JPH0379699B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a processing solution having bleaching ability for silver halide color photographic materials. For more details,
This invention relates to an effective bleaching solution and bleach-fixing solution for silver halide color photographic materials, which have improved various processing performance and solution properties. [Prior Art] Generally, in order to obtain a color image by processing an imagewise exposed silver halide color photographic light-sensitive material, after a color development step, the produced metallic silver is treated with a processing solution having bleaching ability. A process is provided. Bleaching solutions and bleach-fixing solutions are known as processing solutions having bleaching ability. When a bleaching solution is used, a step of fixing the silver halide with a fixing agent is usually added after the bleaching step, but with a bleach-fixing solution, bleaching and fixing are performed in one step. In processing solutions having bleaching ability for processing silver halide color photographic materials, inorganic oxidizing agents such as red blood cells and dichromates are widely used as oxidizing agents for bleaching image silver. However, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, red blood salt and dichromate have relatively good bleaching power and irritation for image silver, but there is a risk that they will decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body. ,
It has unfavorable properties in terms of pollution prevention. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizers such as thiosulfates in the same processing solution, and it is difficult to use these oxidizing agents in bleach-fixing baths. This makes it difficult to achieve the goal of speeding up and simplifying the process. Furthermore, processing liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse the waste liquid after treatment without discarding it. On the other hand, metal complex salts of organic acids, such as aminopolycarboxylic acid metal complex salts, are used as oxidizing agents, as they have fewer pollution problems and meet the demands of speeding up and simplifying treatment, and enabling the reuse of waste liquids. In recent years, treatment solutions have come to be used. However, processing solutions using metal complex salts of organic acids have a slow oxidizing power, so they have the disadvantage that the bleaching rate (oxidation rate) of image silver (metallic silver) formed in the development process is slow. . For example, iron() complex salt of ethylenediaminetetraacetate, which is considered to have the strongest bleaching power among aminopolycarboxylic acid metal complex salts, has been put into practical use as a bleaching solution and a bleach-fixing solution in some places, but silver bromide, High-sensitivity silver halide color photographic materials based on silver iodobromide emulsions, especially color papers for photography, color negative films for photography, and color reversal films containing silver iodide as silver halide, have a high bleaching power. If the amount is insufficient, traces of image silver will remain even after long-term processing, resulting in poor desilvering performance. This tendency is particularly noticeable in bleach-fix solutions in which oxidizing agents and thiosulfates and sulfites coexist because the redox potential decreases. On the other hand, despite great efforts to develop bleaching accelerators to increase the silver bleaching power of bleaching solutions or bleach-fixing solutions containing metal complex salts of organic acids, satisfactory results have not yet been obtained. The reality is that it is not. The present inventors have discovered diethylenetriaminepentaacetic acid iron() complex salt as an oxidizing agent that has excellent oxidizing power particularly in a high pH range among aminopolycarboxylic acid metal complex salts. Bleach and bleach-fix solutions that use diethylenetriamine iron pentaacetate complex salt as an oxidizing agent have a rapid silver bleaching reaction, produce less stain when directly bleached, and have good storage stability. It has extremely excellent performance. However, it has been found that when diethylenetriaminepentaacetic acid iron () complex salt is used as an oxidizing agent in a bleach solution or a bleach-fix solution, yellow staining likely occurs, which is thought to be caused by the coloring of the iron () complex salt. In particular, when the amount of washing with water was insufficient, remarkable yellow staining was observed, which was found to be a serious problem in terms of photographic performance. Therefore, in order to put diethylenetriamine iron pentaacetate () complex salt to practical use as a bleaching solution or bleach-fix solution, it is necessary to prevent yellow staining caused by diethylene triamine iron pentaacetate () complex salt, and to
There is a strong desire to develop a technology that does not impair the silver bleaching ability, stain resistance, and liquid storage stability of complex salts. [Object of the Invention] The object of the present invention is to provide a solution that has rapid silver bleaching power, does not generate stains, and has good storage stability even when used as a bleach-fix solution as a processing solution with bleaching ability. Excellent, and does not cause contamination with diethylenetriaminepentaacetic acid iron () complex salt.
