JPH0451017B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a processing liquid having bleaching ability for silver halide color photographic light-sensitive 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, there is a step of treating the metallic silver produced after the color development step with a processing solution having bleaching ability. will be 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. 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. There is. 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 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. In contrast, metal complex salts of organic acids such as aminopolycarboxylic acid metal complex salts are used as oxidizing agents to reduce pollution problems, speed up and simplify processing, and enable recycling 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, ethylenediaminetetraacetic iron() complex salt, 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 High-sensitivity silver halide color photographic materials based on silver iodide emulsions, especially color papers for photography, color negative films for photography, and color reversal films containing silver iodide as silver halide, have 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. Among aminopolycarboxylic acid metal complex salts, one of the inventors of the present invention has discovered diethylenetoamine pentaacetic acid iron() complex salt as an oxidizing agent having excellent oxidizing power particularly in a high pH region. Bleach and bleach-fix solutions that use diethylenetriaminepentaacetic acid complex salt as an oxidizing agent have a pH of 4 or higher, especially 7 or higher, and have a rapid silver bleaching reaction, generate less stain when directly bleached, and are more effective at bleaching. It has extremely excellent performance in that the fixer has good storage stability. However, even with this diethylenetriaminepentaacetic acid iron() complex salt, the bleaching speed is insufficient as a bleaching agent for high-sensitivity silver halide color photographic light-sensitive materials, and it cannot sufficiently satisfy the required rapid processing. It became clear. On the other hand, in order to increase the silver bleaching power of bleaching solutions or bleach-fixing solutions containing organic acid metal complex salts,
No. 45-8506, JP-A No. 46-280, JP-A No. 46-556
No., Belgian Patent No. 770910, Special Publication No. 1978-8836,
It is known to add various bleaching accelerators, as described in JP-A-54-71634, JP-A-49-42349, US Pat. No. 376,740, and JP-B-Sho 53-9854. However, the reality is that the acceleration effect does not provide a sufficient bleaching speed. Therefore, the present inventors attempted to apply these bleach accelerators to a bleach solution or a bleach-fix solution containing the diethylenetriaminepentaacetic acid iron() complex salt. This diethylenetriaminepentaacetic acid iron () complex salt is particularly effective compared to other organic acid metal complex salts.
Because it has high silver bleaching power in the high pH area,
It was expected that by adding these bleach accelerators, a bleaching speed sufficient for processing high-speed color photographic materials could be obtained. However, when high-sensitivity color photographic materials were processed by adding these bleach accelerators to bleach baths and bleach-fix baths using diethylenetriaminepentaacetic acid complex salt as an oxidizing agent, a sufficient accelerating effect did not appear. . Therefore, in order to rapidly process high-sensitivity silver halide color photographic light-sensitive materials, the silver bleaching speed of bleach and bleach-fix solutions using diethylenetriaminepentaacetic acid iron () complex salt as an oxidizing agent is sufficiently and effectively promoted. Technology is strongly desired. [Object of the Invention] An object of the present invention is to provide a processing solution having rapid silver bleaching ability for silver halide color photographic light-sensitive materials. [Structure of the Invention] As a result of intensive research, the present inventors have found that the above object is as follows.
