JPS606506B2 - Silver halide color photographic material processing method - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for processing a silver halide color photographic material (hereinafter referred to as a color photographic processing method) in which the exposed silver halide color photographic material is developed, bleached, and fixed. The present invention relates to a color photographic processing method that can shorten the processing time and perform sufficient bleaching to form color photographic images of good quality. Generally, in order to obtain a color image by developing a silver halide color photographic material that has been exposed to light, after the color development step,
The developed silver image is bleached with an oxidizing agent (bleaching agent), and then desilvered and fixed with a fixing agent. In contrast to this type of method in which bleaching and fixing are performed in separate processing steps, a method called bleach-fixing is a method that simplifies the processing steps and completes bleaching and fixing simultaneously in one step for the purpose of speeding up processing and saving labor. A processing method has been proposed. The bleaching solution used in the bleaching process contains bleaching agents such as red blood salts, ferric chloride, or metal complex salts of organic acids such as ethylenediaminetetraacetate iron complexes. The bleach-fixing solution is generally an aqueous solution containing a bleaching agent and a fixing agent as main ingredients. Metal complex salts of organic acids such as these are used, and fixing agents that coexist with these bleaching agents include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate and sodium thiocyanate, or thiourea. A fixing agent commonly used for fixing silver halide photographic light-sensitive materials is used. Red blood salt and ferric chloride as bleaching agents are good bleaching agents in that they have a large oxidizing power. However, they are good bleaching agents. Bleach solutions or bleach-fix solutions that use red blood salt as a bleaching agent release cyanide through photodecomposition, which poses a pollution problem. In addition, products using iron chloride as a bleaching agent have a very low pH and extremely high oxidizing power, so they have the disadvantage that the parts of the processing machine that is filled with them are easily corroded. It has the disadvantage that iron hydroxide is precipitated into the emulsion layer during the water washing process, producing so-called stain.For this reason, a washing process with an organic chelating agent must be performed after bleaching, which is not suitable for the purpose of rapid processing and labor saving. , and also poses a problem in terms of pollution control.Compared to red blood salt and ferric chloride, metal salts of organic acids such as ethylenediaminetetraacetic acid iron key salt are less toxic and are advantageous in terms of pollution control, so bleaching is recommended. In recent years, it has been recommended that organometallic rust salts be used as bleaching agents.However, organic metal rust salts have relatively low oxidizing power and insufficient bleaching power. When bleaching or bleach-fixing a low-sensitivity silver halide color photographic light-sensitive material, it is possible to achieve the desired purpose, but silver chlorobromoiodide or silver iodobromide emulsions are the main emulsions. When processing silver halide color photographic materials with high sensitivity and color sensitization, especially silver halide color reversal photographic materials for reversal using emulsions with a high silver content, the bleaching action is insufficient and desilvering is poor. However, the bleaching or bleach-fixing efficiency is low and it is difficult to achieve the desired purpose.From the viewpoint of pollution prevention, it is desirable to use a metal salt of an organic acid such as ethylenediaminetetraacetic acid iron complex salt as a bleaching agent. However, as described above, this results in insufficient bleaching power, and unless this problem is solved, the purpose of rapidly processing high-sensitivity color photographic materials cannot be achieved. 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. As such a bleaching accelerator, for example, Japanese Patent Publication No. 45-8
Thiourea derivatives such as those described in Japanese Patent No. 06, selenourea derivatives such as those described in Tokusekki Publication No. 46-28; Member-ring capto compound
