JPH0410062B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a color photographic processing method, and more particularly to a desilvering process for silver halide color photographic light-sensitive materials (hereinafter simply referred to as light-sensitive materials) using a simplified processing bath. [Prior Art] After exposure, a photosensitive material is subjected to color development, bleaching, fixing, washing and/or stabilization. In the bleaching process, bleaching and fixing have conventionally been carried out in the same bath for the purpose of speeding up and simplifying the process in the case of light-sensitive materials that have a low silver content and do not contain silver iodide. Such processing is known as bleach-fixing. By the way, in the bleach-fixing process, various problems have arisen due to the coexistence of a bleaching agent, which is an oxidizing agent, and a fixing agent, which is a reducing agent, and a preservative such as sulfite.
For this reason, stable processing cannot be performed, and it has been known that processing of highly sensitive photographic materials is particularly difficult. For example, if a relatively strong oxidizing agent is added to increase the redox potential of the solution in order to increase the bleaching speed, the fixing component will be easily oxidized and sulfurized, and in severe cases, silver sulfide will be generated, making it impossible to recover. This could lead to an unforeseen accident. Furthermore, if the concentration of the fixing agent is increased too much in an attempt to increase the fixing speed, the fixing speed will actually decrease, becoming the rate-limiting step in the bleach-fixing reaction, and the processing speed may drop. For this reason, red blood salts, persulfates, bromate salts, etc., which have high oxidizing power, cannot be used, and organic acids with weak oxidizing power cannot be used.
This is the reason why it is becoming necessary to use iron rust salts. In other words, it can be seen that the bleach-fix solution has the drawbacks of low stability and insufficient bleaching performance in terms of speed, so it has not been put to practical use as a treatment for high-sensitivity photosensitive materials. . It is generally known that the desilvering rate of a bleach-fix solution increases as the pH decreases, and decreases as the pH increases. Normally, color development is directly followed by bleach-fixing, so a color developing solution with a high pH is brought in. As a result, the pH of the bleach-fixing solution tends to increase and the bleach-fixing reactivity also fluctuates. Furthermore, since the pH in the film is high, there is also the drawback that the initial bleach-fixing speed is slow. Particularly in recent years, the replenishment method for bleach-fixing processing has become so-called a non-regeneration method, which only replenishes the fixing agent necessary to chain the missing components and silver ions eluted in the bleach-fix solution when processing photosensitive materials. After its adoption, it was discovered that the replenishment amount for bleach-fixing was extremely small, and that when the silver ion concentration in the bleach-fixing solution increased during continuous processing, the fixing speed was significantly suppressed. Therefore, it is desired to develop a rapid processing method that can increase the fixing speed of a bleach-fixing solution using the ferric chain salt of ethylenediaminetetraacetic acid and has an excellent bleach-fixing speed. In order to solve these drawbacks, facilitate the management of the bleach-fix solution, and solve the various problems mentioned above, the bleach-fix solution is divided into two tanks and made into a countercurrent system.
JP-A-58-105148 proposes a method in which the fixing agent is supplied to the front tank and the bleach is mainly supplied to the rear tank, while the overflow liquid is allowed to flow from the latter tank into the front tank and exit from the front tank. has been done. However, in these methods, the first tank is essentially a bleach-fix tank, and the only way to supply fixing agent to the second tank is to bring in the photosensitive material, and the second tank essentially has the composition of a bleaching solution. In addition, even if metallic silver is bleached in the latter stage tank, problems such as poor fixing are likely to occur, and the silver thiosulfate complex brought in from the earlier stage tank may form insoluble salts and precipitate due to insufficient fixing agent, or the fixing agent may be oxidized. Since it is easily decomposed by chemical agents, it has the disadvantage of forming silver sulfide, which can lead to serious failures. On the other hand, the pre-stage tank has a high concentration of silver ions and a sufficient supply of fixing agent and preservative, so it can be said that the preservability of the liquid and the silver recovery rate are certainly high. However, since it is essentially a bleach-fix solution containing a bleaching agent, it is not possible to dramatically improve the silver recovery efficiency, although the silver recovery efficiency is higher than that of a low-concentration silver-containing solution. This is because the decrease in the silver recovery efficiency of the bleach-fix solution
In the replacement method with iron wool, the iron wool is oxidized and dissolved by the ferric salt, and the portion that is not used for silver replacement becomes extremely large.In the electrolytic recovery method, the ferric salt is oxidized and dissolved at the cathode. This is because reduction takes precedence over silver reduction, resulting in a decrease in current efficiency, and furthermore, the persistently electrodeposited metallic silver is redissolved by the ferric salt, both of which are caused by the presence of the ferric salt. This is an important issue. However, the method disclosed in JP-A-58-105148 only divides the bleach-fix solution into two parts and increases the silver ion concentration in the first tank, but does not solve the fundamental problem. In bleach-fix solutions for printing light-sensitive materials, which have a particularly low silver content, the concentration of silver ions accumulated is less than 10 g/min, which is not a major problem, but in bleach-fix solutions for light-sensitive materials for high-sensitivity photography, the concentration of silver ions accumulated is It is expected that the amount will be as high as 10 to 30 g/m, which also has the disadvantage that the desilvering reaction will be significantly reduced. In order to solve these drawbacks, or to enhance the stopping effect after color development and prevent bleaching otein, or to make it unnecessary to recover silver in a bleach-fix solution and to facilitate regeneration. For a long time, acidic fixing treatment has been carried out as a pretreatment for bleach-fixing solutions. In this case, it has been considered particularly preferable to perform acidic fixing treatment. These methods are described in Japanese Patent Application Laid-Open No. 48-49437. However, in this method, the pre-fixing solution and the bleach-fixing solution have completely different compositions and different pH values, so each replenisher is required to be made from a different kit. Adjusting, dissolving, and managing the replenisher becomes extremely complicated, going against the trend of reducing bath use. Therefore, the present inventors connected the pre-fixing tank to the bleach-fixing tank in a downflow manner so that the overflow liquid of the pre-fixing tank flows into the bleach-fixing tank. The present patent application proposes that each of the fixing agent and bleaching agent packaged in a bleach-fixing kit can be used as is for each replenishment solution of the bleach-fixing solution, thereby simplifying replenishment and solving the above-mentioned problems. It was proposed in No. 59-172995. However, the pre-fixing process requires a processing time of at least 10 seconds or more and 3 minutes or less, which has the disadvantage of impairing speed. On the other hand, it has been proposed to add various bleaching accelerators to bleaching solutions or bleach-fixing solutions that use metal complex salts of organic acids such as ethylenediaminetetraacetic acid iron() complexes as a bleaching agent. . Examples of such bleaching accelerators include, for example,
-thiourea derivatives as described in No. 8056;
Aliphatic amines as described in No. 46-556,
Selenourea derivatives as described in JP-A No. 46-280, five-membered ring mercapto compounds as described in British Patent No. 1138842, or thiourea derivatives and thiazole derivatives as described in Swiss Patent No. 336257. , thiadiazole derivatives, etc. However, many of these bleach accelerators do not always have a satisfactory bleaching accelerating effect using conventional processing methods, and even if they do have a bleaching accelerating effect, they lack stability in the processing solution, so they cannot be processed. Those that have short useful lifespan and cannot withstand long-term storage, or have a bleaching accelerating effect when included in the so-called pre-bath used in the process before processing with bleaching solution or bleach-fixing solution. Many of them have drawbacks such as not being able to be obtained. Furthermore, German Patent No. 213940 proposes that onium compounds can be used as bleaching accelerators. However, although these onium compounds have an effect of accelerating bleaching, the effect is still not sufficient, and especially when a metal complex salt of an organic acid is used as a bleaching agent, almost no effect of accelerating bleaching is observed. On the other hand, the present inventors have previously discovered diethylenetriamine iron pentaacetate () complex salt as a bleaching agent with relatively high oxidizing power among aminopolycarboxylic acid iron () complex salts in addition to ethylenediaminetetraacetic acid iron () complex salt. . This iron () complex salt is characterized by a rapid silver bleaching reaction when the pH is high, especially at pH 4 or higher. However, even with this diethylenetriaminepentaacetate iron() complex salt, the bleaching speed is insufficient as a bleaching agent for ultra-high sensitivity silver halide color photographic light-sensitive materials, and it is difficult to fully satisfy the required speed. It became clear that it couldn't be done. In addition, the present inventor added the compounds of the general formulas (1) to (5) of the present invention to a processing solution having bleaching ability containing diethylenetriaminepentaacetic acid ferric complex salt, and the bleaching ability of developed silver was significantly accelerated. We discovered this and proposed this technology earlier, but as photosensitive materials entered the era of ultra-high sensitivity and new silver halide emulsifiers were used, it became clear that the bleaching speed of the above bleaching technology was not sufficient. I found out that it would happen. In particular, it was found that this is not sufficient when the sensitivity is ultra-high and the ASA sensitivity is 400 or higher or 1000 or higher. [Object of the Invention] The present invention has been made in view of the above-mentioned circumstances, and its purpose is to improve the bleaching properties of high-sensitivity photosensitive materials in processing steps with a reduced bath, and to speed up desilvering processing. The purpose of the present invention is to provide an ivy treatment process. Other purposes will become apparent from the description below. [Structure of the Invention] An object of the present invention is to provide a method in which a silver halide color photographic light-sensitive material is subjected to color development after exposure, and subsequently treated with a pre-fixing solution and then treated with a bleach-fixing solution, wherein the bleach-fixing solution contains at least one type of material. A compound containing an organic acid ferric complex salt of and the pre-fixing solution processing tank and the bleach-fixing solution processing tank are connected by a forward flow system, and the overflow liquid of the pre-fixing processing tank is introduced into the bleach-fixing solution processing tank. This is achieved by a method for processing a silver halide color photographic light-sensitive material. General formula (1)

