JPH0566579B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for processing silver halide color photographic materials, and more specifically, an effective method for processing silver halide color photographic materials that improves various processing performances in the bleaching process. It is related to. [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 bleach 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-fix solution, bleaching and fixing are performed in one step. Inorganic oxidizing agents such as red blood salts and dichromates are widely used as oxidizing agents for bleaching image silver in processing solutions that have bleaching ability in processing silver halide color photographic light-sensitive materials. . 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 are relatively good in terms of bleaching power 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 thiosulfate in the same processing solution, and it is difficult to use these oxidizing agents in bleach-fixing baths. is almost impossible, which makes it difficult to achieve the objective 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 have been used as oxidizing agents as they have fewer pollution problems and meet the demands of speeding up and simplifying the treatment and making it possible to reuse the waste liquid. Treatment liquids have come to be used. However, processing solutions using metal complex salts of organic acids have slow oxidizing power, so the image silver (metallic silver) formed during the development process
The disadvantage is that the bleaching rate (oxidation rate) 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, iodine, etc. High-sensitivity silver halide color photographic materials based on silver bromide emulsions, especially color papers for photography, color negative films for photography, and color reversal films for photography that contain silver iodide as silver halide, lack bleaching power. However, even after long-term processing, traces of image silver remain, resulting in poor desilvering properties. This tendency is particularly noticeable in bleach-fix solutions in which oxidizing agents, thiosulfates, and sulfites coexist because the redox potential decreases. On the other hand, although great efforts have been made 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 achieved. The reality is that we are not getting it. 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. A bleaching solution and a bleach-fixing solution using diethylenetriaminepentaacetic acid iron() complex salt as an oxidizing agent have a pH of 4 or more, especially 7 or more, and have a rapid silver bleaching reaction and extremely excellent performance. On the other hand, in recent years, efforts have been made to reduce the number of processing steps in order to speed up processing and reduce the installation space of processing equipment, and in particular, after the color development step, the process is directly connected to the development step without going through a stop or washing step. Bleaching or bleach-fixing treatments have become common. One serious problem in such processing is that the color developing solution is brought directly into the bleach or bleach-fix solution during the transportation of the photographic material, so that the developing agent is oxidized in the bleach or bleach-fix solution. This means that tar is more likely to be generated, and this tendency becomes especially strong when the throughput decreases and the update rate becomes low. That is, in recent years, for the purpose of preventing environmental pollution and conserving resources, progress has been made in reducing replenishment processing, in which the amount of replenishment required for each processing of a certain area of silver halide color photographic light-sensitive materials is as small as possible. In particular, there is a problem in processing that the ratio of bleaching or bleach-fixing solution mixed into the color developing solution as described above becomes high, which tends to generate tar. The generation of such tar causes problems such as tar adhesion to photographic light-sensitive materials, which not only significantly impairs the finishing quality of the photographic light-sensitive materials, but also, especially in the case of photographic light-sensitive materials for photography, since enlarged prints are usually made. Even a small amount of tar often causes a serious problem. The generation of tar is significant in bleaching solutions, and the commonly used iron ethylenediaminetetraacetate ()
Bleach-fix solutions that use complex salts as oxidizing agents have weak oxidizing power, and sulfites, which are used as preservatives in the fixer, coexist, so this problem generally does not occur. If the mixing ratio is high, it becomes a problem. Furthermore, bleaching solutions and bleach-fixing solutions that use diethylenetriaminepentaacetic acid complex salt as an oxidizing agent cause particularly significant generation of tar.
It has become clear that this phenomenon is also likely to occur in bleach-fix solutions. [Object of the Invention] The object of the present invention is to provide a silver halide color photographic light-sensitive material which is free from problems caused by tar adhesion and which has an excellent desilvering speed even when the silver halide color photographic light-sensitive material is subjected to direct bleaching or bleach-fixing treatment after color development. An object of the present invention is to provide a method for processing color photographic materials. Still another object of the present invention is to provide a method for processing silver halide color photographic materials that is rapid and highly effective in conserving resources and preventing the environment. [Structure of the Invention] As a result of extensive research, the present inventors have found that the above-mentioned objects of the present invention have been achieved by producing a paraphenylene compound having at least one water-soluble group in the amino group after imagewise exposure of a silver halide color photographic light-sensitive material. A processing solution that is developed with a color developing solution containing a diamine-based color developing agent, and then has a bleaching ability and contains a diethylenetriaminepentaacetate iron () complex salt and at least one iron () complex salt selected from the following iron () complex salt group. In a direct bleaching type low replenishment type continuous processing system that is connected to the above development process, the following iron () complex salt diethylenetriaminepentaacetate (iron()) is used.
It has been found that this can be achieved by a method for processing a silver halide color photographic material, characterized in that the molar ratio to the complex salt is from 0.01 to 0.5. [Iron () complex salt] Ethylenediamine iron tetraacetate () complex salt trans-cyclohexanediamine iron tetraacetate () complex salt diaminopropanol iron tetraacetate () complex salt ethylenediamine orthohydroxyphenylacetate iron () complex salt glycol ether diamine iron tetraacetate () complex salt Diaminopropane iron tetraacetate () complex triethylenetetramine iron hexaacetate () complex salt N-hydroxyethyliminodiacetic acid iron () complex salt That is, the present inventors have discovered that the color developing solution containing the color developing agent according to the present invention is diethylene triamine When mixed with a bleaching solution or a bleach-fix solution containing at least one iron () acetate complex salt and the iron () complex salt according to the present invention, a conventional bleaching solution using an ethylenediaminetetraacetic acid iron () complex salt as an oxidizing agent may be used. Or, when a color developer is mixed into a bleach-fix solution, or when a color developer is mixed into a bleach-fix solution or a bleach-fix solution that uses diethylenetriaminepentaacetic acid (iron) complex salt as an oxidizing agent, the generation of tar is significant. I found that it is less. That is,
The inventors have discovered that the above objects of the invention can be achieved by an effective combination of the processing steps of the invention. 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. Potassium salts, sodium salts and ammonium salts are preferably used, with ammonium salts being particularly preferred. 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 needs to 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 aminopolycarboxylic acid complex salts because of its high oxidizing power. Can be used. For example, liquid 1
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 iron () complex salt according to the present invention is an iron () complex salt of the chelating agent shown below. Ethylenediaminetetraacetic acid