Examples include aliphatic amines as described in Japanese Patent No. 556, thiourea derivatives, thiazole derivatives, and thiadiazole derivatives as described in Swiss Patent No. 336,257. 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. Those that have the disadvantage of not being able to withstand long-term storage, or the disadvantage that bleaching accelerating effects cannot be obtained when they are included in the so-called pre-treatment liquid used in the process before treatment with bleach or bleach-fix solution. Many have. The first object of the present invention is to provide a color photographic processing method that is low in toxicity, meets the requirements for pollution prevention, and has an excellent bleaching speed. It is an object of the present invention to provide a color photographic processing method using a bleaching accelerator that can increase the bleaching rate in bleaching or bleach-fixing using a metal complex salt. The fourth object of the present invention is to provide a color photographic processing method using a bleaching accelerator that can increase the bleaching rate and obtain a highly stable processing solution even when the bleaching accelerator is contained in a bleaching agent. The purpose is to provide a color photographic processing method using a bleaching accelerator that can increase the bleaching rate even when it is included in a prebath used in a step before processing with a bleaching solution or a bleaching accelerator. A fifth object of the present invention is to "promote bleach-fixing that can increase the bleach-fixing speed, shorten the processing time, and obtain color photographic images with good image quality," particularly in a color photographic processing method that includes a bleach-fixing step. It is an object of the present invention to provide a color photographic processing method using a processing agent.It is an object of the present invention to perform a bleaching step and a fixing step using separate processing solutions after developing an exposed silver halide photographic material. or the bleaching step is carried out using a single processing solution, i.e., a bleach-fix solution, in which case the bleach or bleach-fix solution and This is achieved by containing a compound represented by the following general formula [1] (hereinafter referred to as the compound of the present invention) in the treatment solution and using a metal salt of an organic acid as a bleaching agent.General formula [1] ] In the above general formula, R. and R2 represent a hydrogen atom, a hydroxyl group or a lower alkyl group, A represents an n-valent heterocyclic residue, m represents an integer of 1 to 5, and n' represents an integer of 1 to 4. The compound of the present invention represented by the formula is a compound in which an alkyl group substituted with a mercapto group is introduced into a heterocycle, and the heterocycle referred to in the present invention also includes an integrated heterocycle. is not only a hetero ring containing one hetero atom such as a nitrogen atom or a sulfur atom, but also a hetero ring containing two or more of the same hetero atom or a hetero ring containing two or more different hetero atoms. In addition, the alkyl group substituted with a mercapto group includes not only compounds directly bonded to a heteroatom of a hetero-mimetic, but also compounds bonded to a carbon atom constituting a heterocycle. do. Next, specific representative examples used in the present invention will be listed, but the compounds used in the present invention are not limited to these. Exemplary Compounds Compounds of the present invention include, for example, Journal. of the American Chemical Society (Jo
Urnal of the American Che
mical Society) No. 69, page 2674 (
1947) “Journal of Organ Chemistry”
mistry) Vol. 33, p. 1275 (1968),
Journal of is also a society. Of Kame Chemical'Industry Mitransaction (
Journal of the Society
of Chemical Industry:Tran
52, p. 272 (1933) and The 8 Chemistry. Of-functional mother group. The. Chemistry. The Chemistry of the Funetio
naI Groups. The Chemistry
oftheThioI Groups. ) (John
Wiley & Sons. Inc. 1974), pp. 163-296. In the present invention, a color photographic image is obtained by subjecting an exposed silver halide material to a photographic process including the steps of developing, bleaching, and fixing. Bleaching and fixing may be performed in independent steps, or both may be may be carried out in a step using a bleach-fix solution.Development usually means color development, but also includes a combination of black and white development and color development, such as in reversal color processing.These developments, bleaching and Each step of fixation does not necessarily have to be carried out consecutively, and other steps can be carried out before and after each step. In addition to washing with water (including rinsing), bleaching and fixing steps can be added as necessary.The compound of the present invention can be contained in a bleaching solution or a bleach-fixing solution, or can be added to a bleaching solution or a bleach-fixing solution. Alternatively, it may be contained in a pre-treatment liquid used in the step immediately before the processing step with a bleach-fix solution.In this case, the pre-treatment liquid is the processing solution after the development step, and it is included in the pre-treatment solution used in the process immediately before the processing step with the bleach-fix solution. It means the processing solution immediately before. When a bleaching or bleach-fixing step is performed immediately following the developing step, the so-called bleaching accelerating effect cannot be obtained even if the compound of the present invention is contained only in the developing solution. The compound of the present invention may be contained only in the bleach solution or bleach-fix solution or their pretreatment solution, or may be contained in both the bleach solution or bleach-fix solution and the pretreatment solution.