【formula】 General formula (2)

【formula】 General formula (3)

【formula】 General formula (4)

【formula】 General formula (5)

[Formula] [In the above general formula, Q is an atom necessary to form a heterocycle containing one or more N atoms (including those to which at least one 5- to 6-membered unsaturated ring is fused) represents a group, the heterocycle may have a substituent, and A is

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] -SZ' or _n represents a monovalent substituted or unsubstituted heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused), M is a divalent represents a metal atom, B represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, X and X' each represent =S, O or =NR'', R'' is a hydrogen atom,
Represents an alkyl group, cycloalkyl group, aryl group, heterocyclic residue (at least one 5- to 6-membered unsaturated ring may be fused thereto) having 1 to 6 carbon atoms, or an amino group, Y is >N- or >
CH- represents a hydrogen atom, an alkali metal atom, an ammonium group, a substituted or unsubstituted amino group, a nitrogen-containing heterocyclic residue, or

[Formula], Z′ represents Z or a substituted or unsubstituted alkyl group, R ¹ is a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic residue (with at least one 5- to 6-membered unsaturated ring) R ² , R ³ , R ⁴ , R ⁵ , R and R' each represent a hydrogen atom, a substituted or unsubstituted amino group having 1 to 6 carbon atoms, and a substituted or unsubstituted amino group. Represents a substituted alkyl group, hydroxy group, carboxy group, amino group, acyl group having 1 to 3 carbon atoms, substituted or unsubstituted aryl group, or substituted or unsubstituted alkenyl group, (provided that R and
R′, R ² and R ³ , and R ⁴ and R ⁵ are each cyclized with each other to substitute or unsubstituted heterocyclic residues (5 to 6
R ⁶ and R ⁷ are each

【formula】

【formula】

[Formula] (where R ⁹ is an alkyl group or -(CH ₂ )
n ₈ SO ₃ (however, when R ⁹ is an alkyl group,
l represents an integer from 0 to 2, and R ⁹ is -(CH ₂ )
When n ₈ SO ₃ , l represents 0 or 1), G represents an anion). m ₁ to m ₄ and n ₁ to n ₈ each represent an integer of 1 to 6, and m ₅ represents an integer of 0 to 6. ^R8 is a hydrogen atom, an alkali metal atom,

[Exemplary compounds]

