JPS6120862B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for processing silver halide photographic materials, and in particular to a method for processing silver halide photographic materials, particularly when heavy metal ions such as iron ions that have a harmful effect are mixed into the developer during the development process of processing the silver halide photographic materials. The present invention relates to a method of sequestering these heavy metal ions and improving the stability of the developer by adding a certain type of chelating agent to the color developer in advance. Normally, it is recommended to use pure water, distilled water, or potable water when preparing processing solutions for photographic materials, especially developer-related processing solutions, but in the case of potable water, it is often A considerable amount of iron ions may be mixed in due to iron rust, etc., and if this water is used to prepare the treatment solution, some iron ions may already be present in the treatment solution at the new solution stage at the start of treatment. contains iron ions. Furthermore, in the processing process of color photographic materials, bleaching or bleach-fixing is generally performed immediately after color development, and automatic processors naturally include a bleach tank or bleach tank in the color development tank. Because the bleach-fix tank is adjacent to the bleach-fix tank, there is a possibility that during processing, the bleach solution or bleach-fix solution may get mixed into the color developing tank, which is the previous process, as droplets, or the automatic developing machine (container) that transports the photosensitive material using an endless belt or chain. In Aspro Processor), the bleach solution or bleach-fix solution adhering to the conveyor belt or conveyor chain is brought into color development, and iron ions, their main component, gradually accumulate in the color development solution. . Such development also occurs due to elution of heavy metal ions from the photographic material. Sulfites, which are used as preservatives in color developing solutions for processing color photographic materials, inhibit the reaction between color developing agent oxides and couplers when used in large amounts, so sulfites and hydroxylamine salts are generally Often used together. However, hydroxylamine salts are known to be oxidized when even a trace amount of heavy metal ions such as iron ions are mixed into the color developing solution, causing fog and adversely affecting photographic properties. Therefore, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid are generally used as sequestering agents for these heavy metal ions, but in processing solutions with high pH such as color developing solutions, the sequestering power of these heavy metal ions is weak. Rather, it is known to promote the decomposition of hydroxylamine salts. An object of the present invention is to provide a method for processing photographic materials in which heavy metal ions such as iron ions contained in a developer are sequestered and adverse photographic effects caused by the heavy metal ions are prevented. Another object of the present invention is to sequester heavy metal ions such as iron ions, which promote the decomposition of hydroxylamine salts contained as a preservative of a developing agent in a developing solution, and to provide long-term stable processing of photographic materials. The purpose is to provide a method. As a result of various studies, the present inventors added at least one selected from bishydroxyethylethylenediaminediacetic acid (the following structural formula) and its salts (e.g., alkali metal salts, ammonium salts, etc.) to the developer. It has been found that the object of the present invention can be achieved by doing so. That is, by adding this compound to the developer, even if heavy metal ions such as iron ions are mixed into the developer, they can be effectively sequestered, preventing the adverse effects (for example, fogging) caused by these heavy metal ions, and It is possible to suppress the decomposition of hydroxylamine salts, improve the storage stability of the developer, and obtain stable photographic properties for a long period of time. The amount of this compound to be added in carrying out the present invention is not particularly limited, but it is usually 0.1 to 5 g/, particularly preferably 0.5 to 3 g/. This compound is a developer for black and white photographic light-sensitive materials that uses metol, phenidone, hydroquinone, etc. as a developing agent, and a color developer that uses an aromatic primary amine developing agent such as N,N-disubstituted paraphenylene diamine as a color developing agent. It is effectively used in developing solutions for photographic light-sensitive materials, especially when used in developing solutions containing at least one of hydroxylamine and its salts (e.g. hydrochloride, sulfate, oxalate, etc.) as a preservative. A favorable result is obtained. The present invention will be explained in detail below with reference to Examples. Example 1 A color developing solution for color negative film having the following composition was prepared as a photographic processing agent composition. Color developer Potassium carbonate 30g Sodium sulfite 4.5g Potassium bromide 1.5g Hydroxylamine sulfate 2.5g 3-Methyl-4-amino-N-ethyl-N-hydroxyethylaniline sulfate 4.5g Potassium hydroxide 0.2g All in water Dissolve to make 1. The above color developing solution is used as sample (1), and EDTA/
Sample (2) to which 0.1 g of disodium salt was added,
Sample (3) to which 1.0 g of nitrilotriacetic acid trisodium salt was added was bishydroxyethylethylenediamine diacetic acid disodium salt according to the present invention.
Sample (4) was prepared by adding 1.0 g of chloride, and four types of samples were prepared. Experiment 1 Five types of samples were prepared at 30°C, including the color developer samples (1) to (4) above with 7.0 ppm of iron ions added to them, and a comparison sample (1) that did not contain iron ions. The sample was left to stand and the rate of decrease in hydroxylamine over time was examined. The results are shown in Table 1. Experiment 2 A commercially available color negative film was subjected to stepwise exposure, left to stand at 30° C. in the same manner as in Experiment 1, and processed using each of the color developing solutions (1) to (4) in the following processing steps. Processing process Color development 38℃ 3 minutes 15 seconds Bleaching 〃 6〃30〃 Water washing 〃 3〃15〃 Fixing 〃 6〃30〃 Water washing 〃 4〃20〃 Stable 〃 2〃10〃 Drying 60℃ or less The compositions of the bleaching solution, fixing solution and stabilizing solution used in the above processing steps are as follows. Bleaching solution Ammonium bromide 150g EDTA/iron salt 120g 90% acetic acid 12ml Dissolve all in water to make 1. Fixing solution Ammonium thiosulfate 100g Caustic soda 5g 90% acetic acid 2ml Sodium metabisulfite 15g Dissolve all in water to make 1. Stable liquid 37% formalin 5ml Surfactant 3 Dissolve all in water to make 1. The fog density was measured for each sample after the above treatment. The results are shown in Table 2.