Bleaching solution and bleach containing diethylenetriaminepentaacetic acid iron () complex salt and at least one selected from the following metal ion group and at least one compound represented by the following general formula (1) at 0.1 to 30 g/l It has been found that this can be achieved using a fixer. [Metal ions] Magnesium, calcium, barium, manganese, zirconium, aluminum, tungsten. [General formula (1)] In the formula, Q is a thiadiazole ring, a pyrimidine ring,
Benzimidazole ring, benzothiazole ring, benzoxazole ring, naphtho[8,1-e,d]
Oxazine ring, imidazole ring, thiazole ring,
Oxazole ring, triazole ring, diazole ring, oxazolone ring, thiazoline ring, oxazine ring, oxadiazole ring, triazine ring, pyrazine ring, thiadiazine ring, pyridazine ring, thiazaindene ring, azaindene ring, pentaazaindolizine ring, tetraazaindo represents a lysine ring or a triazaindolizine ring, R is a hydrogen atom, an alkali metal atom, Or represents an alkyl group (having 1 to 4 carbon atoms). however
Q' has the same meaning as Q above. However, Q and Q' may be substituted, and substituents include halogen atoms,
Mercapto group, nitro group, cyano group, alkoxy group, carbamoyl group, amino group (primary, secondary and tertiary), carbonyl group, hydroxy group, acylamino group, anilino group, N-acylanilino group, alkyl group, aryl group , cyclic alkenyl group, heterocyclic residue, etc., but alkyl group, aryl group,
The cyclic alkenyl group and heterocyclic residue may be substituted with the above-mentioned substituents. The present invention relates to iron diethylenetriaminepentaacetate ()
It exhibits the desired effect only when the complex salt, the bleach accelerator of the present invention represented by the general formula (1), and the metal ion of the present invention are present,
Even if one of them is missing, the effect will not be obtained. For example, when the bleach accelerator of the present invention is added to a bleach solution and a bleach-fix solution using ethylenediaminetetraacetic acid iron() complex salt as an oxidizing agent, even if the metal ion of the present invention is contained, or the metal ion of the present invention is Even if it is not included, a sufficient promoting effect cannot be obtained.
Further, even if only the metal ion of the present invention is contained in a bleaching solution and a bleach-fixing solution using diethylenetriaminepentaacetic acid iron() complex salt as an oxidizing agent, no promoting effect can be obtained. Furthermore, even if metal ions other than the present invention are contained in a bleaching solution or a bleach-fixing solution containing diethylenetriaminepentaacetic acid iron() complex salt and the bleaching accelerator of the present invention, the effect will not be as high as when containing the metal ions of the present invention. A sufficient promoting effect cannot be obtained. Furthermore, it has been found that when metals other than the present invention are contained in the bleach-fixing solution, precipitation occurs during continuous processing, but such precipitation did not occur with the metals of the present 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, 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 needs to be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but in general, its concentration is lower than that of other aminopolycarboxylate salts because of its high oxidizing power. Can be used in For example, use 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 metal ions used in the present invention may be supplied by any method. For example, it can be supplied in any form such as halides, hydroxides, sulfates, carbonates, phosphates, acetates, etc., but it is particularly effective to supply it with the following compounds (hereinafter,
These metal compounds that supply metal ions of the present invention are referred to as metal compounds of the present invention. ). However, the supply method is not limited to these methods, and other methods such as an electrical method may also be used. <Exemplary compounds> A-1 Magnesium chloride A-2 Magnesium sulfate A-3 Magnesium acetate A-4 Calcium chloride A-5 Calcium nitrate A-6 Barium chloride A-7 Barium acetate A-8 Barium nitrate A-9 Manganese chloride A -10 Manganese sulfate A-11 Manganese acetate A-12 Zirconium sulfate A-13 Zirconium nitrate A-14 Sodium tungstate A-15 Ammonium tungstate A-16 Aluminum chloride A-17 Aluminum sulfate A-18 Aluminum acetate The metal compounds may be used alone or in combination of two or more. The amount used is only a small amount, per 1 liquid used.
It is used in an amount of 0.1 g or more, particularly preferably 0.5 g or more. The effects of the present invention can be achieved with an upper limit of about 100 g, preferably about 50 g. The bleach accelerator used in the present invention has the general formula (1).
Any substance may be used as long as it is represented by the following, and typical examples thereof include, but are not limited to, the following. <Exemplary compounds> These bleach accelerators of the present invention may be used alone or in combination of two or more, and the amount of the accelerator added to the bleach solution or bleach-fix solution is 0.1 to 1 per 1 processing solution It is in the range of 50g. The amount added
If it is less than 0.1g/, the bleaching promotion effect will be small.
