Bleach-fixing solution for silver halide color photographic light-sensitive material

Abstract: A solution used for processing a silver halide photographic light sensitive material. The solution comprises a ferric complex salt of a compound represented by the following formula A: wherein A₁, A₂, A₃ and A₄ are independently a -CH₂OH group, a -PO₃M₂ group or a -COOM group, which may be the same or different; M is a cation: and X is an alkylene group having 1 to 6 carbon atoms or a -(B₁O) n -B₂- group, in which is an integer of 1 to 8, B₁ and B₂ are independently an alkylene group having 1 to 5 carbon atoms, which may be the same or different. The solution can be used as a bleaching solution or bleach-fixing solution for color photographic material. The solution further used as a reducing solution for reducing an image formed photographic light-sensitive material.

Description: FIELD OF THE INVENTION The present invention relates to a processing liquid for a silver halide color photographic light-sensitive material, more specifically to a bleach-fixer improved in processing performance, desilvering property and biodegradability. BACKGROUND OF THE INVENTION In the processing of a light-sensitive material, bleaching is normally conducted to remove silver of images therefrom. Nowadays, a bleaching solution or bleach-fixer that contains a metal complex salt of an aminopolycarboxylic acid, such as a ferric complex salt of ethylenediaminetetraacetic acid and a ferric complex salt of 1,3-propylenediaminetetraacetic acid, is widely employed in the photographic industry. A ferric complex salt of 1,3-propylenediaminetetraacetic acid is useful for the rapid processing of a high-speed film since it has an extremely high oxidizing activity. However, such high oxidizing activity inevitably causes a color developing agent that has been brought into a bleaching solution or bleach-fixer bath from the preceding processor bath to get oxidized. The oxidized color developing agent is coupled with unreacted couplers to form a dye, causing an unfavorable "bleach fogging" phenomenon. A ferric complex salt of ethylenediaminetetraacetic acid, which has smaller oxidizing activity than a ferric complex salt of 1,3-propylenediaminetetraacetic acid, is widely employed as a bleaching agent for a bleach-fixer. A bleach-fixer is a processing liquid which is employed in the bleach-fixing step where bleaching and fixing are conducted simultaneously using the same processing liquid for the simplification and speed-up of processing procedure. In a bleach-fixer, a bleaching agent serves as an oxidant and a fixing agent, normally thiosulfate ions, serves as a reducing agent. Thiosulfate ions are decomposed into sulfur when they are oxidized by a bleaching agent. To prevent this phenomenon, sulfite ions are generally added to a bleach-fixer as a preservative. Meanwhile, a ferric complex salt of ethylenediaminetetraacetic acid changes itself from a divalent state to a trivalent state extremely rapidly. Therefore, it maintains its trivalent state in a bleach-fixer, and keeps on decomposing sulfite ions. As a result, decomposition of thiosulfate ions is accelerated, causing the bleach-fixer to have poor storage stability. To solve this problem, Japanese Patent Publication Open to Public Inspection (hereinafter abbreviated as Japanese Patent O.P.I. Publication) Nos. 149358/1984, 151154/1984 and 166977/1984 each disclose the use of a ferric complex salt of diethylenetriaminepentaacetic acid. A bleach-fixer that contains a ferric complex salt of diethylenetriaminepentaacetic acid has better storage stability than that which contains a ferric complex salt of ethylenediaminetetraacetic acid. However, the use of a ferric complex salt of diethylenetriaminepentaacetic acid in the processing of color paper causes a so-called "edge penetration" phenomenon, in which the edge portion of color paper is stained. A ferric complex salt of ethylenetriaminetetraacetic acid and a ferric complex salt of diethylenepentaacetic acid are known to have extremely poor biodegradability, which is unfavorable in respect of environmental protection. Some countries are, therefore, trying to impose restrictions on the use of these salts. Under such circumstances, there is a strong demand for a bleach-fixer which is improved in desilvering property, storage stability and biodegradability, and free from the "edge penetration" problem. SU-A-1043137 discloses micro-element-rich fertilisers for lucerne based on aq. Fe chelate solutions which use ethylene-diamine-disuccinic acid as the chelating agent. Chem. Zvesti, Vol. 20, No. 6, 1966, pages 414-422 disclose the synthesis of ethylenediamino-N,N'-disuccinic acid (I) and the formation of new complexes with heavy metals and their spectrophotometric determination. Chem. Zvesti, Vol. 34, No. 2, 1980, pages 184-189 disclose the synthesis of the solid complexes of the racemic ethylenediamino-N,N'-disuccinic acid with Fe(III), Co (III), and Bi(III). The complexes Na[FeY]·2H 2 O, Na[CoY]·3H 2 O, and [BiHY]·H 2 O were prepared. SUMMARY OF THE INVENTION One object of the present invention is to provide a processing liquid with a bleach-fixing power for a silver halide color photographic light-sensitive material which is improved in desilvering property, storage stability and biodegradability and hardly causes the edge portion of color paper to be stained. The above object can be attained by a bleach-fixing