(2-28) H ₂ N−CSNHNHCS−NH ₂ (2-34) H ₂ N-CSNH (CH ₂ ) ₂ NHCS-NH ₂ (2-35) H ₂ N-CSNH (CH ₂ ) ₄ NHCS-NH ₂ (2-36) H ₂ N-CSNH (CH ₂ ) _5NHCS − _NH2 (3-1) H ₂ N−CH ₂ CH ₂ −SH (3-5) HOOC・CH ₂ CH ₂・SH Among the compounds represented by the above general formulas (1) to (5), the above (2-27), (2-142), (2-143), (3-2)
，
(3-3), (3-5), (3-6), (3-33), (
3
-34), (5-71) and (5-74) are particularly preferred. All of the above compounds are known and can be easily synthesized by known synthetic methods. The inventors of the present invention have repeatedly investigated a method for processing photosensitive materials containing silver iodide using a single-bath bleach-fix solution, which is a simple processing step, and which does not cause the various troubles mentioned above. In particular, when a bleaching agent consisting of a ferric complex salt of an organic acid such as a ferric complex salt of an aminopolycarboxylic acid and/or a ferric complex salt of an aminopolymethylene phosphate is used at a high concentration, the fixing reaction may be affected by the increase in the concentration. We found that it was significantly suppressed. It has also been found that the delay in the fixing reaction is due to the delay in diffusion of the fixing agent. It was found that the delay in the fixing reaction forms the rate-determining step in the bleach-fixing reaction, and in particular, it significantly suppresses the initial reaction and forms an induction period. It has been found that this phenomenon is particularly remarkable in the processing of photosensitive materials containing silver iodide. Furthermore, it was found that, as a matter of course, it was suppressed as the amount of silver increased. In addition, this phenomenon is particularly observed when organic acid ferric complex salts such as aminopolycarboxylic acid ferric complex salts are
From the above, it has also been found that this is particularly significant at 80g/or more. Based on this phenomenon, the present inventors previously proposed treatment with a processing solution having fixing ability as a pretreatment for bleach-fixing as an effective means of preventing suppression of the fixing reaction. If the treatment is carried out in separate baths, it will not meet the demands of the era of reduced bathing and simplification, and the treatment will become complicated. Therefore, it has been proposed to solve the above-mentioned drawbacks by connecting the pre-fixing solution and the bleach-fixing solution in a forward flow manner and processing the overflow of the pre-fixing solution while flowing into the bleach-fixing solution. However, these methods have the drawback that the processing time is extended due to the pre-fixing reaction, and the speed is impaired. In the present invention, after the treatment with the pre-fixer, bleach-fixing treatment is performed, and the pre-fixer and/or
Alternatively, by incorporating at least one of the compounds represented by the general formulas (1) to (5) of the present invention into the bleach-fixing solution, rapid bleach-fixing properties and stable bleach-fixing processing were obtained. It has been known for a long time that the compounds represented by the general formulas (1) to (5) of the present invention have a bleaching accelerating effect, but the fixing ability, especially when pre-fixing treatment, removes silver halide. The present inventors have found that the bleaching accelerating effect of this compound is extremely high, perhaps because of the fact that it is In particular, when the molecular weight of the organic acid of the ferric complex salt contained in the bleach-fix solution is 300 or more, a remarkable accelerating effect can be obtained. Furthermore, a significant accelerating effect can be obtained even in pre-fixing treatment in which silver ions are bleached at a low concentration. The compounds represented by the above general formulas (1) to (5) (hereinafter referred to as the bleach accelerator of the present invention) need only be present when bleaching the silver image obtained by development; A method of adding the compound to the bleach-fixing bath is preferred, or a method of adding it to a bath prior to the bleach-fixing bath (ie, a pretreatment solution bath) and allowing it to be incorporated into the bleach-fixing bath is also preferred. Alternatively, a method may also be used in which the compound is incorporated into the photosensitive material in advance during production and then eluted into the bleach-fixing bath. The bleach accelerators of the present invention may be used alone or in combination of two or more. Good results are generally obtained when the accelerator is added to the bleach-fix solution or pre-fix solution in an amount in the range of about 0.01 to 100 g per 1 processing solution. However, in general, when the amount added is small, the effect of promoting bleaching is small, and when the amount added is larger than necessary, it may cause precipitation and contaminate the photographic material being processed. The amount is preferably 50 g, more preferably 0.05 to 20 g per treatment liquid, and most preferably 0.1 to 10 g per treatment liquid. When adding the bleaching accelerator of the present invention to the processing solution, it may be added and dissolved as is, but it is common to dissolve it in water, alkali, organic acid, etc. before adding it, and add it as necessary. Even if it is dissolved in an organic solvent and added, the bleach-fixing effect is not affected at all. Metal ions may be supplied to the bleach-fix solution of the present invention by any method. For example, it can be supplied in any form such as a halide, hydroxide, sulfate, carbonate, phosphate, acetate, etc., but it is preferable to supply it as a complex salt of the chelating agent using the compound shown below. (A-1) Nickel chloride (A-2) Nickel nitrate (A-3) Nickel sulfate (A-4) Nickel acetate (A-5) Nickel bromide (A-6) Nickel iodide (A-7) Phosphorus Nickel acid (A-8) Bismuth chloride (A-9) Bismuth nitrate (A-10) Bismuth sulfate (A-11) Bismuth acetate (A-12) Zinc chloride (A-13) Zinc bromide (A-14) Zinc sulfate (A-15) Zinc nitrate (A-16) Cobalt chloride (A-17) Cobalt nitrate (A-18) Cobalt sulfate (A-19) Cobalt acetate (A-20) Cerium sulfate (A-21) Chloride Magnesium (A-22) Magnesium sulfate (A-23) Magnesium acetate (A-24) Calcium chloride (A-25) Calcium nitrate (A-26) Barium chloride (A-27) Barium acetate (A-28) Barium nitrate (A-29) Strontium chloride (A-30) Strontium acetate (A-31) Strontium nitrate (A-32) Manganese chloride (A-33) Manganese sulfate (A-34) Manganese acetate (A-35) Lead acetate ( A-36) Lead nitrate (A-37) Titanium chloride (A-38) Stannous chloride (A-39) Zirconium sulfate (A-40) Zirconium nitrate (A-41) Ammonium vanadate (A-42) Metavanazine Ammonium acid (A-43) Sodium tungstate (A-44) Ammonium tungstate (A-45) Ammonium chloride (A-46) Aluminum sulfate (A-47) Aluminum acetate (A-48) Yttrium sulfate (A-49) ) Yttrium nitrate (A-50) Yttrium chloride (A-51) Samarium chloride (A-52) Samarium bromide (A-53) Samarium sulfate (A-54) Samarium acetate (A-55) Ruthenium sulfate (A-56) ) Ruthenium chloride These metal compounds may be used alone or
Two or more types can also be used in combination. The amount of metal ion used is preferably 0.0001 to 2 moles, particularly preferably 0.001 to 1 mole, per 1 mole of metal ion used. The bleaching accelerator of the present invention is represented by the general formulas (1) to (5), among which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ ,