That is, a desirable bleaching accelerating effect can be obtained in any of these addition modes. The amount of the compound of the present invention to be added to these solutions varies depending on the type of processing solution, the type of photographic material to be processed, the processing temperature, the time required for the desired processing, etc. Good results can be obtained in the range of about 0.01 to 250 g/kg of liquid.
However, in general, when the amount added is 4.0%, the bleaching effect is 4.0%, and when the amount added is larger than necessary, precipitation may occur and contaminate the photographic materials being processed. It is preferable to determine the optimal range as appropriate depending on each individual case. When adding the compound of the present invention to a treatment solution, it is generally dissolved in water, alkali, organic acid, etc. beforehand, but if necessary, it is dissolved in an organic solvent before being added. However, the bleaching accelerating effect is not affected in any way.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 does not affect the metallic silver produced by development. It has the effect of oxidizing and converting to silver halide and at the same time coloring the uncolored parts of the coloring agent. Its structure is aminopolycarboxylic acid or organic acids such as hakama acid and citric acid, and it is a substance that contains iron, cobalt, copper, etc. The most preferable organic acid used to form such a metal mirror salt of an organic acid is, for example, the following general formula [
There are aminopolycarboxylic acids represented by [D] or [m]. [In each of the above general formulas, "A,, A2, A39 A4, A
5, and A6 each represent a substituted or unsubstituted hydrocarbon group tZ represents a hydrocarbon group, an oxygen atom, a sulfur atom, or >N-A7 (A? is a hydrocarbon group or a lower carboxylic acid). ] These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. The above general formula

Typical examples of aminopolycarboxylic acids represented by [0] or [m] include the following. Ethylenediaminetetraacetic acidDethylenediaminebentaacetic acidEthylenediamine-N-(8-oxyethyl)-N,N
',N'-propylenediaminetetraacetic acid nitrilotriacetic acid. Hexanediaminetetraacetic acidiminodiacetic aciddihydroxyethylglycine ethyl etherdiaminetetraacetic acidglycol ether diaminetetraacetic acidethylenediaminetetrapropionic acidphenylenediaminetetraacetic acidethylenediaminetetraacetic acid disodium saltethylenediaminetetraacetic acidtetra( trimethylammonium) salt Ethylenediaminetetraacetic acid tetrasodium salt Dethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N-(3oxyethyl)-N,N',Nr-
Sodium triacetate Propylene diamine sodium tetraacetate Sodium nitrilotriacetate Sodium cyclohexanediamine tetraacetate 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. Additionally, pH buffering agents such as shelf salts, oxalates, acetates, carbonates, and phosphates, polyaminocarboxylic acids or their salts, alkylamines, and polyethylene oxides are added to ordinary bleaching solutions. Those known to be effective 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 anchor salt of an organic acid as described above as a bleaching agent, and also contains thiosulfates, thiocyanates, thioureas, etc. A solution having a composition containing a silver halide fixing agent of 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. Bleach-fix solution
Furthermore, 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 may also be used. As the halogen compound mentioned above, in addition to potassium bromide, hydrochloric acid, lithium bromide, sodium bromide, ammonium bromide to potassium iodide, ammonium iodide, etc. can also be used. Examples of silver fixing agents include compounds that react with silver halides to form water-based complex salts, such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, thiosulfate, thiocyanine, etc. Typical examples include thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, and thiourea thioethers, bromides, and chlorides. Similarly, the pH consists of various salts such as shelf acid, sand, sodium hydroxide, potassium hydroxide to sodium carbonate, sodium carbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
Buffers may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants may be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, or stabilizers such as nitroalcohol nitrates, methanol, dimethylformamide, dimethyl sulfate, etc. An organic solvent such as an oxide may be appropriately contained.The black and white developer used in the development process of the present invention may be a so-called black and white first developer which is commonly used in the processing of color photographic light-sensitive materials. < is used in the processing of black-and-white photographic materials, and can contain various well-known additives that are generally added to black-and-white developing solutions.A typical additive is 1-phenyl-3. Pyrazolidones: Developing agents such as methol and hydroquinone, securing agents such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, potassium bromide, 2-methylbenzimidazole, methylbenzthiazole. inorganic or organic inhibitors such as
Examples include water softeners such as borisonic acid salts, and surface overdevelopment inhibitors consisting of iodine and mercapto compounds. The first compound used in the color developer in the present invention
Aromatic amino color developers include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. Since these compounds are more stable in the free state, they are generally used in the form of a salt, such as a hydrochloride or a sulfate. "These compounds generally contain about 0.1 to about 30
The color developer is preferably used at a concentration of about 100 to about 1500 g per 1 part of the color developing solution. Examples of aminophenol-based developers include o-aminophenol, p-aminophenol, and 5-amino-2-oxytoluene.