An object of the present invention is to provide a processing solution having bleaching ability for silver halide color photographic materials. Other objects of the invention will become apparent from the following description of the specification. [Structure of the Invention] As a result of intensive research, the present inventors have found that the above-mentioned objects, etc. are achieved by providing a bleaching solution and a bleach-fixing solution containing diethylenetriaminepentaacetic acid iron () complex salt as an oxidizing agent, and containing the following metal ions of the present invention. It was found that this can be achieved by [Metal ions] Calcium, bismuth, strontium, manganese, aluminum, tin, barium, zirconium. The present invention will be explained in detail below. In general, contamination by ethylenediaminetetraacetic acid iron () complex salts, which are some of the aminopolycarboxylic acid iron () complex salts that have been put into practical use, is rarely seen in normal processing, and the washing time and amount of water in the washing process are limited. When reduced, it tends to remain in the photosensitive material or paper support, exhibiting the color of iron () salt itself and causing staining. It is particularly well known that this phenomenon occurs at the edges of color paper. In addition, a method of adding metal ions or a soluble complex salt of metal ions and aminopolycarboxylic acid using an aminopolycarboxylic acid iron complex salt as an oxidizing agent is
34-180, JP-A No. 53-13418, and JP-A-53-31134, all of these methods use ethylenediaminetetraacetic acid iron () complex salt as the main oxidizing agent to oxidize metal ions or metal ions and aminopolymer. This method involves adding a soluble complex salt with a carboxylic acid, which poses no pollution problem and is intended to prevent the formation of leuco pigments. Therefore, the present invention uses diethylenetriaminepentaacetic acid iron() complex salt as an oxidizing agent among aminopolycarboxylic acid iron complex salts, and it has been found that yellow staining is particularly large when diethylenetriaminepentaacetic acid iron() complex salt is used. The above-mentioned known example differs from the above-mentioned technical concept in that it was discovered that yellow staining could be prevented only by adding the metal ion of the present invention or a soluble complex salt of a metal ion and an aminopolycarboxylic acid to prevent yellow staining. The difference is that Further, although the yellow stain described above can be prevented to some extent by extending the washing time and increasing the amount of water washed, in the case of diethylenetriaminepentaacetic acid iron() complex salt, even if the above measures are taken, the yellow stain cannot be sufficiently prevented; This becomes a big problem when the purpose of rapid treatment is to secure water resources and reduce costs. The present invention has investigated various methods for preventing yellow staining caused by diethylenetriamine iron pentaacetate complex salt without increasing the amount of water washing while maintaining various excellent properties of diethylene triamine pentaacetic acid iron complex salt. As a result, this has been achieved. The diethylenetriaminepentaacetic acid iron() complex salt according to the present invention is a free acid (hydrogen salt), an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt, or an ammonium salt, or a water-soluble amine salt such as a triethanolamine salt, etc. However, preferably the potassium, sodium and ammonium salts are used. At least one type of these iron() complex salts may be used, but two or more types can also be used in combination. The amount used can be arbitrarily selected and must be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but generally it is used at a lower concentration than other aminopolycarboxylate salts because of its high oxidizing power. Can be used. For example, per liquid used