A, B, Z, Z', R, R', and R and
The heterocyclic residue formed by R', _R2 and _R3 , _R4 and _R5 , and Q and Q', an amino group, an aryl group, an alkenyl group, and an alkylene group may each be substituted. Its substituents include alkyl groups, aryl groups,
alkenyl group, cyclic alkyl group, aralkyl group,
Cyclic alkenyl group, halogen atom, nitro group, cyano group, alkoxy group, aryloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, heterocyclic residue, aryl Sulfonyl group, alkylsulfonyl group, alkylamino group, dialkylamino group,
Examples include anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxyl group, and mercapto group. In addition, the above R ₁ to R ₅ , R ₈ , R ₉ A, B, Z,
The alkyl group represented by Z', R, and R' may also have a substituent, and examples of the substituent include all those listed above except for the alkyl group. The bleach-fix solution of the present invention preferably contains a complex salt of an organic acid and ferric ion having a molecular weight (weight average molecular weight) of 300 or more (hereinafter referred to as an organic acid ferric complex salt). The following are representative examples of the organic acids that form the organic acid ferric complex salt of the present invention. (1) Diethylenetriaminepentaacetic acid (Mw=393.7) (2) Diethylenetriaminepentaacetic acid (Mw=573.12) (3) Cyclohexanediaminetetraacetic acid (Mw=364.35) (4) Cyclohexanediaminetetraacetic acid (Mw=508.23) (5) Triethylenetetraminehexaacetic acid (Mw=494.45) In the present invention, the bleach accelerator of the present invention is contained in the pre-fixing solution and/or the bleach-fixing solution, but when the pre-fixing solution has two or more baths, The bleach accelerator of the present invention may be contained in at least one of them and/or the bleach-fixing solution. The pretreatment liquid with the most individual composition used in the present invention is an aqueous solution in which the bleach accelerator of the present invention is simply dissolved. Aqueous solutions containing appropriate salts such as sodium, sodium thiosulfate, sodium borate, sodium carbonate, and sodium bicarbonate can also be advantageously used as the pretreatment liquid. Any PH can be used for the pretreatment liquid, and the effects of the present invention can be effectively achieved with any of them, but stains may occur if the PH is too high, so PH12 is generally used. Preferably used below. In the pre-fixing solution, further fixing agents such as anti-settling agents made of various chelate compounds, hardening agents made of various compounds including alum and aldehyde compounds, PH buffering agents, and halogen salts are added as necessary. Antioxidants such as sulfites, hydroxylamine and hydrazine, anti-swelling agents such as sodium sulfate and magnesium sulfate, surfactants and the like can be contained. Although the pre-fixing solution may be subjected to a stop-fixing process, the effects of the present invention can also be obtained by adding the bleach accelerator of the present invention to such a pre-fixing solution. However, when the bleach accelerator of the present invention is contained only in the pre-fixing solution, it is more desirable that the pre-fixing solution is used in the step immediately before the bleach-fixing solution. In the method of the present invention, the pre-fixing solution used in the pre-bath of the bleach-fixing solution contains substantially no bleaching agent (specifically 0.2 mol or less, more preferably 0.05 mol or less, most preferably 0.05 mol or less). preferably 0.001
It is preferable that the amount is mol or less. In this case, since most of the silver salt is dissolved here, the silver concentration is significantly higher than in the latter stage tank, so of course the silver recovery efficiency is high and desirable, but since it does not contain bleach, metal replacement method, electrolysis method, The efficiency of any silver recovery method such as ion exchange method or electrodialysis method is extremely high. In addition, the effect of PH fluctuation due to color developer brought in is virtually nil because the pre-bath mainly consists of the fixer composition;
In particular, it is preferable that the amount is 10% or more. Furthermore, the PH in the film after color development is high and inhibits the bleach-fix reaction, but since pre-fixing is performed, it has the advantage that it has little effect on the silver reaction in the film. In the present invention, the PH of the pre-fixing solution and the bleach-fixing solution may be different or the same, and the pre-fixing tank solution and replenisher have a pH lower than that of the bleach-fixing solution in order to neutralize color development. Preferably, the pH of the bleach-fix solution in the bleach-fix tank is higher than that of the pretreatment.
In either case, the PH can be arbitrarily selected as required, and the optimum value may be selected to achieve the above-mentioned purpose. However, the preferred bleach-fix pH is PH2
-9.8, more preferably 3-8.5, particularly preferably 6-8.5, and the pH of the pre-fixer is preferably in the range of 2-9.0, more preferably 3-8. Preferably, the pre-fixer is treated while recovering silver, and usually electrolysis, ion exchange, or electrodialysis is used. In these silver recovery methods, it is preferable that silver be processed while being continuously recovered by an in-line system, and as a result, silver recovery in a bleach-fix solution in a subsequent tank is not necessary. It is desirable that air oxidation of the bleach-fix solution in the subsequent tank be carried out efficiently, and forced aeration can be performed. In the present invention, the pre-fixing solution (hereinafter, a bath containing the processing solution is also referred to as a pre-fixing bath, the processing tank containing the processing solution is also referred to as a pre-fixing tank, etc.) mainly contains a fixing agent, and the bleach-fixing solution mainly contains a fixing agent. Although it is preferable to replenish the pre-fixing tank with bleach, it is possible to supply and replenish the pre-fixing tank with bleach in an amount not exceeding 50%, preferably not exceeding 30% of the total amount used. The amount of bleach used in the bleach-fix solution of the present invention is 60 g or more, preferably 80 g or more, particularly preferably 90 g or more per processing solution. Preferred bleaching agents used in the present invention are:
Ferric complex salts of organic acids, especially ferric complex salts of aminopolycarboxylic acids or aminopolymethylene phosphoric acids, especially ferric complex salts of aminopolycarboxylic acids. As a bleaching agent used in the bleach-fix solution of the present invention, preferred organic acids that form a ferric complex salt include the following. These organic acids (eg, organic acetic acids, organic phosphonic acids, etc.) may be alkali metal salts, ammonium salts, or water-soluble amine salts. Specific representative examples of these include the following. (1) Ethylenediaminetetraacetic acid (2) Ethylenediaminetetramethylenephosphonic acid (3) Diethylenetriaminepentaacetic acid (4) Diethylenetriaminepentamethylenephosphonic acid (5) Ethylenediamine-N-(β-oxyethyl)