solution for a silver halide light-sensitive material which contains a ferric complex salt of a compound represented by formula A: wherein A 1 to A 4 , whether identical or not, each represent -CH 2 OH, -PO 3 M 2 or -COOM; M represents a hydrogen atom, or a cation; X represents a substituted or unsubstituted alkylene group with 2 to 6 carbon atoms or -(B 1 O)n-B 2 - (where B 1 and B 2 , whether identical or not, each represent a substituted or unsubstituted alkylene group with 1 to 5 carbon atoms); and n represents an integer of 1 to 8. DETAILED DESCRIPTION OF THE INVENTION An explanation will be made of compounds represented by formula A. In the formula, A 1 to A 4 , whether identical or not, each represent -CH 2 OH, -PO 3 M 2 or -COOM. M represents a hydrogen ion, an alkali metal ion, e.g. a sodium ion, a potassium ion, or another cation, e.g. an ammonium ion, a methyl ammonium ion, a trimethyl ammonium ion. X represents a substituted or unsubstituted alkylene group with 2 to 6 carbon atoms or -(B 1 O)n-B 2 -, where B 1 and B 2 each represent an alkylene group with 1 to 5 carbon atoms. The alkylene group represented by X include ethylene, trimethylene and tetramethylene. The alkylene group represented by B 1 or B 2 include methylene, ethylene and trimethylene. Examples of substituents for the alkylene group represented by X, B 1 or B 2 include a hydroxy group and an alkyl group with 1 to 3 carbon atoms, e.g. methyl, ethyl. n represents an integer of 1 to 8, preferably 1 to 4, still preferably 1 to 2, most preferably 1. Preferred examples of compounds represented by formula A are given below: Compounds represented by formula A can be prepared by a known method. Of compounds A-1 to A-17, compounds A-1, A-3 and A-14 are especially preferable in the invention. Compounds represented by formula A can be contained in a bleach-fixing liquid which is employed for bleach-fixing a silver halide photographic light-sensitive material. These compounds are added to a bleach-fixer preferably in amounts of 0.05 to 2.0 mol, still preferably 0.1 to 1.0 mol, per liter of the bleach-fixer. In the present invention, besides compounds represented by formula A, a bleach-fixer may also contain a ferric complex salt of any one of the following organic acids: [A'-1] Ethylenediaminetetraacetic acid [A'-2] Trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] Dihydroxyethylglycinic acid [A'-4] Ethylenediaminetetraxismethylenephosphonic acid [A'-5] Nitrilotrismethylenephosphonic acid [A'-6] Diethylenetriaminepentaxismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid [A'-8] Ethylenediaminediorthohydroxyphenylacetic acid [A'-9] Hydroxyethylethylenediaminetriacetic acid [A'-10] Ethylenediaminepropionic acid [A'-11] Ethylenediaminediacetic acid [A'-12] Hydroxyethyliminodiacetic acid [A'-13] Nitrilotriacetic acid [A'-14] Nitrilotripropionic acid [A'-15] Triethylenetetraminehexaacetic acid [A'-16] Ethylenediaminetetrapropionic acid A ferric complex salt of the above organic acid is contained in a bleach-fixer preferably in an amount of 0.05 to 2.0 mol, still preferably 0.10 to 1.5 mol, per liter of the bleach-fixer. For rapid processing, a bleach-fixer may preferably contain, as a bleaching accelerator, at least one member selected from imidazole compounds described in Japanese Patent O.P.I. Publication No. 295258/1989, derivatives thereof and compounds represented by any one of formulae I to IX (including example compounds) described in this publication. Example compounds described on pages 51 to 115 of Japanese Patent O.P.I. Publication No. 123459/1987, example compounds described on pages 22 to 25 of Japanese Patent O.P.I. Publication No. 17445/1988, as well as compounds described in Japanese Patent O.P.I. Publication Nos. 95630/1978 and 28426/28426 are also usable. The temperature of a bleach-fixer should preferably be 20 to 50°C, still preferably 25 to 45°C. The pH of a bleach-fixer should preferably be 5.0 to 9.0, still preferably 6.0 to 8.5. Here, the pH of a bleach-fixer is distinguished from that of a bleach-fixing replenisher. A bleach-fixer may also contain a halide such as ammonium bromide, potassium bromide and sodium bromide, a fluorescent brightener, a defoaming agent and a surfactant. A bleach-fixing replenisher should normally be employed in an amount of 500 ml or less, preferably 20 ml to 400 ml, still preferably 40 ml to 350 ml, per square meter of a light-sensitive material. The smaller the amount of a replenisher, the more successfully the effects of the invention can be manifested. If desired, air or oxygen may be blown into a processing tank or storage tank to enhance the activity of a bleach-fixer. An oxidizing agent, such as a hydrogen peroxide, a bromate and a persulfate, may be added to a bleach-fixer if need arises. Examples of a fixing agent to be contained in a bleach-fixer of the invention include thiocyanates and thiosulfates. The amount of a thiocyanate should preferably be at least 0.1 mol/l; for processing a color negative, the amount of a thiocyanate should preferably be 0.5 mol/l or more, still preferably 1.0 mol/l or more. The amount of a thiosulfate should preferably be at least 0.2 mol/l; for processing a color negative, the amount of a thiosulfate should preferably be 0.5 mol/l or more. In the invention, a bleach-fixer may contain one or more kinds of pH buffers, which normally consists of a salt. It is desired that a large amount of a rehalogenating agent