If the amount exceeds 50 g, precipitation may occur and contaminate the photographic material being processed. The amount added is preferably 0.1 to 30 g per treatment liquid, most preferably 0.1 to 15 g per treatment liquid. When adding the bleaching accelerator of the present invention to the processing solution, it may be added and dissolved as is, but it is common to dissolve it in water, alkali, organic acid, etc. before adding it, and add it as necessary. Even if it is dissolved in an organic solvent and added, the bleaching (fixing) promoting effect is not affected in any way. The bleaching solution and bleach-fixing solution of the present invention have a pH of from 0.2 to
It can be used with a value of 9.5, preferably 4.0 or more, more preferably 5.0 or more. 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, the metal ion of the present invention, and a bleaching accelerator, and may also contain various additives. As additives, it is particularly desirable to include alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, and the like. In addition, pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, solubilizing agents such as triethanolamine, acetylacetone, phosphonic carboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, Chelating agents such as dicarboxylic acids and aminopolycarboxylic acids or salts thereof, alkylamines, polyethylene oxides, and other agents known to be added to ordinary bleaching solutions can be appropriately added. The bleach-fix solution of the present invention contains diethylenetriaminepentaacetic acid iron () complex salt as a bleaching agent as described above, the metal ion of the present invention and a bleach accelerator, and also contains thiosulfate, thiocyanate, thiourea, iodide, etc. A solution having a composition containing a silver halide fixing agent of 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/l or more, as long as they 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, acetylacetone, phosphonic carboxylic acids, polyphosphoric acids,
Organic chelating agents such as organic phosphoric acids, oxycarboxylic acids, polycarboxylic acids, dicarboxylic acids and aminopolycarboxylic acids, stabilizers such as nitroalcohol nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, etc. additives, methanol, dimethyl formamide,
An organic solvent such as 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, and 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 and white 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 → stable (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 → stable (11) Color development → stop → bleaching → washing with a small amount of water → Establishment →
Small amount of water washing → Water washing → Stable (12) Black and white development → Water washing → Reversal → Color development → Bleaching →
Fixation → Water washing → Stabilization (13) Pre-hardening film → Neutralization → Black and white development → Stopping → Color development → Bleaching → Fixation → Water washing → Stabilization Black and white developer used before processing with the processing solution having bleaching ability of the present invention is a so-called black-and-white first developer used in the processing of commonly known color photographic light-sensitive materials, or is used in the processing of black-and-white photographic light-sensitive materials, and includes various additives that are generally added to black-and-white developers. It can be made to contain. 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 mercabuto compounds. 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 generally have a concentration of 0.1 g to 30 g of the drug per color developer,
More preferably, 1 g of drug per 1 color developer
~Used at a concentration of 15g of the drug. 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 amine color developers are N,N-dialkyl-p-phonylene diamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. good. 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 sulfate, N-ethyl-
N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N
-β-hydroxyethylaminoaniline sulfate,
4-amino-3-methyl-N,N-diethylaniline sulfate, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate. The alkaline color developing solution used before the treatment with the processing solution having bleaching ability of the present invention is
In addition to aromatic amine color developing agents, various components commonly added to color development, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal sulfites, and alkali metal bisulfites, may also be used. Water softeners and thickeners such as salts, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid can also be optionally contained. The pH value of this color developer is usually 7 or higher, 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, see specification No. 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 bivalyl acetanilide that have active methylene chains. Those having an anilide or acylacetanilide structure, etc., 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.
Silver halide emulsions that can be used include silver chloride, silver bromide, silver iodide, silver chlorobromide, gold chloroiodide, silver iodobromide,
Any silver halide such as silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, 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. Silver halide emulsions include stabilizers, sensitizers, hardeners, sensitizing dyes,
Common photographic additives such as surfactants may also be included. 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] 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 An antihalation layer and a gelatin layer are provided on a triacetate film base, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer,
The filter layer containing yellow colloidal silver and the blue-sensitive silver halide emulsion layer were combined to have a total silver amount of 100 cm ³ equivalents.
