to 3 mg/l or less.

[0193] The results are shown in Table 8 below.

[0194] As is clear from the results in Table 8, the amount of the residual silver in the sample processed was noticeably reduced by application of the jet stream of the fixing solution to the sample. When the crossover time of the fixing solution was shortened, the insufficiency in recoloration increased. However, when the time required until arrival at the jet stream of the fixing solution was made 10 s or less, the insufficiency in recoloration was noted to be remarkably overcome.

Example 7

[0195] Sample Nos. 101 to 108 in Example 1 and Examples Nos. 201 to 208 in Example 2 of EP-B-285,1786 were imagewise exposed and then processed by the procedure described below, whereupon the processing was continued until the replenisher was consumed in an amount of two times the tank capacity of the color developer tank for running test. In the procedure, the composition of the bleaching solution was varied, as indicated in Table 9 below.

[0196] 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.

[0197] The processing steps were as follows.

[0198] The crossover time in the respective steps was 5 s, and the above processing times include the crossover time.

[0199] The compositions of the processing solutions used were as follows.

Color Developer:

[0200] 

Bleaching Solution:

[0201] 

Fixing Solution:

[0202] 

Stabilizing Solution: Tank solution and replenisher were the same.

[0203] 

[0204] The above samples were exposed with light at 20 CMS and then processed with the running-equilibrated solution, and the amount of the residual silver in the thus processed samples was measured by a fluorescent X-ray method.

[0205] As a result, the difference in the photographic characteristic between the samples Nos. 101 to 108 and that between the sample Nos. 201 to 208 were relatively small despite of the extreme difference between the bleaching solutions (A) to (I) used.

[0206] Regarding the amount of the residual silver, 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.

Claims

1. A method of processing a silver halide colour photographic material comprising the steps of:

(a) colour-developing an imagewise exposed silver halide colour photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer;

(b) bleaching said colour-developed colour photographic material with a bleaching solution containing (1,3-diamino-propanetetraacetato)iron(III) complex and having a pH of from 5.5 to 2.0 by contacting the emulsion surface of said material with a jet stream of said bleaching solution within 10 s after introduction of said material into the bleaching solution; and

(c) immersing said material from step (b) in a solution having a fixing ability and contacting the emulsion surface of said material from step (b) with a jet stream of a solution having a fixing ability within 15 s after introduction into said solution having a fixing ability.

2. The method of claim 1, wherein said solution having a fixing ability is a fixing solution.

3. The method of claim 1, wherein said jet streams have a flow velocity of from 0.3m/s to 3m/s at the nozzle.

4. The method of claim 1, wherein said photographic material is contacted by said jet stream of a solution having a fixing ability within 10 s after being introduced into said solution having a fixing ability.

5. The method of claim 1, wherein said solution having a fixing ability is a fixing solution containing a thiosulfate in an amount of from 50 to 500 g per l of the fixing solution.

6. The method of claim 1, wherein the processing time from the beginning of step (b) to the end of step (c) is from 1 min to 4 min.

7. The method of claim 1, wherein said (1,3-diamino-propanetetraacetato)iron(III) complex is an ammonium salt complex.

8. The method of claim 1, wherein said bleaching solution contains from 0.05 mol to 1 mol of said (1,3-diaminopropanetetraacetato)iron(III) complex per l of said bleaching solution.

9. The method of claim 1, wherein said bleaching solution further contains at least one ferric complex of an acid selected from the group consisting of
ethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid,
cyclohexanediaminetetraacetic acid and
1,2-propylenediaminetetraacetic acid.

10. The method of claim 9, wherein said bleaching solution contains from 0.1 to 3.0 mols of said ferric complex per mol of (1,3-diaminopropanetetraacetato)iron(III) complex.

11. The method of claim 1, wherein the pH of said bleaching solution in step (b) is from 5.0 to 3.0.

12. The method of claim 11, wherein the pH of said bleaching solution in step (b) is from 4.5 to 3.5.

13. The method of claim 1, wherein the interval between said developing step (a) and said bleaching solution processing step (b) is at most 10 s.

14. The method of claim 1, wherein the interval between said bleaching solution processing step (b) and said processing step (c) with the jet stream of the solution having a fixing ability is 10 s or less.