such as an alkaline halide or ammonium halide, e.g. potassium bromide, sodium bromide, sodium chloride, ammonium bromide, be contained in a bleach-fixer. Also, a compound generally contained in a bleach-fixer such as alkylamines and polyethylene oxides, may be added to a bleach-fixer if the occasion arise. Silver may be recovered from a bleach-fixer by a known method. It is preferred that a compound represented by the following formula FA described in Japanese Patent O.P.I. Publication No. 295258/1989, page 56, including example compounds, be added to a bleach-fixer. By doing this, not only can the effects of the invention be manifested successfully, but also only a small amount of sludge will be formed in a bleach-fixer when a few light-sensitive materials are processed for a long period of time. In the above formula, R' and R'' are each a hydrogen atom an alkyl group, an aryl group, an aralkyl group or a heterocyclic group; and n' is an integer of 2 or 3. A compound represented by formula FA can be prepared by a method described in U.S. Patent Nos. 3,335,161 and 3,260,718. Compounds represented by formula FA may be employed either alone or in combination. A compound represented by formula FA should be employed preferably in an amount of 0.1 to 200 g per liter of a bleach-fixer. Bleach-fixing time by a bleach-fixer is not limitative either; but preferably 4 minutes or less, still preferably in the range of 10 seconds to 2 minutes and 20 seconds. In a bleach-fixer of the invention, if the amount of ammonium ions accounts for 50 mol% or less of the total amount of cations, the effects of the invention can be manifested successfully, and the unfavorable odor of the liquid can be minimized. The amount of ammonium ions accounts for still preferably 30 mol% or less, most preferably 10 mol% or less, of the combined amount of cations. EXAMPLES In the following examples, the amounts of ingredients are grams per square meter of a light-sensitive material, unless otherwise indicated. The amounts of silver halide and colloidal silver were translated into the amounts of silver. Example 1 Preparation of Silver Halide Color Photographic Material (Color Paper) One side of a paper support was coated with polyethylene, and the other side thereof was coated with polyethylene that contained titanium oxide. On the titanium oxide-containing polyethylene-coated side of the support, layers of the following compositions were provided in sequence to form a multi-layer color photographic light-sensitive material. The coating liquid for the 1st layer was prepared by the method described below. Coating liquid for 1st layer In 6.67 g of a high-boiling solvent (DNP),26.7 g of a yellow coupler (Y-1), 100 g of a dye image stabilizer (ST-1), 6.67 g of another dye image stabilizer (ST-2) and 0.67 g of an additive (HQ-1) were dissolved, to which 60 ml of ethyl acetate had been added. The resulting solution was dispersed in 220 ml of an aqueous 10% gelatin solution containing 7 ml of a 20% surfactant (SU-1) by means of a ultrasonic homogenizer, whereby a yellow coupler dispersion was obtained. This yellow coupler dispersion was mixed with a blue-sensitive silver halide emulsion (silver content: 10 g) which had been prepared by a method described later, thus forming a coating liquid for the 1st layer. Coating liquids for the 2nd to 7th layers were prepared in a similar manner as mentioned above. As a hardener, H-1 was added to the 2nd and 4th layers, and H-2 was added to the 7th layer. Also, surfactants SU-2 and SU-3 were added for the adjustment of surface tension. Layer Composition Amount 7th layer (protective layer) Gelatin 1.0 6th layer (UV absorbing layer) Gelatin 0.35 UV absorber (UV-1) 0.10 UV absorber(UV-2) 0.04 UV absorber(UV-3) 0.18 Anti-stain agent (HQ-1) 0.01 DNP 0.18 PVP 0.03 Anti-irradiation dye(AI-2) 0.02 5th layer (red-sensitive layer) Gelatin 1.21 Red-sensitive silver chlorobromide emulsion (EmC) 0.19 Cyan coupler(C-1) 0.20 Cyan coupler(C-2) 0.25 Dye image stabilizer(ST-1) 0.20 Anti-stain agent (HQ-1) 0.01 HBS-1 0.20 DOP 0.20 4th layer (UV absorbing layer) Gelatin 0.90 UV absorber (UV-1) 0.28 UV absorber (UV-2) 0.08 UV absorber (UV-3) 0.38 Anti-stain agent (HQ-1) 0.03 DNP 0.35 3rd layer (green-sensitive layer) Gelatin 1.40 Green-sensitive silver chlorobromide emulsion(EmB) 0.15 Magenta coupler (M-C) 0.32 stabilizer (ST-3) 0.15 Dye image stabilizer(ST-4) 0.15 Dye image stabilizer (ST-5) 0.15 DNP 0.20 Anti-irradiation dye (AI-1) 0.02 2nd layer (intermediate layer) Gelatin, 1.20 Gelatin, Anti-stain agent (HQ-2) 0.12 DIDP 0.15 1st layer (blue-sensitive layer) Gelatin, 1.20 Blue-sensitive silver chlorobromide emulsion (EmA) 0.25 Yellow coupler(Y-1) 0.82 Dye image stabilizer (ST-1) 0.30 Dye image stabilizer (ST-2) 0.20 Anti-stain agent (HQ-1) 0.02 Anti-irradiation agent(AI-3) 0.02 DNP 0.20 Support Polyethylene-laminated paper DOP: dioctyl phthalate DNP: dinonyl phthalate DIDP: diisodecyl phthalate PVP: polyvinyl pyrrolidone H - 1 C(CH 2 SO 2 CH=CH 2 ) 4 Preparation of Blue-Sensitive Silver Halide Emulsion To 1,000 ml of an aqueous 2% gelatin solution that had been heated to 40°C, solutions A and B were added by the double-jet method over a period of 30 minutes, while controlling pAg and pH to 6.5 and 3.0, respectively. Then, solutions C and D were added over a period of 180 minutes while controlling pAg and pH to 7.3 and 5.5, respectively. pAg control was performed by the method described in