2-amino-3-oxytoluene, 2-oxy-3-
Includes amino-1,4-dimethyl-benzene and the like. A particularly useful first aromatic amino color developer is an N,N-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, particularly useful examples include N,N-jethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, -amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-B-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-8-hydroxy Examples include ethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, and 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate. In addition to the first aromatic amino color developer, the alkaline color developer used in the present invention further contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, and potassium carbonate. It may optionally contain alkaline agents such as alkali metal sulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickening agents, and the like. The pH value of this color developer is usually 7 or higher, most commonly about 10 to about 13. The silver halide color photographic material processed according to the present invention in the presence of the compound of the present invention is a known color photographic material, preferably a multilayer negative-working color photographic material containing a coupler or a color print. It can be used particularly advantageously when processing photographic materials or when processing color photographic materials made for reversal color processing, as well as color x-ray photographic materials, single-layer special color photographic materials. Photosensitive materials can also be processed. Alternatively, there is no problem in processing the coupler in the presence of the developer. The silver halide photographic light-sensitive material applicable to the present invention uses an internal development method (in which a color former is contained in the light-sensitive material).
For example, U.S. Patent Nos. 2,376,679 and 2,80
No. 1,171, etc.), as well as external development methods in which a coloring agent is contained in the developer (for example, U.S. Pat. No. 2,
No. 252,718, No. 2,592,243, No. 2
, 590, 97). Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan color formers are based on a naphthol or phenol structure and form indoaniline dyes through coupling, magenta color formers have a 5-pyrazoroso ring with an active methylene group as a backbone structure, and yellow color formers have may be penzoylacetanilide or acylacetanilide having an active methylene chain, and may or may not have a substituent at the coupling position. As described above, both so-called 2-equivalent couplers and 4-equivalent couplers can be used as color formers. 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 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, hardening agents, sensitizing dyes, and surfactants. When the compound of the present invention is incorporated into a premix of a bleach or bleach-fix solution, various compositions can be used as the premix. The simplest composition is an aqueous solution in which the compound of the present invention is simply dissolved. Aqueous solutions suitably containing salts such as sodium acid, sodium carbonate, sodium bicarbonate, etc. can also be advantageously used as a precursor. Any prefix pH can be used, and any of them can effectively bring out the effects of the present invention, but if the pH is too high,
In this case, stain may occur, so it is generally preferable to use it under PHI conditions. In addition, if necessary, anti-settling agents made of various chelate compounds, hardening agents made of various compounds such as alum and aldehyde, pH buffering agents, fixing agents of halogen salts,
Antioxidants such as sulfites, hydroxylamine and hydrazine, anti-swelling agents such as sodium sulfate and magnesium sulfate, surfactants and the like can be contained. For example, a washing treatment, a stopping treatment, a stopping fixing treatment, etc. can be interposed between the pretreatment and the bleaching or bleach fixing, but even in such cases, the compound of the present invention can be added during the pretreatment. When this happens, a similar bleaching promoting effect can be obtained. However, when the compound of the present invention is contained only in the prebath, it is more desirable that the prebath be used in the step immediately before bleaching or bleach-fixing. Incorporating the compound of the present invention into a bleach or bleach-fixing solution,
When these common treatments are performed immediately following the color development step, the bleaching accelerator effect does not deteriorate due to contamination of the color developing solution as with conventional bleaching accelerators. 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. Furthermore, no compound precipitation occurs during the treatment. Next, the present invention will be illustrated by examples, but the embodiments of the present invention are not limited thereto. 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, a filter layer containing yellow colloidal silver, and a sound-sensitive silver halide emulsion are formed thereon. The layers were applied to give a total silver content of 90 ponds per 100 cm. At this time, the blue-sensitive silver halide emulsion layer contains Q-(4-nitrophenoxy)-Q-beaveryl 5 as a yellow coupler.