-N,N',N'-triacetic acid (6) Ethylenediamine-N-(β-oxyethyl-N,N',N'-trimethylenephosphonic acid (7) Propylenediaminetetraacetic acid (8) Propylenediaminetetramethylenephosphonic acid Acids (9) Nitrilotriacetic acid (10) Nitrilotrimethylenephosphonic acid (11) Cyclohexanediaminetetraacetic acid (12) Cyclohexanediaminetetramethylenephosphonic acid (13) Iminodiacetic acid (14) Iminodimethylenephosphonic acid (15) Dihydroxyethylglycine citric acid (16) Dihydroxyethylglycine methylenephosphonic acid (17) Dihydroxyethylglycine tartaric acid (18) Ethyl ether diamine tetraacetic acid (19) Ethyl ether diamine tetramethylene phosphonic acid (20) Glycol ether diamine tetraacetic acid (21) Glycol ether diamine tetramethylene Phosphonic acid (22) Ethylenediaminetetraprobionic acid (23) Ethylenediaminetetraacetic acid (24) Ethylenediaminetetramethylenephosphonic vinegar (25) Ethylenediaminetetraacetic acid disodium salt. (26) Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt (27) Ethylenediamine Tetraacetic acid tetrasodium salt (28) Diethylenetriaminepentaacetic acid pentasodium salt (29) Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid sodium salt (30) Propylenediaminetetraacetic acid sodium salt (31 ) Nitrilotriacetic acid sodium salt (32) Cyclohexanediaminetetraacetic acid sodium salt (33) Diamipropanoltetraacetic acid (34) Diaminopropanoltetramethylenephosphonic acid (35) Ethylenediamine-diortho-hydroxyphenylacetic acid (36) Ethylenediamine-diortho-hydroxy Phenylmethylenephosphonic acid (37) Ethylenediaminetetrakis (methylenephosphonic acid) (38) Triethylenetetraminehexaacetic acid (39) Triethylenetetraminehexamethylenephosphonic acid Preferred organic acids have a molecular weight of 300 or more. It is composed of an organic acid and a ferric complex salt, and these complex salts may be ammonium salts, sodium salts, or potassium salts.It is also a preferable method to use one type or a combination of two or more of these bleaching agents. In addition to the bleaching agent, the bleach-fix solution may contain a fixing agent and any additives such as: As fixing agents, compounds which react with silver halides to form water-soluble silver chains, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate are used. Examples include thiocyanates such as thiocyanates, thioureas, thioethers, and the like. In addition to these fixing agents, fixing solutions and bleach-fixing solutions include ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, etc. PH buffers consisting of various salts such as sulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. alone or Two or more types can be included. Furthermore, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or ammonium halide, such as potassium bromide, sodium bromide, sodium chloride, or ammonium bromide. In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to normal bleach-fix solutions may be added as appropriate. can. When replenishing the bleach-fixing solution with the bleach-fixing film solution, in the present invention, it may be divided into at least two component solutions and then replenished. The amount of bleach used in one of the bleach-fixing replenishers (B) is preferably 0.2 mol or more, particularly preferably 0.4 mol or more and 1.5 mol or less. In addition, aminopolycarboxylic acid ferric complex salts generally have low solubility, so it is not easy to prepare the above-mentioned concentrated solution by itself. A concentrated solution can be obtained relatively easily by adding potassium borate, sodium borate, potassium metaborate, and sodium metaborate to increase the pH. As the thiosulfate preferably used in the other (A) of the bleach-fix replenisher, potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate are useful, and the amount used is preferably 1.0 mol or more per 1 bleach-fix replenisher (A). Particularly preferably 1.5 mol or more and 5.0 mol or less. In addition, sulfites include ammonium sulfite, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite,
Ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, etc. are useful, and the amount used is 0.3 mol or more, preferably 0.4 mol or more and 3.5 mol or less, per 1 bleach-fixing replenisher (A). The concentration range is determined by variations in the liquid composition of the bleach-fixing bath;
This is a preferable range in terms of bleach-fixing ability. The pH of the bleach-fixing replenisher is preferably set to be maintained at 4.0 to 9.0. More specifically, since a highly alkaline color developing solution is carried into the bleach-fixing bath by the sensitive material being processed, in order to maintain the pH of the bleach-fixing solution mentioned above, (A) of the bleach-fixing replenisher is required. This is because it is preferable to maintain the PH of the bleach-fixing bath constant by adjusting the PH and the PH of (B). Bleach-fix replenisher containing ferric amino acid complex salt
(B) has a PH of 6.5 or below, which is disadvantageous from the point of view of solubility, so it is kept above that level, and therefore the bleach-fix replenisher (A) containing thiosulfate and sulfite is used.
Bleach-fix replenisher (B) can lower the pH to around 4.0 from the viewpoint of solubility and stability.
By adjusting the pH value, it becomes possible to maintain the pH of the bleach-fixing bath at a desired value. PH of these replenishers
Of course, the value must also vary depending on the amount of replenishment. It is preferable not to add bleach to the bleach-fixing replenisher (A) at any time from the viewpoint of preserving the processing solution. The bleach-fix replenisher (B) preferably contains, in addition to a ferric complex of an organic acid such as the aminopolycarboxylic acid as described above and a suitable alkaline agent, a PH buffer such as ammonium borate or ammonium nitrate; 2
Nonchelating agents for aminopolycarboxylic acids other than iron complex salts can be included, such as ethylenediaminetetraacetic acid diammonium salt. In addition, the bleach-fixing replenisher (B) contains fixing agents such as thiosulfates, sulfites, glacial acetic acid, non-chelating agents for sulfamic acid, aminopolycarboxylic acids, boric acid, phosphoric acid, sulfuric acid, etc. PH buffers, thiocyanates, amines, silver halide solvents such as mercaptotriazole, known stain inhibitors such as 1-phenyl-3-pyrazolidone, formamidinosulfinic acid, paraphenylenediamine, polyalkylamine compounds ( polyamine compounds (described in JP-A-45-8836), ethylene oxides (described in German Patent No. 966410),
Known additives such as nitrogen-containing heterocyclic compounds (described in German Patent No. 1290812) can be included. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or a suitable oxidizing agent, such as Hydrogen oxide, bromate, persulfate, etc. may be added as appropriate. When carrying out the method of the present invention, silver may be recovered from the pretreatment solution and/or the bleach-fix solution by a known method. For example, electrolysis method (described in French Patent No. 2299667), precipitation method (described in JP-A-52-73037, German Patent No. 2331220), ion exchange method (described in JP-A-51-17114) Description, German patent
2548237) and the metal substitution method (described in British Patent No. 1353805) can be effectively used. After bleach-fixing, stabilization treatment may be performed without washing with water, or washing with water and subsequent stabilization treatment may be performed. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary. Typical specific examples of preferred treatment methods include:
The following steps are included. (1) Color development → pre-fixing → bleach-fixing → first stable → second stable → third stable (2) color development → pre-fixing → bleach-fixing → washing with a small amount of water → washing with water (3) color development → pre-fixing → bleach-fixing →Water washing - Stable (4) Color development → Pre-fixing → Bleach-fixing → Stable (5) Color development → Pre-fixing → Bleach-fixing → 1st stable → 2nd stable (6) Color development → Pre-treatment Washing - Pre-fixing → Bleaching Establishment →
Washing with water (or stabilizing) (7) Color development → stop pretreatment → prefixing → bleach fixing →
Stable However, during each process, pre-fixing and bleach-fixing steps in processing include forward flow connection. In addition, in the above specific examples, when the stabilization process is divided into two or more, each of them may be performed using the same type of liquid or different types of liquids, and the stabilizing liquid may be a stabilizer that is commonly used, for example, by removing components of a bleach-fixing solution. This includes functional items and items that have a function to prevent uneven water droplets. It is preferable to add various inorganic metal salts to the bleach-fix solution of the present invention. After forming these inorganic metal salts into metal complex salts with various chelating agents,
Addition is also a preferred method. The effects of the present invention are most effective in processing light-sensitive materials having a silver halide emulsion layer containing at least 0.3 mol % of silver iodide. Particularly preferred are photosensitive materials having a silver halide emulsion layer containing 2.0 mol% or more of silver iodide, and more specific photosensitive materials include emulsions consisting of core-shell type grains and emulsions consisting of tabular silver halide grains. It will be done. As a core-shell type silver halide grain, JP-A-Sho
The method of the present invention is effective for photosensitive materials having silver halide grains such as those described in No.
The method of the present invention is suitable for light-sensitive materials having core-shell type silver halide grains having cores consisting essentially of silver iodobromide containing 0.3 to 20 mol%, more effectively 0.5 to 20 mol%. In addition, as tabular silver halide grains, JP-A Nos. 58-113930, 58-113934, and 58-127921
No. 58-108532, etc., and the particle size is 0.5 μm or more, especially 0.6 μm.
The method of the present invention is suitable for processing photosensitive materials having the following properties. The method of the present invention can also be preferably applied to photosensitive materials containing epitaxially bonded silver halide grains as described in JP-A-53-103725 and the like. The silver halide emulsion used in the light-sensitive material processed by the method of the present invention can contain various commonly used additives depending on the purpose. For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy compounds; aldehyde-based, aziridine-based, isoxazole-based, vinylsulfone-based, acryloyl-based,
Hardeners such as arpodiimide, maleimide, methanesulfonic acid ester, and triazine; Development accelerators such as benzyl alcohol and polyoxyethylene compounds; Chroman, Claman, bisphenol, and phosphite ester hardeners; Image stabilizer;
Lubricants include waxes, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids. In addition, anionic, cationic, nonionic, or A variety of both sexes can be used. Moreover, it is particularly preferable that these surfactants are eluted into a processing solution having bleaching ability. As antistatic agents, diazetylcellulose, styrene perfluoroalkylridium maleate copolymers, alkali salts of reaction products of styrene-maleic anhydride copolymers and p-aminobenzenesulfonic acid, etc. are effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to further use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc. and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers. Supports for photosensitive materials include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene, etc.
These supports are appropriately selected depending on the intended use of each silver halide color photographic light-sensitive material. The silver halide emulsion to which the present invention is applied is a red-, green-, and blue-sensitized emulsion containing a combination of cyan, magenta, and yellow couplers in order to be applied to a color photosensitive material. The methods and materials used for photosensitive materials such as The photosensitive materials to which the method of the present invention can be applied include internal development methods in which a color former is contained in the light-sensitive material (see U.S. Pat. External development method (see U.S. Patent No. 2252718, U.S. Patent No. 2592243, U.S. Patent No. 2590970)
It may be of. Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan coloring agents are those based on a naphthol or phenol structure and form indoaniline dyes by coupling, magenta coloring agents are those having a 5-pyrazolone ring with an active methylene group as a skeleton structure, and yellow coloring agents are As such, those having an acylacetanilide structure such as benzoylacetanilide and pivalyl acetanilide having an active methylene chain, with or without a substituent at the coupling position can be used. Thus, as the coloring agent, both so-called 2-equivalent couplers and 4-equivalent couplers can be used. The aromatic primary amine color developing agent used in the color developing solution used before processing with the bleach-fixing solution of the present invention is a known one that is widely used in various color photographic processes. is included. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Further, these compounds are generally used in a concentration of about 0.1 g to about 30 g per color developer, more preferably about 1 g to about 15 g per 1 color developer.
Use at a concentration of Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxytoluene, 2-amino-3
-oxytoluene, 2-oxy-3-amino-
Includes 1,4-dimethylbenzene and the like. Particularly useful aromatic primary amine color developers are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. Among them, particularly useful compounds are N, N
-diethyl-p-phenylenediamine hydrochloride, N
-methyl-p-phenylenediamine hydrochloride, N,
N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β -Hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N
-(2=methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate and the like can be mentioned. The color developer used before the processing of the present invention is
In addition to the aromatic primary amine color developer,
Furthermore, various components normally added to color developing solutions, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal sulfites,