【formula】 trans-cyclohexanediaminetetraacetic acid

【formula】 diaminopropanoltetraacetic acid

〔Example〕

Hereinafter, the details of the present invention will be explained with reference to Examples, but the embodiments of the present invention are not limited thereby. Example 1 A bleach-fix solution and a bleach solution were prepared as follows. [Bleach-fix solution (1)] Ethylenediaminetetraacetic acid iron () ammonium dihydrate 130g Ethylenediaminetetraacetic acid 10g Ammonium sulfite (40% solution) 20ml Ammonium thiosulfate (70% solution) 300ml Color developer 3ml Adjust pH to 7.2 with aqueous ammonia Adjust and add water to bring the total volume to 1. [Bleach-fix solution (2)] Ammonium diethylenetriamine iron pentaacetate 135g Ammonium sulfite (40% solution) 20ml Ammonium thiosulfate (70% solution) 300ml Color developer 3ml Adjust the pH to 7.2 with aqueous ammonia and add water. Let the total amount be 1. [Bleach-fix solution (3)] Sodium diethylenetriamine iron pentaacetate 130g Ammonium sulfite (40% solution) 20ml Ammonium thiosulfate (70% solution) 300ml Color developer 3ml Adjust the pH to 7.2 with aqueous ammonia and add water. Let the total amount be 1. [Bleach solution (1)] Ethylenediaminetetraacetic acid iron () ammonium dihydrate 130g Ethylenediaminetetraacetic acid 15g Ammonium bromide 150g Color developer 3ml Adjust the pH to 6.2 with aqueous ammonia and add water to bring the total volume to 1. [Bleach solution (2)] Ammonium diethylenetriamine iron pentaacetate 135g Ammonium bromide 150g Color developer 3ml Adjust the pH to 6.2 with aqueous ammonia and add water to bring the total volume to 1. [Bleach solution (3)] Sodium diethylenetriaminepentaacetate 130g Ammonium bromide 150g Color developer 3ml Adjust the pH to 6.2 with aqueous ammonia and add water to bring the total volume to 1. The bleach-fix solution and the color developing solution added to the bleach solution were prepared as follows. [Color developer]

[Stabilizing liquid]

Formalin (37% aqueous solution) 2 ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) Add 5 ml water to make 1. [Fixer] Ammonium thiosulfate (70% solution) 120ml Ammonium sulfite (40% solution) 25ml Adjust the pH to 65 with ammonia water and add water to bring the total volume to 1. After processing the 10 films unexposed for each bleach-fix and bleach solution, 0.1
The number of tar spots larger than cm ² was counted and the results are shown in Table 1. Bleach-fix solutions using EDTA/FeNH ₄ as bleaching agents and bleach solutions No. 1 to No. 4 contain relatively little tar, but there is no change even when other iron () complex salts are added. In contrast, bleach-fix solutions and bleaching solutions that use DTPA Fe(NH ₄ ) ₂ as a bleaching agent do not contain other iron()
Bleach-fix solution using EDTA/FeNH ₄ as a bleaching agent in the case where no complex salt is added (No. 5) and in the case where comparative iron () complex salts other than the present invention are added (No. 6 and No. 7). There is more tar than bleaching solution, but when the iron () complex salt of the present invention is added (No. 8
(No. 15), it can be seen that tar is significantly reduced. Furthermore, in the case of bleach-fix solutions and bleaching solutions using DTPA/Fe NaH as a bleaching agent (No. 16 and No. 17), slightly inferior results were obtained compared to DTPA/Fe(NH ₄ ) ₂ .