1-(2, 2,
4,6-trichlorophenyl)-3-{[QI-(2,
4-di-t-amylphenoxy)-acetamide]penzamide}-5-pyrazolone and 1-(2,476-
trichlorophenyl)-3-{1[and-(2,4-di-t-amylphenoxy)acetamide]penzamide}
-4-(4-Methoxyphenylazo)-5-pyrazolone was used, and in the red-sensitive silver halide emulsion layer, 1-hydroxy-N-{Q-(2,4-t-amylphenoxy)butyl}- was used as a cyan coupler. The silver halide color negative light-sensitive material thus obtained, in which 2-naphthamide was used and ordinary additives such as a sensitizing color system, a hardening agent, and a spreading agent were added to each emulsion layer, was used as a sample. Using a tungsten light source on this sample, the color temperature was set to 490 using a filter.
After adjusting the temperature to a certain level and exposing the film to a certain amount of light, the following processing was performed. Processing process Processing time Color development 3 minutes 19 Sand bleach fixing 1 minute to 2 minutes Washing 2 minutes Stable 1 minute Drying was adjusted according to the following recipe and the processing temperature was 37.8 CO, and each processing solution was used. [Color development] Sodium metasherate 25.0 Sodium sulfite 2.0 Hydroxylamine sulfate 2.0 Potassium bromide
0.5 ta sodium hydroxide
3.4tN-ethyl-N-8-methoxyethyl-3-methyl-4-aminoaniline. Add Tosil Salt 6.0 Yusui
1. pHIO. with sodium hydroxide. Adjust to 1 [stable] Formalin 7.0'
・Add evening water 1. As a bleach-fix solution, use a processing solution with the following formulation. None/Shi (1) is a bleach-fix solution containing the compound of the present invention. Next, the composition of each bleach-fix solution used is shown. Iron tetraacetate [blood] Key salt 100.0% Sodium sulfite 10.0 Ammonium tathiosulfate 1000% Water
1. PH6.2 with ammonium hydroxide Bleach-fix solution Diammonium salt of ethylenediaminetetraacetate 7.5 Iron diaminetetraacetate [blood] Zenishio 100.0Sodium sulfite 10.0Sodium tathiosulfate 90.0Tathiourea
10.0 Yusui
1 night with ammonium hydroxide to pH 6.2 bleach-fix solution) Ethylenediaminetetraacetic acid diammonium salt 7.5 tethylenediaminetetraacetate iron [m] Anchor salt 100.0 night Sodium sulfite 10.0 Ammonium tathiosulfate 100. 0 evening 5.0
PH6.2 with ammonium hydroxide Bleach-fix solution {D} Diammonium ethylenediaminetetraacetate 7.5 Iron diaminetetraacetate [m] Rust salt 100.0 Sodium sulfite 10.0 Ammonium tathiosulfate 100.0 CH3
CH2CH2SH 5.0
pH with water and ammonium hydroxide
6.2 Bleach-fix solution {E} Diammonium salt of ethylenediaminetetraacetate 7.5 Iron diaminetetraacetate [m] Anchor salt loo. 0 Sodium sulfite 10.0 Ammonium tatiosulfate 100.0 Exemplary compound ■ 10.0 #Water
PH6.2 with ammonium hydroxide for 1 night Bleach-fix solution {F) Diasomonium ethylenediaminetetraacetate 7.59 Iron ethylenediaminetetraacetate [m] Anchor salt 100.0m Sodium sulfite 10.0 Ammonium tathiosulfate 100.0t Exemplary compound m 5.0 ta water
1. PH6.2 with ammonium hydroxide Bleach-fix solution (G) Ethylenediaminetetraacetic acid diammonium salt 7.59 Ethylenediaminetetraacetic acid iron [mountain] Complex salt 100.0% Sodium sulfite 10.0 Ammonium tathiosulfate 100.0% Exemplary compound {7} 1.0 t water
1. PH6.2 with ammonium hydroxide Bleach-fix solution (H) Diammonium ethylenediaminetetraacetate salt 7.5 Iron diaminetetraacetate [m] Complex salt 100.0 Sodium sulfite 10.0 Ammonium tathiosulfate 90.0 Evening odor Ammonium oxide 150.09 Exemplary compound ■
5.0 ta water
PH6.2 with ammonium hydroxide for 1 hour Bleach-fix solution (1) Ethylenediaminetetraacetic acid diammonium salt 7.5 evening Ethylenediaminetetraacetic acid iron [m] Zen's salt 100-0 evening Ammonium thiocyanate 90.0 evening Ammonium bromide 150.0 5.0 ta water on the exemplified compound side