Optionally contains water softeners and thickeners such as alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, and 1-hydroxyethylene-1,1-diphosphonic acid. be able to. The pH of this color developer is usually 7 or higher, most commonly about 10 to about 13. [Examples] Examples of the present invention will be described below, but the present invention is not limited thereto. Example 1 An example of the present invention will be described in detail with reference to drawings of a processing apparatus used in the method of the present invention and the comparative method. FIG. 2 shows the main parts of a color paper processing apparatus, and FIG. 1 shows the main parts of a color negative film processing apparatus. The conventional bleach-fixing method for color negative film has not been put into practical use, so it will be omitted here. In FIG. 1, a color negative film processing apparatus 20 includes a color developing tank 21, a pre-fixing tank 22, a bleach-fixing tank 23, washing tanks 24, 25, and a stabilizing tank (draining tank) 26. In addition to the replenisher supply pipe 21A and the overflow pipe 21B, it is provided with a stirring means, a filter, a liquid temperature adjusting means, etc. (not shown). The pre-fixing tank 22 is connected to the bleach-fixing tank 23 through an overflow pipe 22C.
The overflow liquid flows into the bleach-fixing tank 23 in a downward flow manner. Furthermore, the fixing solution and bleaching agent are stored in the bleach-fixing replenishment pipe 22A.
The fixing replenishment pipe 22A is supplied to the processing tank 22, and the bleach-fixing replenishment pipe 22B is supplied to the processing tank 2.
Replenishment fluid is supplied to each of the three ports. The overflow liquid from the bleach-fixing tank 23 is discharged to the outside by 22D, and silver is recovered. Furthermore, it is provided with stirring means, liquid temperature adjustment means, etc. (not shown). Further, hot water is supplied to the washing tanks 24 and 25 from 24A, flows from 25 to 24 by a countercurrent method, and overflows from the water pipe 24B. The stabilizing tank 26 is supplied with replenisher through 26A, overflow is discharged through 26B, and further includes stirring means and temperature adjustment means. FIG. 2 is a diagram showing the processing form of color paper, which was found in Japanese Patent Application Laid-open No. 105148/1983, which was devised to facilitate the management of bleach-fixing, and is shown for comparison purposes. The apparatus shown in FIG. 2 includes a color developing tank 11, a first bleach-fix tank 12, a second bleach-fix tank 13, a washing tank 14,
It consists of 15 and 16. The basics are the same as in Fig. 1, and although the explanation is omitted, the feature in Fig. 2 is that the replenisher for the bleach-fix solution containing both bleach and fixing agent is in the second bleach-fix tank 1.
The overflow liquid from the second bleach-fix tank 13 flows into the first bleach-fix tank 12 through 12C in a countercurrent manner, and is finally discharged from the first bleach-fix tank 12 to the outside. The bleach-fix replenisher is divided into two parts, a bleaching agent and a fixing agent, and the first bleach-fixing tank is mainly replenished with the fixing component, and the second bleach-fixing tank is mainly replenished with the bleaching component. Therefore, the replenishment method is exactly the same as that shown in Fig. 1, and the difference in Fig. 2 is the communication between the countercurrent method and the forward flow method. That is, one of the basic differences between the comparison process and the process of the present invention.
One can be seen as a difference between a countercurrent method and a forward flow method in a processing device. This will be explained in detail by an experiment in which the same color film was processed using the respective apparatuses shown in FIG. 1 used in the method of the present invention and FIG. 2 used in the comparative method. First, the color film used in the following experiment will be described. An average shell thickness of silver halide grains with an average grain size of 1.0 μm consisting of silver iodobromide containing 3.6 mol% of silver iodide.
Gold sensitization and sulfur sensitization were applied to a silver iodobromide emulsion having silver halide grains formed by shelling silver bromide of 0.05 μm, and 4-hydroxy-6-methyl-1,3,
After adding 3a,7-tetrazaindene, the amount of silver
A sample was prepared as follows so that the concentration was 112 mg/100 cm ² . Anhydro-3,3'-di-(3-sulfopropyl)-5,5'-dichloro-9, a red-sensitive sensitizing dye
-ethylthiacarbocyaniline hydroxide (dye p-1) 285 mg/mol AgX, anhydro-3,
3'-di-(3-sulfopropyl)-4,5,4',
5'-Dibenzothiacarbocyene hydroxide (dye p-2) 38.5 mg/1 mol AgX and anhydro-1,3-ethyl-3'-(3-sulfopropyl)
Optical sensitization was carried out using -5-trichloromethyl-4,5-benzobenzimidazolothiacarboxyanine hydroxide (dye p-3) 116 mg/1 mol AgX. In this photographic emulsion, 2-
(α, α, β, β, γ, γ, δ, δ-octafluorohexanamide)-5-[2-(2,4-di-
A dispersion in which t-amylphenoxy)hexaneamide]phenol was dissolved in tricresyl phosphate and protected and dispersed in a conventional manner was added in an amount of 0.3 mol of coupler per mol of AgX. Furthermore, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was used as a stabilizer, 1-phenyl-5-mercaptotetrazole was used as a fog inhibitor, and poly-N was used as a physical development inhibitor.
- Vinylpyrrolidone was added and coated on a subbed cellulose acetate film. The color film sample thus produced was exposed to light in a conventional manner and subjected to the following development treatment. [Development processing] Color development 3 minutes and 15 seconds pre-fixing or first bleach-fixing 2 minutes Second bleach-fixing 6 minutes Washing (first) 1 minute Washing (second) 1 minute Stable 1 minute Drying 3 minutes Processing solution is The following formulation was used. [Color developer] Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.0g 1-hydroxyethylidene-1,1-phosphonic acid (60% aqueous solution) 1.0g Magnesium chloride 0.3g Hydroxyethyliminodiacetic acid 3g Potassium bromide 1.2g Sodium hydroxide 3.4g N-ethyl-N-β-hydroxyethyl-3-
Methyl-4-aminoaniline hydrochloride 4.6g Add water to make 1 and pH with sodium hydroxide
Adjusted to 10.1. [Color developer replenisher] Add 0.91g of potassium bromide to the color developer replenisher
10.20 was used. [Replenisher (A)] Ammonium thiosulfate (30% aqueous solution) 490ml Ammonium sulfite (50% aqueous solution) 200ml Diammonium ethylenediaminetetraacetate 10g was adjusted to 1 with water, and PH4.9 with ammonium hydroxide.
Adjusted to. [Replenisher (A')] Ammonium thiosulfate (30% aqueous solution) 490ml Ammonium sulfite (50% aqueous solution) 200ml Diammonium ethylenediaminetetraacetic acid 10g Bleach accelerator of the present invention (listed in Table 2) 2.0g was mixed with water, The pH was adjusted to 4.9 with ammonium hydroxide. [Replenisher (B)] Diethylenetriaminepentaacetic acid ferric complex salt (ammonium salt) 250g Ethylenediaminetetraacetic acid 40g Bleach accelerator of the present invention (listed in Table 2) 2.0g Potassium carbonate 30g was made 1 part with water, and ammonium hydroxide PH6 Adjusted to .7. [Pre-fixing tank liquid] (for the present invention) Replenisher (A) and water were mixed at a ratio of 1:1, and the pH was adjusted to 6.0 with potassium carbonate. [First bleach-fixing tank solution] (for comparison) 1 part of replenisher (A), 1 part of replenisher (B) and 2 parts of water were mixed and the pH was adjusted to 7.0. [Bleach-fix tank solution] (For the present invention) Same as the above first bleach-fix tank solution. [Second bleach-fix tank solution] (for comparison) Same as the first bleach-fix tank solution above. [Stabilizer] Formalin (35%) 8mg