It can be used in an amount of 0.01 mol or more, preferably 0.05 mol or more. In addition, it is desirable to use the replenisher after concentrating it to maximize its solubility in order to achieve high concentration and low replenishment. The metal ions used in the present invention may be supplied by any method. For example, inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, and acetates, or chelating agents such as polycarboxylic acids, aminopolycarboxylic acids, oxycarboxylic acids, polyphosphoric acids, and organic phosphonic acids. It can be supplied as a soluble complex salt. The metal ions of the present invention can be supplied as the following compounds, but are not limited to these supply methods, and can also be supplied as soluble complex salts,
It may also be supplied using an electrical method or the like. <Exemplary compounds> A-1 Ca(CH ₃ COO) ₂・H ₂ O A-2 CaCO ₃ A-3 CaCl ₂・2H ₂ O A-4 Ca(C ₆ H ₅ O ₇ ) ₂・4H ₂ O A -5 Ca(OH) ₂ A-6 CaC ₄ H ₂ O ₄ A-7 Ca(NO ₃ ) ₂・4H ₂ O A-8 BiCl ₃ A-9 BiC ₆ H ₅ O ₇ A-10 Bi(NO ₃ ) ₃・5H ₂ O A−11 Sr(CH ₃ COO) ₂・1/2H ₂ O A−12 SrCO ₃ A−13 SrCl ₂・6H ₂ O A−14 SrSO ₄ A−15 Mn(CH ₃ COO) ₂・4H ₂ O A−16 MnCO ₃・nH ₂ O A−17 MnCl ₂・4H ₂ O A−18 Mn(NO ₃ ) ₂・nH ₂ O A−19 MnSO ₄・nH ₂ O A−20 AlCl ₃・6H ₂ O A−21 Al(NO ₃ ) ₃・9H ₂ O A−22 AlPO ₄ A−23 SnCl ₂・2H ₂ O A−24 SnCl ₄ A−25 SnSO ₄ A−26 BaCl ₂ A−27 Ba ( _NO3 ) _2A -28Zr( _SO4 ) _2.4H2O These metal compounds of the present invention may be used alone or in combination _of two or more. The amount used is preferably from 5 x 10 ^-3 mol to 2 mol, particularly preferably from 3 x 10 ^-2 mol to 1 mol per solution used. The bleaching solution and bleach-fixing solution of the present invention have a pH of from 0.2 to
It can be used at a pH of 9.5, preferably 4.0 or higher, more preferably 5.0 or higher, and the most preferable PH range is 5.5 or higher and 9.0 or lower. The treatment temperature is 80°C or lower, preferably 55°C or lower to prevent evaporation. The bleaching solution of the present invention contains diethylenetriaminepentaacetic acid iron () complex salt as a bleaching agent as described above and the metal ion of the present invention, and may also contain various additives. As additives, chelating agents such as polycarboxylic acids, aminopolycarboxylic acids, oxycarboxylic acids, aminocarboxylic acids, polyphosphoric acids, organic phosphonic acids, aminophosphonic acids, phosphonocarboxylic acids, alkali halides or ammonium halides, e.g. It is desirable to contain potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, thiourea, and the like. Additionally, PH buffers such as borates, oxalates, acetates, carbonates, and phosphates, solubilizers such as triethanolamine, alkylamines, polyethylene oxides, etc. are known to be added to ordinary bleaching solutions. It is possible to add as appropriate. The bleach-fixing solution of the present invention includes iron diethylenetriaminepentaacetate () as a bleaching agent as described above.
A liquid having a composition containing a complex salt and the metal ion of the present invention, a silver halide fixing agent such as thiosulfate, thiocyanate, thiourea, thioether, and the above-mentioned chelating agent is applied. In addition, a bleach-fixing solution consisting of the bleaching agent of the present invention and the above-mentioned silver halide fixing agent to which a small amount of a halogen compound such as potassium bromide is added, or conversely, a halogen compound such as potassium bromide or ammonium bromide may be used. It is also possible to use a bleach-fix solution having a composition in which a large amount of potassium bromide is added, or a special bleach-fix solution having a composition in combination with a large amount of a halogen compound such as potassium bromide. As the halogen compound mentioned above, in addition to potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. The silver halide fixing agent to be included in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as those used in normal fixing processing.
For example, thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate,
Typical examples include thiocyanates such as ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides.