It was applied at a dose of 99 mg. At this time, the blue-sensitive silver halide emulsion layer contains α-(4-
Nitrophenoxy)-α-bivalyl-5-[γ-
1-(2,4,6-trichlorophenyl)-3- as a magenta coupler in the green-sensitive silver halide emulsion layer.
{[α-(2,4-di-t-amylphenoxy)-acetamido]benzamide}-3-pyrazolone and 1-(2,4,6-trichlorophenyl)-3
-{[α-(2,4-di-t-amylphenoxy)
Acetamide]benzamide}-4-(4-methoxyphenylazo)-5-pyrazolone was used, and 1-hydroxy-N-{α-(2,4-t- using amylphenoxy)butyl}-2-naphthamide,
Conventional additives such as sensitizing dyes, hardeners, and spreading agents were added to each emulsion layer. The silver halide color negative light-sensitive material thus obtained was used as a material. After this sample was exposed to light using a conventional method, the following treatments were performed. Processing process Processing temperature (°C) Processing time 1 Color development 37.8 3 minutes 15 seconds 2 Bleach fixing 37.8 1 minute to 30 minutes 3 Washing with water 30 to 34 2 minutes 4 Stable 30 to 34 1 minute 5 Drying Color developer, bleach The following fixer and stabilizer were used. [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-hydroquinoethyl-3-
Methyl-4-aminoanilinosulfate 4.6g Water was added to make up to 1000ml, and the pH was adjusted to 10.1 with sodium hydroxide. [Bleach-fix solution (1)] Ethylenediaminetetraacetic acid iron () complex salt 70g Nitrilotriacetic acid 10g Ammonium sulfite (50% solution) 3ml Ammonium thiosulfate (70% solution) 140ml Finish with water to 1000ml, and dilute with aqueous ammonia (28% solution) Adjust to PH7.0. [Bleach-fix solution (1)] Diethylenetriaminepentaacetic acid () complex salt 85g Nitrilotriacetic acid 10g Ammonium sulfite solution (50% solution) 3ml Ammonium thiosulfate (70% solution) 140ml Make up to 1000ml with water, aqueous ammonia (28% solution) Adjust the pH to 7.0. [Stabilizer] Formalin (35% aqueous solution) 7.0ml

[Formula] Add 1.0ml water to make 1000ml. The bleach accelerator of the present invention and the metal compound of the present invention or a comparative compound shown in Table 1 were added to the bleach-fix solutions (1) and (2). At this time, 5 g of the metal compound and 1 g of the bleaching accelerator were added per 1 processing solution, and the desilvering completion times of the films treated with each were compared.

[Table] As is clear from Table 1 above, a bleach-fixing solution containing diethylenetriaminepentaacetic acid iron() complex salt as an oxidizing agent does not exhibit a bleaching accelerating effect when only a bleaching accelerator is added, but the present invention It can be seen that a large promoting effect can be obtained by using these metal compounds together. In comparison, in a bleach-fix solution containing iron () complex salt of ethylenediaminetetraacetate as an oxidizing agent, an accelerating effect appears when only the bleach accelerator is added, but there is no effect when combined with the metal compound of the present invention, and the bleaching rate increases. It turns out that there is a shortage. Also, add 1 piece of the above film to each bleach-fix solution.
When the treatment solution was left at room temperature for one week after the m ³ treatment, precipitation occurred in the solution containing a metal compound other than the one of the present invention, but no precipitation occurred with the metal compound of the present invention. In addition, in place of the metal compound of the present invention, a vanadium compound, a lanthanum compound,
When a gadolinium compound, a eurobium compound, a disbrosium compound, an itterbium compound, a holmium compound, an erbium compound, an indium compound, a neodymium compound, or a terbium compound were added, they did not show as great a promoting effect as the metal compound of the present invention, but were added in the same manner as above. It was observed that precipitation occurred when the film was left to stand after being processed. Example 2 The same sample used in Example 1 was exposed to light in a conventional manner, and then processed in accordance with the same processing steps as in Example 1. However, regarding the bleach-fix solution, the metal compound (A-5) of the present invention shown in Table 2 below and the bleach accelerator of the present invention or comparison were added to the bleach-fix solution (2). Processing liquid 1 for metal compounds
5g per treatment solution for bleach accelerators
1 g was added, and the desilvering completion time for each was compared.