【table】

[Table] Example 2 A color developing solution for color paper having the following composition was prepared as a photographic processing agent composition. Color developer Benzyl alcohol 15g Ethylene glycol 13g Hydroxylamine sulfate 3g 3-Methyl-4-amine-N-ethyl-N-(B-methanesulfonamide ethyl)aniline sulfate 5g Potassium carbonate 20g Potassium hydroxide 4g Potassium bromide 1.5g Potassium chloride 0.5g Potassium sulfite 2.5g Potassium bicarbonate 5g Fluorescent agent (※※) 1.5g Dissolve all in water and make 1. (※※) Product name: Chinopal MSP (Switzerland,
(manufactured by Ciba Geigy) The above color developing solution was used as sample (5), and EDTA and
Sample (6) to which 1.0 g of disodium salt was added,
Sample (7) to which 1.0 g of nitrilotriacetic acid trisodium salt was added is bishydroxyethylethylenediamine diacetic acid disodium salt according to the present invention.
Four types of samples were prepared, including one with 1.0 g/ added and sample (8). Experiment 3 Each of the above color developer samples (5) to (8) to which 7.0 ppm of iron ions was added was left at 30°C, and the rate of decrease in hydroxylamine over time was examined. The results are shown in Table 3. Experiment 4 Give stepwise exposure to Mitsubishi color paper, Experiment 3
Color developing solution left at 30℃ in the same manner as above (5)
~(8) Each was used to perform the following treatment steps. Processing steps Color development 38°C 3 minutes 30 seconds Bleach-fixing 33°C 1〃30〃 Water Washing 〃 3〃30〃 Drying 80°C The composition of the bleach-fix solution used in the above processing step is as follows. Bleach-fix solution Ammonium thiosulfate 100g Ammonium sulfite 15g EDTA/iron/ammonium salt 90g EDTA/iron/sodium salt 70g Dissolve all in water to make 1. The fog density was measured for each sample that had undergone the color development process described above. The results are shown in Table 4.

【table】

[Table] As shown by the results in Tables 1 to 4 above, the color developer samples (4) and (8) according to the present invention suppress the decomposition of hydroxylamine over time in the color developer mixed with iron ions. It can be seen that the effect of preventing fogging is remarkable.

Claims (1)

[Scope of Claims] 1. A method for processing a photographic material, which comprises processing the material in a developer containing at least one selected from bishydroxyethylethylenediaminediacetic acid and its salts. 2. The processing method according to claim 1, wherein the developer contains at least one selected from hydroxyamine and its salt. 3. The processing method according to claim 1 or 2, wherein the developer is a color photographic material and the photographic light-sensitive material is a color photographic light-sensitive material.