These fixing agents can be used in an amount of 5 g/or more, within the range that can be dissolved. The bleach-fix solution contains boric acid, borax, sodium hydroxide, potassium hydroxide,
PH buffering agents consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, stabilizers such as nitroalcohol nitrates, solubilizers such as alkanolamines, organic amines, etc. Stain inhibitors, other additives, and organic solvents such as methanol, dimethyl formamide, and dimethyl sulfoxide can be appropriately contained. In the processing method using the processing solution of the present invention, the most preferable processing method is to perform bleaching or bleach-fixing immediately after color development. A fixing treatment may be performed, or a prebath containing a bleach accelerator may be used as a processing solution prior to bleaching or bleach-fixing. After bleaching and fixing (or bleach-fixing), stabilization treatment may be performed without washing with water, or washing with water may be performed and then stabilization treatment may be performed. In addition to the above steps, known auxiliary steps may be added as necessary, such as hardening, neutralization, black development, reversal, and washing with a small amount of water. A typical example of a preferred treatment method includes the following steps. (1) Color development → bleach-fix → water washing (2) color development → bleach-fix → small amount of water washing → water washing (3) color development → bleach-fix → water washing → stable (4) color development → bleach-fix → stable (5) color development → Washing with water → Bleach-fix → Washing with water (6) Color development → Stop → Bleach-fix → Wash with water (7) Color development → Bleach → Wash with water → Fix → Wash with water → Stable (8) Color development → Bleach → Fix → Wash with water → Stabilize (9) Color development → bleaching → washing with a small amount of water → fixing → washing with a small amount of water → washing with water → stabilization (10) Color development → washing with a small amount of water → bleaching → washing with a small amount of water → fixing → washing with a small amount of water → washing with water → stabilization (11) Color development → stop → bleaching → washing with a small amount of water → Fixation → Wash with a small amount of water → Wash with water → Stabilize (12) Black development → Wash with water → Reverse → Color development → Bleach → Fix → Wash with water → Stabilize (13) Pre-hardening → Neutralization → Black development → Stop → Color development → Bleach → Fix → Water washing → Stabilization The black developer used before processing with the processing solution having bleaching ability of the present invention is the so-called black first developer used in the processing of color photographic light-sensitive materials, or black It is used in the processing of photographic materials, and can contain various additives that are generally added to black developing solutions. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, etc. Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds, etc. can be mentioned. The aromatic primary amine color developing agent used in the color developer used before processing with the processing solution having bleaching ability of the present invention includes known ones that are widely used in various color photographic processes. be done. 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. In addition, these compounds are generally used at a concentration of about 0.1 g to about 30 g per color developer,
More preferably, about 1 g per color developer 1
Use at a concentration of ~15g. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxy-toluene, 2-amino-
Included are 3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like. Particularly useful primary aromatic amino color developers are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. . Among them, examples of particularly useful compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, -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-
Examples include 3-methylaniline-p-toluenesulfonate. The alkaline color developing solution used before the treatment with the processing solution having bleaching ability of the present invention is
In addition to the aromatic amine color developer, various components normally added to color developers, 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-hydroxyethylidene-1,1-diphosphonic acid. You can also do that. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. The silver halide color photographic light-sensitive material to which the processing solution having bleaching ability of the present invention can be applied uses an internal development method (U.S. Pat.
2376679 and 2801171), as well as
External development method in which a coloring agent is contained in the developer (U.S. Patent No. 2252718, U.S. Patent No. 2592243, U.S. Patent No.
2590970).
Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan color formers are based on naphthol or phenol structure,
Those that form indoaniline dyes by coupling; magenta color formers that have a 5-pyrazolone ring with an active methylene group as their skeleton structure; yellow color formers that include benzoylacetanilide and pivalylacetanilide that have active methylene chains. It is possible to use those having a substituent or acylacetanilide structure, with or without a substituent at the coupling position. Thus, as the coloring agent, both so-called 2-equivalent type couplers and 4-equivalent type couplers can be applied.
Silver halide emulsions that can be used include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Any silver halide such as silver chloroiodobromide or a mixture thereof may be used. Furthermore, as protective colloids for these silver halides, natural products such as gelatin, as well as various products obtained by synthesis can be used. The silver halide emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants. The bleaching solution and bleach-fixing solution of the present invention can be applied to silver halide color photographic materials such as color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and reversal color paper. It can be applied to [Examples] The details of the present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 After pretreatment by corona discharge on a paper support coated on the surface with a polyethylene layer containing anatase titanium oxide as white pigment,
Color photographic paper was made by applying each of the following layers in sequence. 1st layer: α-[4-(1
-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidyl)]-α-pivalyl-2-chloro-5-[γ-(2,4-di-
A blue-sensitive silver chlorobromide emulsion layer containing t-amylphenoxy)butylamide]acetanilide and 5 mol% of silver chloride. Second layer: gelatin intermediate layer containing UV absorbers. 3rd layer: 1-(2,4,
A green-sensitive silver chlorobromide emulsion layer containing 6-trichlorophenyl)-3-(2-chloro-5-octadecenylsuccinamidoanilino)-5-pyrazolone and 15 mol% silver chloride. 4th layer: gelatin middle layer same as 2nd layer. Fifth layer: red-sensitive salt containing 2,4-dichloro-3-methyl-6-[γ-(2,4-diamylphenoxy)butyramide]phenol as cyan coupler and 15 mol% silver chloride. Silver bromide emulsion layer. 6th layer: gelatin protective layer. Each of the above photosensitive emulsion layers has a total silver content of 100 cm ²
It was applied at a dose of 10 mg per coat. In addition, the silver halide color photographic emulsions used in each light-sensitive emulsion layer were chemically sensitized with sodium thiosulfate.