【table】

[Table] As is clear from Table 2 above, in the bleach-fix solution containing diethylenetriaminepentaacetic acid iron() complex salt as an oxidizing agent, no accelerating effect is observed even when only the metal compound of the present invention is added; It can be seen that the combined use of the bleach accelerator of the invention greatly accelerates the desilvering reaction. Example 3 The same sample used in Example 1 was exposed to light in a conventional manner and then subjected to the following treatments. Processing process Processing temperature (°C) Processing time 1 Color development 37.8 3 minutes 15 seconds 2 Bleaching 37.8 1 minute to 20 minutes 3 Washing with water 30 to 34 2 minutes 4 Fixing 37.8 6 minutes 30 seconds 5 Washing with water 30 to 34 2 minutes 6 Stability 30-34 1 minute 7 Drying The color developing solution and stabilizing solution had the same composition as that used in Example 1, and the bleaching solution and fixing solution had the following compositions. [Bleach solution] Diethylenetriamine iron pentaacetate ammonium 70g Nitrilotriacetic acid 10g Potassium bromide 90g Make up to 1000ml with water and adjust the pH with aqueous ammonia (28% solution). [Fixer] Ammonium thiosulfate 150g Anhydrous sodium sulfite 12g Sodium metabisulfite 2.5g Sodium carbonate 10g Add water to make 1. A metal compound (A-5) similar to that used in Example 2 and a bleach accelerator of the present invention or a comparative bleach were added to the above bleaching solution. The metal compound was added in an amount of 5 g per treatment solution, and the bleaching accelerator was added in an amount of 1 g per treatment solution, and the bleaching completion times of the films treated with each were compared.

【table】

[Table] As is clear from Table 3 above, in the bleaching solution containing diethylenetriaminepentaacetic acid iron () complex salt as an oxidizing agent, as in the case of the bleach-fixing solution of Example 2, the metal compound of the present invention and the It can be seen that an excellent bleaching accelerating effect can be obtained by using a bleaching accelerator in combination. [Effects of the Invention] By using the processing solution of the present invention, silver halide color photographic light-sensitive materials can be desilvered and bleached quickly and completely, making it possible to shorten the development processing time. In addition, it has excellent performance without causing precipitation in the processing solution.

Claims (1)

[Claims] 1. Contains diethylenetriaminepentaacetic acid iron () complex salt, and contains at least one kind selected from the following metal ion group and at least one kind of compound represented by the following general formula (1) at 0.1 to 30 g/ 1. A processing solution having bleaching ability for color photosensitive materials, characterized in that it contains: [Metal ions] Magnesium, calcium, barium, manganese, zirconium, aluminum, tungsten [General formula (1)] [Wherein, Q is a thiadiazole ring, pyrimidine ring, beizoimidazole ring, benzothiazole ring, benzoxazole ring, naphtho[8,1-
e, d] Oxazine ring, imidazole ring, thiazole ring, oxazole ring, triazole ring, diazole ring, oxazolone ring, thiazoline ring, oxazine ring, oxadiazole ring, triazine ring,
represents a pyrazine ring, thiadiazine ring, pyridazine ring, thiazaindene ring, azaindene ring, pentaazaindolizine ring, tetraazaindolizine ring or triazaindolizine ring, R is a hydrogen atom, an alkali metal atom, Or it represents an alkyl group having 1 to 4 carbon atoms. However, Q' has the same meaning as Q above. ]