15.  The method of claim 1, wherein said bleaching solution has a bromide ion concentration of from 1.2 to 3.0 mol/l.

16. The method of claim 1, wherein the silver halide contained in said silver halide colour photographic material contains 30 mol% or less of silver iodide.

Ansprüche

1. Verfahren zum Verarbeiten eines farbfotographischen Silberhalogenidmaterials, umfassend die Schritte :

(a) Farbentwickeln eines bildmäßig belichteten farbfotographischen Silberhalogenidmaterials umfassend einen Träger mit mindestens einer darauf befindlichen lichtempfindlichen Silberhalogenidemulsionsschicht;

(b) Bleichen des farbentwickelten farbfotographischen Materials mit einer Bleichlösung, die einen (1,3-Diaminopropantetraacetato)eisen(III)-Komplex enthält und einen pH von 5,5 bis 2,0 hat, durch Zusammenbringen der Emulsionsoberfläche des Materials mit einem Strahl der Bleichlösung innerhalb von 10 s nach dem Einbringen des Materials in die Bleichlösung; und

(c) Eintauchen des Materials von Schritt (b) in eine Lösung mit einer Fixierfähigkeit und Zusammenbringen der Emulsionsoberfläche des Materials von Schritt (b) mit einem Strahl einer Lösung mit einer Fixierfähigkeit innerhalb von 15 s nach dem Einbringen in die Lösung mit einer Fixierfähigkeit.

2. Verfahren nach Anspruch 1, worin die Lösung mit einer Fixierfähigkeit eine Fixierlösung ist.

3. Verfahren nach Anspruch 1, worin die Strahlen eine Fließgeschwindigkeit von 0,3m/s bis 3m/s an der Düse haben.

4. Verfahren nach Anspruch 1, worin das fotographische Material mit dem Strahl einer Lösung mit einer Fixierfähigkeit innerhalb von 10 s nach dem Einbringen in die Lösung mit einer Fixierfähigkeit zusammengebracht wird.

5. Verfahren nach Anspruch 1, worin die Lösung mit einer Fixierfähigkeit eine Fixierlösung ist, die ein Thiosulfat in einer Menge von 50 bis 500 g pro l der Fixierlösung enthält.

6. Verfahren nach Anspruch 1, worin die Verarbeitungszeit vom Beginn des Schritts (b) bis zum Ende des Schritts (c) 1 min bis 4 min beträgt.

7. Verfahren nach Anspruch 1, worin der (1,3-Diaminopropantetraacetato)eisen(III)-Komplex ein Ammoniumsalzkomplex ist.

8. Verfahren nach Anspruch 1, worin die Bleichlösung 0,05 mol bis 1 mol des (1,3-Diaminopropantetraacetato)eisen(III)-Komplexes pro l der Bleichlösung enthält.

9. Verfahren nach Anspruch 1, worin die Bleichlösung ferner mindestens einen Eisen(III)-Komplex einer Säure, gewählt aus der Gruppe bestehend aus Ethylendiamintetraessigsäure,
Diethylentriaminpentaessigsäure,
Cyclohexandiamintetraessigsäure und
1,2-Propylendiamintetraessigsäure, enthält.

10. Verfahren nach Anspruch 9, worin die Bleichlösung 0,1 bis 3,0 mol des Eisen(III)-Komplexes pro mol (1,3-Diaminopropantetraacetato)eisen(III)-Komplex enthält.

11. Verfahren nach Anspruch 1, worin der pH der Bleichlösung in Schritt (b) 5,0 bis 3,0 beträgt.

12. Verfahren nach Anspruch 11, worin der pH der Bleichlösung in Schritt (b) 4,5 bis 3,5 beträgt.

13. Verfahren nach Anspruch 1, worin das Intervall zwischen dem Entwicklungsschritt (a) und dem Bleichlösungsverarbeitungsschritt (b) höchstens 10 s beträgt.

14. Verfahren nach Anspruch 1, worin das Intervall zwischen dem Bleichlösungsverarbeitungsschritt (b) und dem Verarbeitungsschritt (c) mit dem Strahl der Lösung mit einer Fixierfähigkeit 10 s oder weniger beträgt.