Conventional additives such as stabilizers and sensitizing dyes were added. Further, a hardening agent and a spreading agent were added to the coating solution for all layers. After the color photographic paper produced as described above was printed (with borders), it was subjected to continuous replenishment processing using a roll-type automatic developing machine (hereinafter referred to as self-development running processing).

[Color developer replenisher]

Benzyl alcohol 20ml Ethylene glycol 20ml Fluorescent brightener (4,4'-diaminostilbenzylsulfonic acid derivative) 2.0g Hydroxyamine sulfate 4.0g 3-Methyl-4amino-N-ethyl-N-(β-methanesulfonamide) ethyl)aniline sulfate
7.0g Potassium carbonate 30g 1-hydroxyethylidene-1.1-diphosphonic acid (60% solution) 1.1ml Potassium sulfite (50% solution) 5ml Potassium hydroxide 3.0g After adjusting the total amount to 1, add potassium hydroxide as appropriate. Adjust so that the pH is 10.40. Color developing solution: Add the following color developing starter to 800 ml of the above color developing replenisher, add water, and make 1
In this case, a color developing solution 1 having a pH of 10.20 was prepared, and the amount necessary for processing was appropriately prepared and used. [Color development starter] Potassium carbonate 2.2g Potassium bicarbonate 3.4g Potassium bromide 0.64g Potassium chloride 0.50g The bleach-fix solution and bleach-fix replenisher used were as follows. [Bleach-fix solution and bleach-fix replenisher (1)] Ethylenediaminetetraacetic acid () complex salt 70g Ethylenediaminetetraacetic acid 20g Ammonium sulfite (50% solution) 30ml Ammonium thiosulfate (70% solution) 140ml Aqueous ammonia (28% solution) 30ml Aqueous ammonia Or, use acetic acid to adjust the pH to 7.0 and adjust the total volume to 1. [Bleach-fix solution and bleach-fix replenisher (2)] Ammonium diethylenetriaminepentaacetate 80g Diethylenetriaminepentaacetic acid 24g Ammonium sulfite (50% solution) 30ml Ammonium thiosulfate (70% solution) 140ml Aqueous ammonia (28%) solution 30ml Ammonia Adjust the pH to 7.0 with water or acetic acid.
Also, make sure that the total amount is 1. Using the bleach-fix solution and bleach-fix replenisher (1) and (2), carry out automatic running processing until the amount of each bleach-fix replenisher used is twice the tank capacity of the bleach-fix bath, and at the end of the run. A sample of 3 to 5 m of color photographic paper was taken, the edges were cut to a width of 5 mm, the paper was tightly rolled into a roll, and the blue reflection density at the edges was measured, which was taken as the contamination characteristics of the edges.
Further, the amount of water used for washing was 7/m ² and 300 ml/m ² . Furthermore, in order to examine the effect of containing metal ions in the present invention, 6.0 g/metal compound as shown in Table 1 was added to the bleach-fix solution (1) and the bleach-fix replenisher (2), and the The method was evaluated.