1. PH6.2 with ammonium hydroxide Bleach-fix solution for each process ■ - (1) For each process, the bleach-fix completion time (clearing time) of the film to be processed and the neutrality when subjected to short-time (2 minutes) bleach-fix treatment The density was measured and the bleach-fixing performance was compared. The results are shown in Table 1 below. The bleach-fixing completion time is the time required for all bleached silver and unbleached silver in the exposed and unexposed areas to be desilvered and removed from the processing film system, and the neutral density is the time required for all of the bleached silver and unbleached silver in the exposed and unexposed areas to be removed from the processing film system. and unbleached silver combined white light density. Table 1 As is clear from Table 1, the bleach-fix solution containing a high concentration of ethylenediaminetetraacetate iron(m) rust salt as a bleaching agent was found to be poor in the conventional bleach-fix solution. When using a bleach-fix solution containing a bleach-fixing solution as a bleach accelerator, a bleach-fix solution containing a compound similar to the compound of the present invention as a bleach accelerator), and {D}, the completion time of bleach-fixing may be long. Recognize. In addition, in all of these cases, the neutral concentration during short-time processing is high, indicating that so-called bleach-fixing is incomplete. However, when bleach-fixing solutions E} to (1) containing the compounds of the present invention are used, high-sensitivity negative photosensitive materials cannot be sufficiently bleach-fixed in a much shorter time. It can be seen that desilvering is complete.Furthermore, the neutral concentration during short-time processing is low and desirable, indicating that the desilvering performance is very good.Furthermore, the bleach-fix solution (
It was confirmed that the dye images obtained by processing using E} to (1) were comparable in photographic properties such as color density and linearity on the characteristic curve, and the dyes had good storage stability. As described above, the bleach-fixing solutions {E) to (1) containing the compounds of the present invention have very excellent bleach-fixing performance.In addition, after performing color development in the above treatment, water washing treatment, stop treatment or stop treatment is performed. When bleach-fixing was performed after fixing, results similar to those shown in Table 1 were obtained, confirming that there is no substantial difference in bleaching effect even in this type of processing step. In addition, the pH of the bleach-fix solutions Tsukuda-nashi and Shi (1) was set to 5.
Similar results were obtained when the treatment was performed using two different types, 0 and 7.5, and it was confirmed that there was virtually no effect of pH. Incidentally, the lower the pH of the bleach-fixing solution, the higher the oxidizing power can be obtained, but since deterioration of the solution due to hypolysis becomes a problem, it is desirable to use the pH value in the range of 4.0 to 7.5. Example 1 The same sample used in Example 1 was exposed to a certain amount of light using a tungsten light source with the color density adjusted to 4900K using a filter, and then subjected to the following treatment. The processing includes color development for 3 minutes and 15 seconds, bleaching for 1 minute to 6 minutes and 30 seconds, washing with water for 2 minutes, fixing for 8 minutes, washing with water for 4 minutes, and stabilization treatment for 1 minute, and then drying. 08:00 ± 0. In each process, the processing solution used in Example 1 was used for color development and stabilization, the processing solution with the following formulation was used for bleaching and fixing, and the processing solution with the following formulation was used for bleaching and fixing. A treatment solution was used: Bleach solution Ammonium bromide 150.0 Takodak Preating Agent (BL-) 175.
