JPH0318177B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for processing a silver halide color photographic light-sensitive material, particularly a method for processing a silver halide color photographic light-sensitive material using a processing solution used for bleaching image silver. Regarding. BACKGROUND ART Bleaching solutions, bleach-fixing solutions, reducing solutions, and the like are known as processing solutions for photographic light-sensitive materials having bleaching ability. Among these, this type of processing solution for processing silver halide color photographic light-sensitive materials includes red blood salt, dichromate,
Inorganic oxidizing agents such as iron chloride and persulfates are widely used. However, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, persulfates and iron chlorides corrode processing equipment components, and red blood salts and dichromates have relatively good bleaching power for image silver, but they decompose under light and cause cyanide that is harmful to the human body. There is a risk of producing chromium ions and hexavalent chromium ions, which is unfavorable in terms of pollution prevention. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizing agents 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, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse them without discarding the waste liquid after treatment. On the other hand, organometallic chelate compounds such as aminopolycarboxylic acid metal chain salts have been used as oxidizing agents as they do not cause pollution problems and meet the requirements of speeding up and simplifying treatment, and enabling recycling of waste liquid. The processing solution used is widely used. As the aminopolycarboxylic acid metal complex salts used as the oxidizing agent, iron, copper, and cobalt complex salts such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and hydroxyalkylethylenediamine are known. However, treatment solutions using these aminopolycarboxylic acid metal complexes have slow oxidizing power, so
The bleaching rate (oxidation rate) of image silver (metallic silver) formed in the development process is slow, and it is particularly suitable for the purpose of rapid processing of transmission type silver halide color photographic light-sensitive materials, such as high-sensitivity color photographic light-sensitive materials. isn't it. Incidentally, among these, a treatment solution using iron salt of ethylenediaminetetraacetic acid (hereinafter referred to as EDTA iron complex salt) is considered to be superior to other aminopolycarboxylic acid metal complex salts in terms of bleaching power. It has also been put into practical use in the department. However,
Organometallic complex salts have relatively low oxidizing power and insufficient bleaching power, and when used as a bleaching agent,
For example, when bleaching or bleach-fixing a low-sensitivity silver halide color photographic light-sensitive material based on a silver chlorobromide emulsion, the desired purpose can be achieved, but When processing a high-sensitivity silver halide color photographic light-sensitive material that is mainly composed of a silver emulsion and color sensitized, especially a silver halide color reversal photographic light-sensitive material for reversal that uses a high silver content emulsion, the bleaching action is insufficient. Desilvering is poor and the bleaching or bleach-fixing efficiency is low, making it difficult to achieve the objective. From the viewpoint of pollution prevention, it is desirable to use a metal complex salt of an organic acid such as ethylenediaminetetraacetic acid iron complex salt as a bleaching agent, but as mentioned above, this results in insufficient bleaching power, so Unless these problems are solved, it will not be possible to achieve the objective of rapidly processing transmission-type silver halide color photographic materials, such as high-sensitivity color photographic materials. Conventionally, it has been proposed to add various bleaching accelerators to bleaching solutions or bleach-fixing solutions that use a metal complex salt of an organic acid such as ethylenediaminetetraacetic acid iron complex as a bleaching agent. Examples of such bleaching accelerators include thiourea derivatives as described in Japanese Patent Publication No. 45-8506, selenourea derivatives as described in Japanese Patent Publication No. 46-280, and British Patent No. 1138842. 5-membered ring mercabuto compounds as described in Japanese Patent Publication No. 46-556, or thiourea derivatives and thiazole derivatives as described in Swiss Patent No. 336257. , thiadiazole derivatives, etc. However, many of these bleach accelerators do not necessarily have a satisfactory bleach accelerating effect, and even if they have an excellent bleach accelerating effect, they lack stability in the processing solution, resulting in a short effective lifespan of the processing solution. Many of them have drawbacks such as not being able to withstand long-term storage. Furthermore, it is proposed in German Patent No. 213,940 that onium compounds can be used as bleach accelerators. However, although these onium compounds have a bleaching accelerating effect, the effect is still not sufficient, and in particular when a metal complex salt of an organic acid is used as a bleaching agent, almost no bleaching accelerating effect is observed. A first object of the present invention is to provide a method for processing a transmission-type silver halide color photographic light-sensitive material that has low toxicity, meets the requirements for pollution prevention, and has an excellent bleaching speed. A second object of the present invention is to provide a transmission type silver halide color photographic light-sensitive material for photography using a bleach accelerator capable of increasing the bleaching rate in bleaching treatment or bleach-fixing treatment using a metal complex salt of an organic acid as a bleaching agent. The purpose of the present invention is to provide a processing method. A third object of the present invention is to provide a method for processing a transmission-type silver halide color photographic light-sensitive material using a bleach accelerator that can increase the bleaching rate when included in a bleach solution or a bleach-fix solution. It is to be. A fourth object of the present invention is to use a bleach-fix accelerator that can increase the bleach-fix speed, shorten the processing time, and obtain high-quality color photographic images, especially in color photographic processing that involves a bleach-fix step. An object of the present invention is to provide a method for processing a transmission-type silver halide color photographic light-sensitive material. The above-mentioned objects of the present invention are to develop a silver halide color photographic light-sensitive material that has been imagewise exposed, and then to process it with a processing solution having a bleaching ability containing an organic acid metal complex salt. In the method for processing photographic light-sensitive materials, the processing solution having bleaching ability is at least one of a lower aliphatic or aromatic iodine-containing substituted organic compound in which at least one iodine atom has been substituted (hereinafter referred to as the compound of the present invention). This is achieved by a method for processing a transmission-type silver halide color photographic light-sensitive material for photographing, which is characterized in that it contains one kind of silver halide color photographic material. The present invention will be explained in detail below. The compound of the present invention is a lower aliphatic or aromatic iodine-containing substituted organic compound having 1 to 18 carbon atoms, and specific examples include the following, but the present invention is not limited to these compounds. It is not something that will be done.