[Color developer]

Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 5g Sodium bromide 1.3g Potassium iodide 2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g Sodium diethylenetriaminepentaacetate 2.5g 4-Amino-3-methyl-N-ethyl-N-
(β-Hydroxyethyl)aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to make 1, potassium hydroxide or
Adjust the pH to 10.06 using 20% sulfuric acid. [Color developer replenisher] Potassium carbonate 35g Sodium hydrogen carbonate 3g Potassium sulfite 7g Sodium bromide 0.9g Hydroxylamine sulfate 3.1g Sodium diethylenetriaminepentaacetate 3.2g 4-amino-3-methyl-4-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
5.4g potassium hydroxide 2g Add water to make 1, potassium hydroxide or
Adjust the pH to 10.12 using 20% sulfuric acid. [Bleach-fix solution and bleach-fix replenisher (1)] Ethylenediaminetetraacetic acid iron () ammonium dihydrate 120g Ethylenediaminetetraacetic acid 18g Ammonium thiosulfate (70% solution) 300ml Ammonium sulfite (40% solution) 40ml Adjust pH to 6.8 with ammonia water and add water to bring the total volume to 1. [Bleach-fix solution and bleach-fix replenisher (2)] Ammonium diethylenetriaminepentaacetate (2) 142g Diethylenetriaminepentaacetic acid 24g Ammonium thiosulfate (70% solution) 300ml Ammonium sulfite (40% solution) 40ml Adjust the pH to 6.8 with aqueous ammonia. At the same time, add water to bring the total volume to 1. [Bleach-fix solution and bleach-fix replenisher (3)] Ammonium diethylenetriaminepentaacetic acid iron () 142g Diethylenetriaminepentaacetic acid 24g Soluble complex salt of exemplified compound (A-8) and ethylenediaminetetraacetic acid 7g Ammonium thiosulfate (70% solution) 300ml Ammonium sulfate (40% solution) 40ml Adjust the pH to 6.8 with aqueous ammonia, and add water to bring the total volume to 1. [Stabilizing solution] Formalin (37% aqueous solution) 2 ml Konidax [manufactured by Konishiroku Photo Industry Co., Ltd.] 5 ml Add water to make 1. [Stable replenisher] Formalin (37% aqueous solution) 3 ml Konidax [manufactured by Konishiroku Photo Industry Co., Ltd.] 7 ml Add water to make 1. Color developer replenisher is for color negative film 100cm ²
15 ml of color developer bath was replenished per 100 cm 2 of color negative film, 9 ml of bleach-fix replenisher was replenished to the bleach-fix bath per 100 cm 2 of color negative film ^, and 11 ml of stabilizing replenisher was replenished to the stabilizing bath per 100 cm ² of color negative film. In addition, in the washing bath, water is used to store color negative film 100cm ²
30ml per hit was washed away. Using bleach-fixing and bleach-fixing replenishers (1) to (3),
Each film was continuously replenished for 1500 m. After each development run was completed, the bleach-fixing tank solution was stored in a tightly closed refrigerator. After all self-development running processes are completed, adjust the pH of the bleach-fixing tank solutions (1) to (3) to the values shown in Table 2, perform manual processing, and determine the blue transmission density (contamination degree) and the desilvering completion time. After measuring the clearing time, we also measured the maximum red density (cyan dye density) and minimum green density (magenta stain) of the film obtained by bleach-fixing for 35 minutes. Second result
Shown in the table. However, the blue transmission density was measured after complete desilvering to distinguish it from an increase in blue density due to poor desilvering. The processing conditions were the same as those for the self-development running process except for the bleach-fixing processing time, and the processing solution used had the same composition as the self-development running process except for the bleach-fix solution. The processed sample used was Sakura color film (manufactured by Konishiroku Photo Industry Co., Ltd.) cut into pieces and subjected to wedge-shaped exposure according to a conventional method. For comparison, a sample treated with Sakura Color Negative Process CNK-4, which is a standard treatment, was similarly measured. However, the desilvering treatment time was 6 minutes 30 seconds for bleaching and 6 minutes 30 seconds for fixing.

【table】

[Table] As is clear from the results in Table 2, the bleach-fix solution (3) of the present invention to which a soluble complex salt of metal compound (A-8) and ethylenediaminetetraacetic acid has been added is the same as the bleach-fix solution (3) to which no metal compound has been added. Compared to fixer (2), the lowest blue density of the standard treatment is close to 0.67, indicating that contamination by diethylenetriaminepentaacetic acid iron() complex salt is largely prevented. Also, good results were obtained regarding the clearing time, as there was no effect at all due to the addition of the complex salt of the metal compound of the present invention and the chelating agent. Furthermore, we observed the maximum red density (cyan dye density) and minimum green density (magenta stain) of the film obtained by bleach-fixing for 35 minutes, as well as the number of days until silver sulfide was formed, but no adverse effects were observed due to the addition of metal compounds. Nakatsuta.

Claims (1)

[Scope of Claims] 1. Bleaching ability for a silver halide color photographic light-sensitive material, characterized in that it contains a diethylenetriamine iron pentaacetate complex salt and at least one metal ion selected from the following metal ion group: A processing liquid having [Metal ions] Calcium, bismuth, strontium, manganese, aluminum, tin, barium, zirconium.