Japanese Patent O.P.I. Publication No. 45437/1984, and pH control was conducted by using sulfuric acid or an aqueous solution of sodium hydroxide. (Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to make the total quantity 200 ml. (Solution B) Silver nitrate 10 g Water was added to make the total quantity 200 ml. (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to make the total quantity 600 ml. (Solution D) Silver nitrate 300 g Water was added to make the total quantity 600 ml. After the addition, the resulting solution was subjected to desilvering with an aqueous 5% solution of Demor N (manufactured by Kao Atlas) and an aqueous 20% solution of magnesium sulfate. Then, the solution was mixed with an aqueous gelatin solution, whereby an emulsion (EMP-1) comprising monodispersed, cubic silver halide grains with an average grain size of 0.85µm, a variation coefficient (σ/ γ )of 7% and a silver chloride content of 99.5 mol% was obtained, where σ is a standard deviation of grain size distribution and γ is an average grain size. The above emulsion was subjected to chemical ripening at 50°C for 90 minutes using the following compounds, whereby a blue-sensitive silver halide emulsion (Em-A) was obtained. Sodium thiosulfate 0.8 mg/mol AgX Chlorauric acid 0.5 mg/mol AgX Stabilizer (STAB-1) 6 × 10 -4 mol/mol AgX Sensitizing dye (BS-1) 4 × 10 -4 mol/mol AgX Sensitizing dye (BS-2) 1 × 10 -4 mol/mol AgX Preparation of Green-Sensitive Silver Halide Emulsion An emulsion (EMP-2) comprising monodispersed, cubic silver halide grains with an average grain size of 0.43 µm, a variation coefficient of 8% and a silver chloride content of 99.5 mol% was prepared in substantially the same manner as in the preparation of the blue-sensitive silver halide emulsion, except that the time taken in adding solutions A and B and the time taken in adding solutions C and D were changed. The above emulsion was subjected to chemical ripening at 55°C for 120 minutes using the following compounds, whereby a green-sensitive silver halide emulsion (Em-B) was obtained. Sodium thiosulfate 1.5 mg/mol AgX Chlorauric acid 1.0 mg/mol AgX Stabilizer (STAB-1) 6 × 10 -4 mol/mol AgX Sensitizing dye (GS-1) 4 × 10 -4 mol/mol AgX Preparation of Red-Sensitive Silver Halide Emulsion An emulsion (EMP-3) comprising monodispersed, cubic silver halide grains with an average grain size of 0.50 µm, a variation coefficient of 8% and a silver chloride content of 99.5 mol% was prepared in substantially the same manner as in the preparation of the blue-sensitive silver halide emulsion, except that the time taken in adding solutions A and B and the time taken in adding solutions C and D were changed. The above emulsion was subjected to chemical ripening at 60°C for 90 minutes using the following compounds, whereby a red-sensitive silver halide emulsion (Em-C) was obtained. Sodium thiosulfate 1.8 mg/mol AgX Chlorauric acid 2.0 mg/mol AgX Stabilizer (STAB-1) 6 × 10 -4 mol/mol AgX Sensitizing dye (RS-1) 4 × 10 -4 mol/mol AgX The sample was exposed to light in the usual way, and processed under the following conditions and by using the following processing liquids. Processing procedure Processing temperature Processing time Amount of replenisher (1) Color developing 35.0 ± 0.3°C 45 sec 162 ml/m 2 (2) Bleach-fixing 35.0 ± 0.5°C 45 sec 100 ml/m 2 (3) Stabilizing (3-tank cascade) 30 - 34°C 90 sec 248 ml/m 2 (4) Drying 60 - 80°C 30 sec Color Developer Triethanolamine 10 g Ethylene glycol 6 g N,N-diethylhydroxylamine 3.6 g Hydrazinodiacetic acid 5.0 g Potassium bromide 20 mg Potassium chloride 2.5 g Diethylenetriaminepentaacetic acid 5 g Potassium sulfite 5.0 × 10 -4 mol Color developing agent, 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidethyl)aniline sulfate 5.5 g Potassium carbonate 25 g Potassium bicarbonate 5 g Water was added to make the total quantity 1 l, and pH was controlled to 10.10 with potassium hydroxide or sulfuric acid. Color Developer Replenisher Triethanolamine 14.0 g Ethylene glycol 8 g N,N-diethylhydroxylamine 5 g Hydrazinodiacetic acid 7.5 g Potassium bromide 8 mg Potassium chloride 0.3 g Diethylenetriaminepentaacetic acid 7.5 g Potassium sulfite 7.0 × 0 -4 mol Color developing agent, 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidethyl)aniline sulfate 8 g Potassium carbonate 30 g Potassium bicarbonate 1 g Water was added to make the total quantity 1 l, and pH was adjusted to 10.40 with potassium hydroxide or sulfuric acid. Bleach-Fixer Water 600 ml Ferric complex salt of an organic acid (shown in Tables 3 and 4) 0.15 mol Thiosulfate 0.6 mol Sulfite 0.15 mol 1,3-propanediaminetetraacetic acid 2 g pH was adjusted to 7.0 with aqueous ammonia, potassium hydroxide and acetic acid, and water was added to make the total quantity 1 l. To adjust the ratio (mol%) of the amount of ammonium ions to the total amount of cations to those shown in Tables 3 and 4, ammonium salts and potassium salts of the above additives were added. Bleach-Fixer Replenisher Prepared by increasing the concentration of each component in the bleach-fixer by 1.25 times, and by changing the pH of the bleach-fixer to 5.8. Stabilizer and Stabilizer Replenisher Orthophenyl phenol 0.1 g Uvitex MST (manufactured by Ciba Geigy) 1.0 g ZnSO 4 •7H 2 O 0.1 g Ammonium sulfite (40% solution) 5.0 ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60% solution) 3.0 g Ethylenediaminetetraacetic acid 1.5 g Water was added to make the total quantity