15. Verfahren nach Anspruch 1, worin die Bleichlösung eine Bromidionenkonzentration von 1,2 bis 3,0 mol/l hat.

16. Verfahren nach Anspruch 1, worin das in dem farbfotographischen Silberhalogenidmaterial enthaltene Silberhalogenid 30 mol% oder weniger Silberiodid enthält.

Revendications

1. Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent comprenant les étapes de :

(a) réaliser le développement couleur d'un matériau photographique couleur à l'halogénure d'argent exposé pour donner une image latente comprenant un support qui porte au moins une couche d'émulsion à l'halogénure d'argent photosensible ;

(b) blanchir ledit matériau photographique couleur développé en couleur avec une solution de blanchiment qui contient le complexe (1,3-diaminopropanetétraacétato) fer (III) et qui a un pH compris entre 5,5 et 2,0 en mettant en contact la surface d'émulsion dudit matériau avec courant projeté de ladite solution de blanchiment dans les 10 s après l'introduction dudit matériau dans la solution de blanchiment ; et

(c) immerger ledit matériau de l'étape (b) dans une solution qui a une capacité de fixage et mettre en contact la surface d'émulsion dudit matériau de l'étape (b) avec un courant projeté d'une solution ayant une capacité de fixage dans les 15 s après l'introduction dans ladite solution qui a une capacité de fixage.

2. Procédé selon la revendication 1, dans lequel ladite solution qui a une capacité de fixage est une solution de fixage.

3. Procédé selon la revendication 1, dans lequel lesdits courants projetés ont une vitesse d'écoulement de 0,3 m/s à 3 m/s au niveau de la buse.

4. Procédé selon la revendication 1, dans lequel on met en contact ledit matériau photographique avec un courant projeté d'une solution qui a une capacité de fixage dans les 10 s après avoir introduit le matériau dans ladite solution ayant une capacité de fixage.

5. Procédé selon la revendication 1, dans lequel ladite solution ayant une capacité de fixage est une solution de fixage contenant un thiosulfate en une quantité comprise entre 50 et 500 g/l de la solution de fixage.

6. Procédé selon la revendication 1, dans lequel le temps de traitement entre le début de l'étape (b) et la fin de l'étape (c) est compris entre 1 min et 4 min.

7. Procédé selon la revendication 1, dans lequel ledit complexe (1,3-diaminopropanetétraacétato) fer (III) est un complexe de sel d'ammonium.

8. Procédé selon la revendication 1, dans lequel ladite solution de blanchiment contient de 0,05 mol à 1 mol dudit complexe (1,3-diaminopropanetétraacétato) fer (III) par litre de ladite solution de blanchiment.

9. Procédé selon la revendication 1, dans lequel ladite solution de blanchiment contient en outre au moins un complexe ferrique d'un acide choisi dans le groupe constitué de
l'acide éthylènediaminetétraacétique,
l'acide diéthylènetriaminepentaacétique,
l'acide cyclohexanediaminetétraacétique et
l'acide 1,2-propylènediaminetétraacétique.

10. Procédé selon la revendication 9, dans lequel ladite solution de blanchiment contient de 0,1 à 3,0 mol dudit complexe ferrique par mole de complexe (1,3-diaminopropanetétraacétato) fer (III).

11. Procédé selon la revendication 1, dans lequel le pH de ladite solution de blanchiment à l'étape (b) est compris entre 5,0 et 3,0.

12. Procédé selon la revendication 11, dans lequel le pH de ladite solution de blanchiment de l'étape (b) est compris entre 4,5 et 3,5.

13. Procédé selon la revendication 1, dans lequel l'intervalle entre ladite étape de développement (a) et ladite étape de traitement par la solution de blanchiment (b) est au plus 10 s.

14. Procédé selon la revendication 1, dans lequel l'intervalle entre ladite étape de traitement par la solution de blanchiment (b) et ladite étape de traitement (c) avec le courant projeté de la solution qui a une capacité de fixage est de 10 s ou moins.

15. Procédé selon la revendication 1, dans lequel ladite solution de blanchiment a une concentration en ion bromure comprise entre 1,2 et 3,0 mol/l.

16. Procédé selon la revendication 1, dans lequel l'halogénure d'argent compris dans ledit matériau photographique couleur à l'halogénure d'argent contient 30 % molaires ou moins d'iodure d'argent.

Drawing