0 Usui acetic acid 10.5 and sodium nitrate 35.0
1 evening pH 6.2 with ammonium hydroxide Eastman Kodak Company's Kodak Process C-41 Prescription Bleach Solution Tsukuda Ethylenediaminetetraacetic acid diammonium salt 200 Taethylenediamisotetraacetic acid iron [Rainbow] Zenishio 150.0 Polyodor Ammonium chloride 1500 Sodium nitrate 35.0 Polyglacial acetic acid
10.0 Yusui
1. Ammonium hydroxide to pH 6.2 Bleach solution} Ethylenediaminetetraacetate diammonium sea 20.0 tethylenediaminetetraacetate iron [wind] Tsubashio 95.0 Ammonium bromide 150.0 Sodium nitrate 35.09 Ice acetic acid
10.0 pm 5.0 pm Ammonium hydroxide pH 6.2 Bleach solution dish Ethylene diamine tetraacetic acid diammonium salt 20.0 Ta ethylene diamine tetra acetate iron [m] Mirror salt 95.0 Ammonium bromide 150.0 Ta Nitric acid Sodium 35.0 ta glacial acetic acid
10.0 evening CH3CH2C
H2SH 5.0 polyhydric
PH6.2 with ammonium hydroxide Bleach solution (E) Ethylenediaminetetraacetic acid diammonium salt 20.09 Ethylenediaminetetraacetate iron [m] Complex salt 65.0 Ammonium bromide 150.0 Ammonium nitrate 35.0 Glacial acetic acid
10.0 evening Exemplary compound (
6} 5.09 Wednesday
1 pH 6.2 with ammonium hydroxide Bleach solution (F) Ethylene diamine tetraacetic acid diammonium salt 20.0 tethylene diamine tetraacetate iron [m] Anchor salt 65.0 Ammonium bromide 150.0 Sodium nitrate 35.0 ta glacial acetic acid
10.0 evening Exemplary compound■ 10.0 high water
PH6.2 with ammonium hydroxide Bleach solution (G) Diammonium ethylenediaminetetraacetic acid salt 20.0 Iron diaminetetraacetate [m] Rust salt 65.0 Ammonium bromide 150.0 Glacial acetic acid 10.0 Exemplified compound (15) 5.0 t water
pH 6.2 with ammonium hydroxide for 1 night, fixer with ammonium thiosulfate 120.0 t, sodium sulfite 20.0 t water
1. For each treatment using each of the bleaching solutions (G), the bleaching completion time of the film and the neutral density when bleaching for a short time (1 minute) were measured and the bleaching performance was compared. The results are shown in Table 2 below. In Table 2, the bleaching completion time is the bleaching completion time required for all the silver in the exposed and final exposed areas to be removed from the film system by the next fixing process, and the neutral density is the dye and bleached silver. and the combined white light optical density of unbleached silver. As is clear from Table 2, conventionally known bleaching solutions consisting mainly of ethylenediaminetetraacetic acid rust salt bleach and containing ammonium bromide for halogenation, A bleach solution containing a high concentration of ethylenediaminetetraacetate iron (m) rust salt, a bleach solution containing a compound similar to the compound of the present invention, and [
It can be seen that it takes a long time to complete bleaching in both cases. It can be seen that all of these had a high neutral concentration during the bleaching completion time, indicating that the so-called bleaching process was incomplete. On the other hand, when bleaching solution (G) containing the compound of the present invention is used, desilvering can be completed in a much shorter time than in conventional formulations, despite containing less oxidizing agent. Recognize. This means that it is possible to provide a material that is advantageous in terms of reducing processing costs and preventing pollution caused by discharge of bleaching solution.