to 1 l, and pH was adjusted to 7.8 with aqueous ammonia or sulfuric acid. The above-obtained color paper sample was subjected to a continuos treatment. The continuos treatment was run by the method described below: The color developer, the bleach-fixer and the stabilizer were put in their respective tanks, and the above-obtained color paper sample was passed through these tanks. Every three minutes, the color developer replenisher, the bleach-fixer replenisher and the stabilizer replenisher were supplied to the color developer tank, the bleach-fixer tank and the stabilizer tank, respectively, by means of a constant delivery pump. The continuos treatment was conducted until the amount of the bleach-fixer replenisher supplied to the bleach-fixer tank became three times as large as that of the volume of the bleach-fixer tank. "1R" means that the bleach-fixer replenisher has been supplied to the bleach-fixer tank in an amount equal to the volume of the tank. After processing, the exposed portion of each sample was divided into two parts. One of which was examined for the amount of remaining silver by X-ray fluorometry. Also, each sample was examined immediately after the completion of the processing for stain formation in the edge portion. The bleach-fixer was visually checked for contamination caused by the formation of an insoluble decomposition product of thiosulfite. The results obtained are summarized in Tables 3 and 4. Contamination of the bleach-fixer was evaluated according to the following criteria: A: No sulfide was formed. B: An extremely small amount of scum was observed. C: An only small amount of a sulfide was formed. D: A large amount of a sulfide was formed. E: An extremely large amount of a sulfide was formed. Stain formation in the edge portion was evaluated according to the following criteria: A: No stains were formed. B: A very small amount of stains were formed. C: A small amount of stains were formed. D: A large amount of stains were formed. E: A very large amount of stains were formed. Experiment No. Ferric complex salt of an organic acid Ratio (mol%) of the amount of ammonium ions to the total amount of cations in the bleach-fixer Amount of remaining silver (mg/100 cm 2 ) Stain formation in the edge portion Formation of a sulfide Remarks 1-1 EDTA•Fe 100 0.9 C D Comparative Example 1-2 EDTA•Fe 60 0.9 C D Comparative Example 1-3 EDTA•Fe 50 1.0 C D Comparative Example 1-4 EDTA•Fe 30 1.0 B D Comparative Example 1-5 EDTA•Fe 10 1.1 B D Comparative Example 1-6 EDTA•Fe 0 1.2 B D Comparative Example 1-7 PDTA•Fe 100 1.8 C E Comparative Example 1-8 PDTA•Fe 60 1.9 C E Comparative Example 1-9 PDTA•Fe 50 1.9 B E Comparative Example 1-10 PDTA•Fe 30 2.1 B E Comparative Example 1-11 PDTA•Fe 10 2.0 B E Comparative Example 1-12 PDTA•Fe 0 2.2 B E Comparative Example 1-13 DTPA•Fe 100 0 E B Comparative Example 1-14 DTPA•Fe 60 0 E B Comparative Example 1-15 DTPA•Fe 50 0.1 E B Comparative Example 1-16 DTPA•Fe 30 0.1 E B Comparative Example 1-17 DTPA•Fe 10 0.2 D B Comparative Example 1-18 DTPA•Fe 0 0.2 D B Comparative Example 1-19 NTA•Fe 100 1.3 C D Comparative Example 1-20 NTA•Fe 60 1.3 C D Comparative Example 1-21 NTA•Fe 50 1.4 B D Comparative Example 1-22 NTA•Fe 30 1.5 B D Comparative Example 1-23 NTA•Fe 10 1.7 B D Comparative Example 1-24 NTA•Fe 0 1.8 B D Comparative Example Experiment No. Ferric complex salt of an organic acid Ratio (mol%) of the amount of ammonium ions to the total amount of cations in the bleach-fixer Amount of remaining silver (mg/100 cm 2 ) Stain formation in the edge portion Formation of a sulfide Remarks 1-25 (A-1)•Fe 100 0 C B Present Invention 1-26 (A-1)•Fe 60 0 C B Present Invention 1-27 (A-1)•Fe 50 0 B A Present Invention 1-28 (A-1)•Fe 30 0 B A Present Invention 1-29 (A-1)•Fe 10 0.1 A A Present Invention 1-30 (A-1)•Fe 0 0.1 A A Present Invention 1-31 (A-3)•Fe 100 0 C B Present Invention 1-32 (A-3)•Fe 60 0 C B Present Invention 1-33 (A-3)•Fe 50 0 C-B A Present Invention 1-34 (A-3)•Fe 30 0.1 B A Present Invention 1-35 (A-3)•Fe 10 0.1 A A Present Invention 1-36 (A-3)•Fe 0 0.2 A A Present Invention 1-37 (A-10)•Fe 100 0.1 C B Present Invention 1-38 (A-10)•Fe 60 0.1 C B Present Invention 1-39 (A-10)•Fe 50 0.1 C-B A Present Invention 1-40 (A-10)•Fe 30 0.1 B A Present Invention 1-41 (A-10)•Fe 10 0.2 B A Present Invention 1-42 (A-10)•Fe 0 0.2 A A Present Invention Note: In the preceding tables and following tables, "EDTA Fe" means a ferric complex salt of EDTA. The same can be true of PDTA•Fe, DTPA•Fe, NTA•Fe, (A-1)•Fe, (A-3)•Fe and (A-10)•Fe. EDTA, PDTA, DTPA and NTA are ethylendiaminetetraacetate, 1,3- propylenediaminetetraacetate, diethylentriaminepentaacetate and nitrylotriacetate, respectively. From Tables 3 and 4, it can be understood that the use of a ferric complex salt of an organic acid according to the invention led to a decreased amount of remaining silver, a decreased amount of stains formed in the edge portion, and improved storage stability of the bleach-fixer. Such effects were produced more noticeably when the ratio of the amount of ammonium ions to the total amount of cations was 50 mol% or less. Still more satisfactory results were obtained at 30 mol% or less, and the best results were obtained at 10 mol% or less. The same experiment as mentioned above was conducted, except that (A-4)•Fe, (A-5)•Fe, (A-14)•Fe and (A-16)•Fe were used instead of (A-3)•Fe. Results obtained were similar to those obtained with (A-3)•Fe. Example 2 A silver iodobromide color photographic light-sensitive material was prepared by the method described below. Preparation of Silver Iodobromide Color Photographic Light-Sensitive Material One side of a triacetyl cellulose film support (thickness: 60 µm) was subbed. On the other side of the support, layers of the following compositions were provided in sequence. 