[Formula] (2)I-CH ₂ -COOH(3)CH ₃ -I-NH ₂

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(8)C ₂ H ₅ -I-NH ₂ (9)I-CH ₂ -CO-NH ₂ (10)I-
CH ₂ CH ₂ −COOH

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【formula】

【formula】

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[Formula] In the present invention, a color photographic image is obtained by subjecting an imagewise exposed silver halide color photographic material to photographic processing including the steps of developing, bleaching and fixing. Bleaching and fixing may be carried out in separate steps, or both may be carried out in one step using a bleach-fix solution. Development means color development, but also includes combinations of black development and color development, such as in reversal color processing. These steps of development, bleaching and fixing do not necessarily have to be carried out consecutively, and other steps can also be carried out before and after each step. Such additional steps include:
Examples include hardening bath, stop bath, neutralization bath, stabilization bath, water washing (including rinsing), and bleaching and fixing steps may be added as necessary. The compound of the present invention is contained in a processing liquid having bleaching ability, that is, a bleach bath or a bleach-fix bath. The amount of the compound of the present invention to be added to these baths varies depending on the type of bath, the type of photographic material to be processed, the processing temperature, the time required for the desired processing, etc., but in general, the amount of the compound in the processing bath Approx. per 1
Good results are obtained in the range 0.001 g to 50 g, preferably in the range 0.1 g to 10 g. However, in general, when the amount added is small, the effect of promoting bleaching is small, and when the amount added is larger than necessary, precipitation may occur and contaminate the photographic materials being processed, so the amount added must be determined individually. It is preferable to determine the optimal range appropriately depending on the case. Incidentally, one or more of these compounds of the present invention can also be used in combination. When adding the compound of the present invention to a treatment bath, it is generally dissolved in water, an alkali, an organic acid, etc. beforehand, but if necessary, it is added after being dissolved in an organic solvent. However, it has no effect on its bleaching promotion effect. The metal complex salt of an organic acid as a bleaching agent used in the bleaching solution or bleach-fixing solution used in the bleaching process of the present invention oxidizes metallic silver produced during development and converts it into silver halide, and at the same time converts it into a color former. It has the effect of coloring uncolored areas,
Its structure is one in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexane Diaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid)