[Formula] 2g Adjusted to 1 with water. The replenisher and tank liquid used had the same composition. The replenishment amount etc. are as shown in Table 1. The amount of replenishment is for color negative film (35mm width)
This is the amount per meter.

【table】

[In the case of the present invention]

Using the apparatus shown in FIG. 1, the pre-fixing tank liquid is put into the pre-fixing tank 22, and the bleach-fixing tank liquid is put into the bleach-fixing tank 23. The replenisher is in the pre-fixing tank 22.
The replenisher (A') is supplied through 22A in the above amount according to the treatment. Replenisher to bleach-fix tank 23
(B) is supplied through 22B. The overflow liquid from the pre-fix tank 22 flows into the bleach-fix tank 23 through 22C, and the overflow liquid from the bleach-fix tank is discharged through 22D. [For comparison] Using the apparatus shown in Fig. 2, the first bleach-fix tank 12
The first bleach-fixing tank liquid is put into the first bleach-fixing tank, and the second bleach-fixing tank liquid is put into the second bleach-fixing tank. Replenishment is performed in the same manner as in the explanation of FIG. 2 above, and the overflow of the second bleach-fix solution is 12C.
flows into the first bleach-fixing tank 12 through the
This differs from the case of the present invention using the apparatus shown in FIG. 1 in that the overflow solution of the bleach-fix solution is discharged through 12D in a countercurrent manner. Processing was carried out using the two types of apparatuses described above under the conditions described above. The processing was continued until the volume of the replenisher supplied to the color developing tank reached three times or more the capacity of the processing tank. The results were as follows. (1) Desilvering properties (bleach-fixing completion time) are shown in Table 2. (2) Silver recovery efficiency The silver recovery efficiency of each of the present invention and comparative bleach-fix solutions was determined. Silver was recovered using electrolysis.
The device used was BF-50 manufactured by Sun Seiki Co., Ltd. The efficiency was determined by current efficiency, and the results are shown in Table 2.

〔Effect of the invention〕

(1) The desilvering processing speed of high-sensitivity photosensitive materials is improved in a processing step in which the bath is reduced. (2) Stabilization of the bleach-fix solution, simplification of replenisher dissolution and replenisher kit composition, and efficiency of silver recovery are achieved.

[Brief explanation of drawings]

FIG. 1 shows a processing apparatus used in an embodiment of the present invention.
FIG. 2 is a schematic cross-sectional view of each treatment used in the comparative example.

Claims (1)

[Claims] 1. After exposing a silver halide color photographic light-sensitive material,
A method of color development followed by treatment with a pre-fixer and a bleach-fixer, wherein the bleach-fixer contains at least one organic acid ferric complex salt, and the prefixer and/or the bleach-fixer. The liquid has the following general formula
(1), (2), (3), (4), or (5), and the processing tank for the pre-fixing solution and the processing tank for the bleach-fixing solution are connected by a downflow system. A method for processing a silver halide color photographic light-sensitive material, characterized in that the processing is carried out while introducing an overflow solution from the pre-fixing processing tank into the bleach-fix processing tank. General formula (1) [Formula] General formula (2) [Formula] General formula (3) [Formula] General formula (4) [Formula] General formula (5) [Formula] [In the above general formula, Q is an N atom Represents an atomic group necessary to form a heterocycle (including one in which at least one 5- to 6-membered unsaturated ring is condensed) containing ^{one or} more of ~6
represents an alkyl group, cycloalkyl group, aryl group, heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused) or an amino group, and A is [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] -SZ' or _n represents a monovalent heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused), X and X' are each =S, =O or =
NR'', where R'' is a hydrogen atom and has 1 to 6 carbon atoms.
R ² , R ³ , R ⁴ , R ⁵ , R and R' are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, or a group having 1 to 6 carbon atoms.
3 represents an acyl group, aryl group, or alkenyl group. However, R and R′, R ² and R ³ , and R ⁴ and R ⁵ are each cyclized with each other to form heterocyclic residues (including those in which at least one 5- to 6-membered unsaturated ring is fused to this). ) may be formed. Y represents N- or CH-, Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, or [Formula], and B represents an alkylene group having 1 to 6 carbon atoms. , M represents a divalent metal atom, Z′ represents Z or an alkyl group, R ⁶ and R ⁷
are respectively [Formula] [Formula] or [Formula] (where R ⁹ is an alkyl group or -(CH ₂ )
n ₈ SO ₃ (However, when R ⁹ is an alkyl group, l is 0
represents an integer of ~2, and R ⁹ is −(CH ₂ ) n ₈ SO ₃
, l represents 0 or 1) and G represents an anion). m ₁ to m ₄ and n ₁ to n ₈ each represent an integer of 1 to 6, and m ₅ represents an integer of 0 to 6. R ⁸ represents a hydrogen atom, an alkali metal atom, [Formula] or an alkyl group. However, Q' has the same meaning as Q above. In addition,
The compound represented by the above general formula includes enolized compounds and salts thereof. ]