1st layer Alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Co., Ltd.) 0.8 g 2nd layer Diacetyl cellulose 100 mg Stearic acid 10 mg Finely divided silica (average particle size: 0.2 µm) 50 mg On the subbed side of the support, layers of the following compositions were provided in sequence, whereby a multi-layer color photographic light-sensitive material (Sample No. a-1) was obtained. 1st layer: Anti-halation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Colored cyan coupler (CC-1) 0.02 g High-boiling solvent (Oil-1) 0.20 g High-boiling solvent (Oil-2) 0.20 g Gelatin 1.6 g 2nd layer: Intermediate layer (IL-1) Gelatin 1.3 g 3rd layer: Low-speed red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (average grain size: 0.3 µm) 0.4 g Silver iodobromide emulsion (average grain size: 0.4 µm) 0.3 g Sensitizing dye (S-1) 3.0 × 10 -4 mol/mol silver Sensitizing dye (S-2) 3.2 × 10 -4 mol/mol silver Sensitizing dye (S-3) 0.3 × 10 -4 mol/mol silver Cyan coupler (C-1) 0.50 g Cyan coupler (C-2) 0.20 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High-boiling solvent (Oil-1) 0.55 g Gelatin 1.0 g 4th layer: High-speed red-sensitive emulsion layer (R-H) Silver iodobromide emulsion (average grain size: 0.7 µm) 0.9 g Sensitizing dye (S-1) 1.7 × 10 -4 mol/mol silver Sensitizing dye (S-2) 1.6 × 10 -4 mol/mol silver Sensitizing dye (S-3) 0.2 × 10 -4 mol/mol silver Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High-boiling solvent (Oil-1) 0.30 g Gelatin 1.0 g 5th layer: Intermediate layer (IL-2) Gelatin 0.8 g 6th layer: Low-speed green-sensitive emulsion layer (G-L) Silver iodobromide emulsion (average grain size: 0.4 µm) 0.6 g Silver iodobromide emulsion (average grain size: 0.3 µm) 0.2 g Sensitizing dye (S-4) 6.7 × 10 -4 mol/mol silver Sensitizing dye (S-5) 1.0 × 10 -4 mol/mol silver Magenta coupler (M-A) 0.20 g Magenta coupler (M-B) 0.40 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High-boiling solvent (Oil-2) 0.7 g Gelatin 1.0 g 7th layer: High-speed green-sensitive emulsion layer (G-H) Silver iodobromide emulsion (average grain size: 0.7 µm) 0.9 g Sensitizing dye (S-6) 1-1 × 10 -4 mol/mol silver Sensitizing dye (S-7) 2.0 × 10 -4 mol/mol silver Sensitizing dye (S-8) 0.5 × 10 -4 mol/mol silver Magenta coupler (M-A) 0.5 g Magenta coupler (M-B) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High-boiling solvent (Oil-2) 0.35 g Gelatin 1.0 g 8th layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High-boiling solvent (Oil-2) 0.15 g Gelatin 0.9 g 9th layer: Low-speed blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size: 0.3 µm) 0.25 g Silver iodobromide emulsion (average grain size: 0.4 µm) 0.25 g Sensitizing dye (S-9) 5.8 × 10 -4 mol/mol silver Yellow coupler (Y-1) 0.71 g Yellow coupler (Y-2) 0.30 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High-boiling solvent (Oil-2) 0.18 g Gelatin 1.2 g 10th layer: High-speed blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size: 0.8 µm) 0.5 g Sensitizing dye (S-10) 3 × 10 -4 mol per mol silver Sensitizing dye (S-11) 1.2 × 10 -4 mol per mol silver Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.20 g High-boiling solvent (Oil-2) 0.05 g Gelatin 0.9 g 11th layer: 1st protective layer (PRO-1) Silver iodobromide emulsion (average grain size: 0.08 µm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1 g High-boiling solvent (Oil-1) 0.07 g High-boiling solvent (Oil-3) 0.07 g Gelatin 0.85 g 12th layer: 2nd protective layer (PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethyl methacrylate (average grain size: 3 µm) 0.02 g A copolymer of methyl methacrylate, ethylmethacrylate and methacrylic acid (weight ratio:3:3:4; average grain size: 3 µm) 0.13 g The above-obtained color photographic light-sensitive material further contained compounds Su-1 and Su-2, a viscosity controller, hardeners H-1 and H-2, stabilizer ST-1, anti-foggants AF-1 and AF-2 (one with a weight average molecular weight of 10,000 and the other 1,100,000), dyes AI-1 and AI-2 and compound D-1 (9.4 mg/m 2 ). H - 2 (CH 2 =CHSO 2 CH 2 ) 2 O weight average molecular weight: 30,000, DI-1 (a mixture of the following three components) Component A: Component B: Component C=50:23:20(molarratio) Preparation of Emulsion A silver iodobromide emulsion in the 10th layer was prepared by the following method. Monodispersed silver bromide emulsion grains (average grain size: 0.33 µm; silver iodide content: 2 mol%) to be used as seed grains were prepared. To solution G-1 that had been kept at 70°C, pAg 7.8 and pH 7.0, respectively, the seed grains in the amount of equivalent to 0.34 mol were added while sufficient stirring. Solutions H-1 and S-1 were added by the double-jet method over a period of 86 minutes at increasing flow rates such that the flow rates immediately after the start of the addition would be 3.6 times as high as those immediately before the completion of the addition. During the addition, the ratio of the flow rate of H-1 to that of S-1 was kept at 1:1. As a result, a high-iodide-containing phase or core phase of grain inner was formed. Then, while controlling pAg and pH