[9] Ethyl etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) ) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid sodium salt [18] Propylene diamine Tetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt The bleaching solution used in the present invention contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, as well as various additives. can include. As additives, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Buffers, alkylamine agents, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be added as appropriate. In the present invention, when the bleaching step is carried out using a bleach-fix solution, the bleach-fix solution contains a metal complex salt of an organic acid as described above as a bleaching agent, and also contains thiosulfates, thiocyanates, thioureas, etc. A solution containing a silver halide fixing agent is applied. In addition, a bleach-fix solution consisting of a composition in which a small amount of a halogen compound such as potassium bromide is added in addition to a bleaching agent and the above-mentioned silver halide fixer, or conversely, a composition in which a large amount of a halogen compound such as potassium bromide is added. Further, a special bleach-fix solution having a composition consisting of a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide can also be used. As the halogen compound, other than potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, ammonium iodide, etc. can be used. 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, potassium thiosulfate, sodium thiosulfate,
Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and the like. 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, potassium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various antifoaming agents or surfactants can also be contained. Also,
Preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, or a type of stabilizer such as nitroalcohol nitrates, methanol,
Organic solvents such as dimethyl sulfoamide and dimethyl sulfoxide can be contained as appropriate. The black-and-white developer used in the processing of the present invention is a so-called black-and-white first developer used in the processing of color photographic light-sensitive materials, or a developer used in the processing of black-and-white photographic materials. Various additives added to the black and white developer can be contained. 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. Potassium bromide, 2-
Examples include inorganic or organic inhibitors such as methylbenzimidazole and methylbenzthiazole, water softeners such as polyphosphates, and surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds. The aromatic primary amine color developing agents used in the color developer used in the process of the present invention include those known and widely used in various color photographic processes. 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 in an amount of about 0.1g per color developer.
~30g concentration, more preferably color developer 1
It is used at a concentration of about 1 g to about 15 g. 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. In addition to the above-mentioned primary aromatic amine color developer, the alkaline color developer used in the process of the present invention further contains various components normally added to color developers, such as sodium hydroxide and carbonate. Alkaline agents such as sodium and potassium carbonate, alkali metal sulfites, alkali metal bisulfites,
Alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. The transmission-type silver halide color photographic light-sensitive material for photographing that can be applied to the present invention uses an internal development method (U.S. Pat. No. 2,376,679,
2801171), and any coloring agent generally known in the art can be used as the coloring agent. For example, cyan color formers are based on naphthol or phenol structures and form indoaniline dyes by coupling, magenta color formers have a 5-pyrazolone ring with an active methylene group as a skeleton structure, and yellow color formers have Those having a benzoylacetanilide, pivalylacetanilide, or acylacetanilide structure having an active methylene chain, with or without a substituent at the coupling position can be used. Thus, as the coloring agent, both so-called 2-equivalent type couplers and 4-equivalent type couplers can be applied. As the silver halide emulsion that can be used, any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used. It may be something. 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. When the compound of the present invention is contained in a bleach bath or a bleach-fix bath and the treatment with these baths is performed immediately following the color development step, it will not cause contamination of the color developer by carry-over, unlike conventional bleach accelerators. The bleaching accelerating effect does not decrease due to this.
Furthermore, even when the compound of the present invention is used in a relatively large amount, it does not cause fixing inhibition and no capri formation is observed. The present invention will now be illustrated by examples, but the embodiments of the present invention are not limited thereto. Example 1 Sakura Color (manufactured by Konishiroku Photo Industry Co., Ltd.,
After exposing a high-sensitivity color negative film to light using a conventional method, the following processing was performed. <Development processing> Color development 3 minutes 15 seconds, bleach fixing 1 minute to 30 minutes,
Washing with water for 2 minutes and stabilizing treatment for 1 minute are performed in sequence, followed by drying. Each treatment was carried out at 37.8°C, and each treatment liquid was prepared according to the following formulation. [Color developer] Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.0g Potassium bromide 1.2g Sodium hydroxide 3.4g N-ethyl-N-β-hydroxyethyl-3-
Methyl-4-aminoaniline hydrochloride 4.6g Add water 1 Adjust to pH 10.1 with sodium hydroxide [Bleach-fix solution] Ethylenediaminetetraacetic acid diammonium salt
7.5g Ethylenediaminetetraacetate iron () ammonium salt 100.0g Sodium sulfite 10.0g Ammonium thiosulfate 90.0g Adjusted to PH6.2 with ammonium hydroxide [Stable solution] Formalin (35% aqueous solution) 7.0ml 1.0g of water was added, and the compounds of the present invention shown in Table 1 were added to the bleach-fix solution for treatment. For each of the bleach-fix solutions a to o, the time required to complete bleach-fixing of the processed film was compared. At the same time, the film was subjected to a bleach-fixing process for 8 minutes, and after drying, the maximum density of the film was shown in Table 1 as the neutral maximum density. The neutral maximum density is the white light density of the dye plus the unbleached silver and unfixed silver.

【table】

[Table] As can be seen from Table 1, bleach-fixing was completed in both bleach-fix solution a, which did not contain the compound of the present invention, and bleach-fix solution b, which added potassium iodide (KI), a compound other than the compound of the present invention. The time is long,
The maximum neutral density was significantly high due to the unbleached silver remaining, indicating that bleach-fixing was not completed within 8 minutes. On the other hand, in the bleach-fixing solutions c to o according to the present invention, the time to complete bleach-fixing was greatly shortened and the maximum neutral density was close to the desired value of 368, indicating that no unbleached or unfixed silver remained. . Example 2 The film sample and processing method were exactly the same as in Example-1, and the amount of ethylenediaminetetraacetic acid iron () complex salt, which is the bleaching agent in the bleach-fix solutions c to o, was reduced to 50 g/, and the pH was the same as in Example-1. However, the bleach-fixing completion time was not longer than 8 minutes. As described above, by using the compound of the present invention, the concentration of bleaching agent can be reduced, which is advantageous in terms of reducing processing costs and preventing pollution caused by discharge of bleaching solution. Separately from this example, when the compound of the present invention was added to a bleaching solution of a commercially available reversal color film using ethylenediaminetetraacetic acid iron () complex salt and potassium bromide, the results were substantially the same as those of this example. A similar bleaching promotion effect was obtained.

Claims (1)

[Claims] 1. A transmission type silver halide color photographic light-sensitive material for photography which has been imagewise exposed and is then processed with a processing solution having a bleaching ability containing an organic acid metal complex salt. A method for processing color photographic materials, characterized in that the processing solution having bleaching ability contains at least one lower aliphatic or aromatic iodine-containing substituted organic compound in which at least one iodine atom has been substituted. A method for processing a transmission-type silver halide color photographic light-sensitive material for photographing.