【table】

[Bleach-fix solution (1)]

Diethylenetriaminepentaacetic acid iron() ammonium 140g Ammonium sulfite (40% solution) 20ml Ammonium thiosulfate (70% solution) 300ml Diethylenetriaminepentaacetic acid 5g Color developer Table 2 Amounts Adjusted to PH7.2 with aqueous ammonia and added water. Let the total amount be 1. [Bleach-fix solution (2)] Ammonium diethylenetriaminepentaacetate 140g Ammonium sulfite (40% solution) 20ml Ammonium thiosulfate (70% solution) 300ml Diethylenetriaminepentaacetic acid 5g Iron()ammonium ethylenediaminetetraacetate
10g Color developer Amount listed in Table 2 Adjust the pH to 72 with aqueous ammonia and add water to bring the total amount to 1. The color developer mixed in bleach-fix solutions (1) and (2) was the same as that used in Example 1.
The type of color developing agent and the amount of color developer mixed are as shown in Table 2. In addition, bleach-fix solution (1)
Bleach-fix solutions Nos. 1 to 6 in Table 2 were prepared from Bleach-Fix Solution (2), and bleach-fix solutions Nos. 7 to 12 in Table 2 were prepared from Bleach-Fix Solution (2). Among the color developing agents shown in Table 2, Comparisons (1), (2) and (3) are the color developing agents shown below. comparison (1) comparison (2) comparison (3) These bleach-fix solutions were evaluated for tar under the same conditions as in Example 1. However, the color developer used in the processing was the same as that mixed in the bleach-fix solution, and the stabilizer used the same formulation as in Example 1. As is clear from the results shown in Table 2, iron () ammonium ethylenediaminetetraacetate was added and the color developing agent according to the present invention was mixed.
It can be seen that only Nos. 10, 11, and 12 have a significant reduction in tar, and that the tar suppression effect is particularly strong when the color developer mixture rate is 2% or more. In addition, experiments were also conducted on other iron () complex salts of the present invention, and almost the same results were obtained.

[Example 3]

A bleach-fix solution was prepared as follows. Diethylenetriaminepentaacetic acid iron() ammonium Table 3 Amounts listed Diaminopropane tetraacetic acid iron() ammonium Table 3 Listing amounts Diethylenetriaminepentaacetic acid 5g Ammonium sulfite (40% solution) 20ml Ammonium thiosulfate (70% solution) 300ml Color developer 4ml Ammonia Adjust the pH to 7.2 with water and add water to bring the total volume to 1. The amounts of diethylenetriaminepentaacetate iron ()ammonium and diaminopropanetetraacetate iron()ammonium were varied as shown in Table 3 so that the total amount was 0.3 mol. In addition, the same color developer as in Example 1 was used,
Tar generation was evaluated under the same conditions as in Example 1, and the results are shown in Table 3. As is clear from Table 3, tar generation is suppressed by adding 0.01 times or more of iron() ammonium diaminopropanetetraacetate to diethylenetriaminepentaacetate, and a significant suppressive effect is achieved when adding less than 1.0 times. It can be seen that the following can be obtained. It should be noted that experiments were also conducted on other iron() complex salts of the present invention, and almost the same results were obtained.

【table】

Claims (1)

[Scope of Claims] 1 After imagewise exposure of a silver halide color photographic light-sensitive material, it is developed with a color developer containing a paraphenylenediamine color developing agent having at least one water-soluble group in an amino group, and then diethylenetriamine. Direct bleaching type low replenishment type continuous development in which processing is performed in connection with the development process with a processing solution having bleaching ability containing an iron () complex salt of pentaacetate and at least one iron () complex salt selected from the following iron () complex salt group. A method for processing a silver halide color photographic material, characterized in that, in the processing system, the molar ratio of iron () complex salt to diethylenetriaminepentaacetic acid iron () complex salt is from 0.01 to 0.5. [Iron () complex salt] Ethylenediamine iron tetraacetate () complex salt trans-cyclohexane diamine iron tetraacetate () complex diaminopropanol iron tetraacetate () complex salt ethylene diamine diorthohydroxyphenylacetate iron () complex salt glycol ether diamine iron tetraacetate () complex salt Complex salt diaminopropane iron tetraacetate () complex triethylenetetramine iron hexaacetate () complex salt N-hydroxyethyliminodiacetic acid iron () complex salt 2 The color developing solution contains -(CH ₂ ) as the water-soluble group.
n- _CH2OH ,-( _CH2 )m- _NHSO2 ( _-CH2 )n-
_CH3 , ( _-CH2 )mO( _-CH2 )n- _CH3 ,-( _CH2
The silver halide color photographic light-sensitive material according to claim 1, characterized in that it contains a color developing agent having CH ₂ O)n(CH ₂ )mH (m and n are integers of 0 or more). Processing method.