to 10.1 and 6.0, respectively, solutions H-2 and S-2 were added by the double-jet method over a period of 65 minutes at increasing flow rates such that the flow rates immediately after the start of the addition would be 5.2 times as high as those immediately before the completion of the addition. During the addition, the ratio of the flow rate of H-2 to that of S-2 was kept at 1:1. As a result, a low-iodide containing outer phases or shell phase of grain was formed. During the addition, pAg and pH were controlled with an aqueous solution of potassium bromide and an aqueous 56% solution of acetic acid. The formed grains were washed with water with the conventional flocculation method. Then, gelatin was added to make the grains redispersed. pH and pAg were adjusted to 5.8 and 8.06, respectively, at 40°C. The resulting emulsion consisted of monodispersed octahedral silver iodobromide grains with an average grain size of 0.80 µm, a variation coefficient of 12.4% and a silver iodide content of 9.0 mol%. Solution G-1 Ossein gelatin 100.0 g 10 wt% methanol solution of compound 1 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% aqueous acetic acid solution 660.0 ml Water was added to make the total quantity 5000.0 ml. Solution H-1 Ossein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Water was added to make the total quantity 1030.5 ml. Solution S-1 Silver nitrate 28% aqueous ammonia solution Equivalent amount 309.2 g Water was added to make the total quantity 1030.5 ml. Solution H-2 Ossein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Water was added to make the total quantity 3776.8 ml. Solution S-2 Silver nitrate 28% aqueous ammonia solution Equivalent amount 1133.0 g Water was added to make the total quantity 3776.8 ml. Average molecular weight ≒ 1300 Emulsions differing in average grain size and silver iodide content were prepared in substantially the same manner as mentioned above, except that the average size of seed grains, temperature, pAg, pH, flow rate, addition time and halide composition were varied. Each of the resulting emulsions comprised of monodispersed core/shell type grains with a variation coefficient of 20% or less. Each emulsion was chemically ripen to an optimum level in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate. Then, sensitizing dyes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added to each emulsion. The light-sensitive material was exposed to light through an optical wedge in the usual way, and then subjected to a continuous treatment according to the following procedure and by using the following processing liquids. The continuous treatment was run until the amount of the bleach-fixer replenisher supplied doubled the volume of the bleach-fixer tank,namely 2 round. Processing procedure Processing time Processing temperature Amount of replenisher (amount per 135-size film for 24 exposures) Color developing 3 min. 15 sec. 38°C 20 ml Bleach-fixing 3 min. 15 sec. 38°C 30 ml Stabilizing 1 min 38°C 40 ml (3-tank cascade) Drying 1 min 40 - 80°C Color Developer Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N-(β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make the total quantity 1 l, and pH was adjusted to 10.00 with potassium hydroxide or 20% sulfuric acid. Color Developer Replenisher Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.5 g Hydroxylamine sulfate 3.5 g 4-Amino-3-methyl-N-ethyl-(β-hydroxylethyl) aniline sulfate 6.0 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water was added to make the total quantity 1 l, and pH was adjusted to 10.12 with potassium hydroxide or 20% sulfuric acid. Bleach-Fixer Ferric complex salt of an organic acid (shown in Tables 5 and 6) 0.3 mol Thiosulfate 2.0 mol Sulfite 0.15 mol 1,3-propanediaminetetraacetic acid 2 g Water was added to make the total quantity 1 l, and pH was adjusted to 7.0 with aqueous ammonia or sulfuric acid. To adjust the ratio (mol%) of the amount of ammonium ions to the total amount of cations to those shown in Tables 5 and 6, ammonium salts and potassium salts of the above additives were employed. Bleach-Fixer Replenisher Prepared by increasing the concentration of each of the components of the bleach-fixer by 1.07 times, and by adjusting the pH to 6.3. After the treatment, the light-sensitive material was examined for the amount of remaining silver, and the bleach-fixer was examined for the formation of an insoluble decomposition product of thiosulfite. These examinations were conducted by the same method as in Example 1. The results obtained are shown in Tables 5 and 6. Experiment No. Ferric complex salt of an organic acid Ratio (mol%) of the amount of ammonium ions to the total amount of cations in the bleach-fixer Amount of remaining silver (mg/100 cm 2 ) Formation of an insoluble product Remarks 2-1 EDTA•Fe 100 5.0 D Comparative Example 2-2 EDTA•Fe 60 5.0 D Comparative Example 2-3 EDTA•Fe 50 5.2 D Comparative Example 2-4 EDTA•Fe 30 5.2 D Comparative Example 2-5 EDTA•Fe 10 5.3 D Comparative Example 2-6 EDTA•Fe 0 5.4 D Comparative Example 2-5 PDTA•Fe 100 0 E Comparative Example 2-8 PDTA•Fe 60 0 E Comparative Example 2-9 PDTA•Fe 50 0.1 E Comparative Example 2-10 PDTA•Fe 30 0.1 E Comparative Example 2-11 PDTA•Fe 10 0.2 E Comparative Example 2-12 PDTA•Fe 0 0.2 E Comparative Example 2-13 DTPA•Fe 100 4.5 C Comparative Example 2-14 DTPA•Fe 60 4.5 C Comparative Example 2-15 DTPA•Fe 50 4.7 B Comparative Example 2-16 DTPA•Fe 30 4.7 B Comparative Example 2-17 DTPA•Fe 10 4.9 B Comparative Example 2-18 DTPA•Fe 0 5.0 B Comparative Example 2-19 NTA•Fe 100 5.8 D Comparative Example 2-20 NTA•Fe 60 5.8 D Comparative Example 2-21 NTA•Fe 50 6.0 D Comparative Example 2-22 NTA•Fe 30 6.1 D Comparative Example 2-23 NTA•Fe 10 6.2 D Comparative Example 2-24 NTA•Fe 0 6.3 D Comparative Example Experiment No Ferric complex salt of an organic acid Ratio (mol%) of the amount of ammonium ions to the total amount of cations in the bleach-fixer Amount of remaining silver (mg/100 cm 2 ) Formation of an insoluble product Remarks 2-25 (A-1)•Fe 100 0 B Present Invention 2-26 (A-1)•Fe 60 0 B Present Invention 2-27 (A-1)•Fe 50 0 A Present Invention 2-28 (A-1)•Fe 30 0 A Present Invention 2-29 (A-1)•Fe 10 0.1 A Present Invention 2-30 (A-1)•Fe 0 0.2 A Present Invention 2-31 (A-3)•Fe 100 0 B Present Invention 2-32 (A-3)•Fe 60 0 B Present Invention 2-33 (A-3)•Fe 50 0 A Present Invention 2-34 (A-3)•Fe 30 0.1 A Present Invention 2-35 (A-3)•Fe 10 0.2 A Present Invention 2-36 (A-3)•Fe 0 0.2 A Present Invention 2-37 (A-10)•Fe 100 0.1 B Present Invention 2-38 (A-10)•Fe 60 0.1 B Present Invention 2-39 (A-10)•Fe 50 0.1 A Present Invention 2-40 (A-10)•Fe 30 0.2 A Present Invention 2-41 (A-10)•Fe 10 0.4 A Present Invention 2-42 (A-10)•Fe 0 0.4 A Present Invention In Tables 5 and 6, EDTA Fe means a ferric complex salt of EDTA. The same can be applied to PDTA Fe, DTPA Fe, NTA Fe, (A-1) Fe, (A-3) Fe and (A-10) Fe. It is understood from Tables 5 and 6 that the use of a ferric complex salt of a compound of the invention led to a decreased amount of remaining silver and improved storage stability of the bleach-fixer. When the ratio of the amount of ammonium ions to the total amount of cations was 50 mol% or more, the above effects were produced successfully. These effects were produced more successfully at 30 mol% or less, most successfully at 10 mol% or less. Example 3 Conventional photographic chelating agents such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), example compounds A-1, A-3 and A-9 were subjected to the 301C amended MITI test prescribed in the OECD chemicals test guideline (adopted as of May 12, 1981) for the examination of biodegradability. The results obtained revealed that ferric complex salts of the chelating agents according to the present invention were extremely improved in biodegradability, while those of EDTA, DTPA and HEDTA were poor in biodegradability. The use of ferric complex salts of EDTA, DTPA and HEDTA is, therefore, unfavorable from the viewpoint of environmental protection.

Claims: A bleach-fixing solution for a silver halide colour photographic light-sensitive material comprising a ferric complex salt of a compound represented by the following formula A: wherein A 1 , A 2 , A 3 and A 4 are independently a -CH 2 OH group, a -PO 3 M 2 group or a a -COOM group, which may be the same or different; M is hydrogen or a cation; and X is a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms or a -(B 1 O) n -B 2 - group, in which n is an integer of 1 to 8, B 1 and B 2 are independently a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, which may be the same or different. The solution of claim 1, wherein said bleach-fixing solution contains said ferric complex salt in an amount of 0.05 to 2.0 mol per liter. The solution of claim 1, wherein said bleach-fixing solution contains ammonium ions in a ratio of not more than 50 mol% of whole cations contained in said bleach-fixing solution. The solution of claim 1, wherein said bleach-fixing solution further contains a compound represented by the following formula FA: wherein R' and R" are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a heterocyclic group; and n' is an integer of 1 or 2. The solution of claim 4, wherein said bleach-fixing solution contains said compound of FA in an amount of 0.1 g to 200 g per liter. A method for processing a silver halide colour photographic light-sensitive material comprising the steps of: developing the light-sensitive material and bleach-fixing the light-sensitive material, wherein a bleach-fixing solution used in said bleach-fixing comprises a ferric complex salt of a compound represented by the following formula A: wherein A 1 , A 2 , A 3 and A 4 are independently a -CH 2 OH group, a -PO 3 M 2 group or a -COOM group, which may be the same or different; M is hydrogen or a cation; and X is a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms or a -(B 1 O) n -B 2 - group, in which n is an integer of 1 to 8, B 1 and B 2 are independently a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, which may be the same or different. A use of a bleach-fixing solution for processing a silver halide colour photographic light-sensitive material wherein said solution comprises a ferric complex salt of a compound represented by the following formula A: wherein A 1 , A 2 , A 3 and A 4 are independently a -CH 2 OH group, a -PO 3 M 2 group or a -COOM group, which may be the same or different; M is hydrogen or a cation; and X is a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms or a -(B 1 O) n -B 2 - group, in which n is an integer of 1 to 8, B 1 and B 2 are independently a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, which may be the same or different.

Inventors: KUWAEACAC, UEDA YUTAKA, UEDA, YUTAKA
Applicants: KONISHIROKU PHOTO IND, KONICA CORPORATION
Application year: 1992
Main classification: G03C7
IPC codes: G03C7, G03C5