Furthermore, the neutral concentration during short-time treatment is low and shows a desirable value. As you can see from this, it is clear that the bleaching performance is high. It has also been confirmed that commercially available reversal color films can be similarly bleached successfully by using a bleaching solution containing the compound of the present invention. As described above, by using the compound of the present invention, it is possible to eliminate the need for the red dish chlorine bleach solution conventionally used for processing reversal color films, and to provide a processing composition that is very advantageous in terms of pollution control. . Also, bleach solution {E) or (
When the pH of G) was changed to 4.5 and 7.5, the same results as those shown in Table 2 were obtained, confirming that ``there is virtually no effect depending on the pH.'' The lower the pH of the bleaching solution, the higher the oxidizing power, but it is preferable to use the pH value in the range of 2.0 to 7.5. The dye image obtained by the process is comparable to the dye image obtained by the control process of Example 1 in terms of photographic performance such as color development density and linear retention on the characteristic curve, and the storage stability of the dye is also good. Example 3 An antihalation layer and a gelatin layer were provided on a triacetate film base, and on top of this, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer were sequentially formed. The emulsion layer was coated so that the total amount of silver was 60/100. At this time, the sonic silver halide emulsion layer was coated with 4-(-2-methoxybenzoyl-Q-) as a 2-equivalent yellow coupler.
chloroacetamide)-3''-(4...1t-amylphenoxy)penzanilide, and a 4-equivalent magenta coupler, 1-phenyl-3-, was used in the green-sensitive silver halide emulsion layer.
n-amyl-5-pyrazolone was used, a 4-equivalent cyan coupler was used in the red-sensitive silver halide emulsion layer, and 5-(n-penzyl-Nn-valerylamino)-1 naphthol was used in each emulsion layer. were added with conventional additives such as sensitizing dyes, hardeners, and spreading agents. The thus obtained silver halide reversal color sensitive material was used as a sample. This sample was exposed to a certain amount of light using a tungsten light source with the color temperature adjusted to 490 pK using a filter, and then subjected to the following treatments. (Processing process) Pre-processing time Hardening 3 minutes Incubation 1 minute 1st development 6 minutes stop 2 minutes 1st washing 4 minutes color development 9 minutes before bath 2 minutes bleach-fixing 1-2 minutes 2nd washing 3 minutes softening Drying for 1 minute Each treatment solution had the following formulation. [Anterior dura mater] 6-Nitrobenzimidazole nitrate 0.03 Sodium polysulfite (anhydrous) 0.8 Tatetrahydro 2,3-dimethoxyfuran 5'sodium sulfate (
anhydrous) 136 tuff formalin (35% aqueous solution) 30 [potassium bromide
Adjust the pH to 4.9 with 3.0 evening water and 1.1 carp sulfuric acid. [Neutralization] Hydroxylamine sulfate 20 Sodium polybromide 18 Yugla acetic acid
10 [sodium acetate
24 Sodium polysulfate (anhydrous)
45 Sodium polyhydroxide
Adjust the pH to 5.0 with glacial acetic acid or sodium hydroxide. [First development] Cardrafos 2 Fenidone 0.25 Sodium sulfite (anhydrous) 50.0 Hydroquinone 6.0 Sodium polycarbonate (monohydrate) 30.0 Potassium bromide 2.0 Sodium thiocyanate 1.3 Sodium polyhydroxide
6.0 units of potassium chloride (0.1%
Aqueous solution) 1 with 6.0 tap water [Stop] Sodium acetate 1
09 Glacial acetic acid 1 night with 36 liters of tap water [Color development] Curdraphos 5.09 Tertiary sodium phosphate 40. M Sodium Hydroxide 5.0 Taethylenediamine 2.0 Tabenzyl Alcohol 5.8 Zt-Butylamine Borane 0.1 Tacitradinic Acid
1.3 Takodatsu CD-3
11.3 Sodium sulfite
1.5.0 t water [fix] ammonium thiosulfate 120 t. sodium sulfite 20 t. water
1. [Stable] Holimarin (35% aqueous solution) 7.0.5.
IZ [Bleach-fixing] Ethylene diamine tetraacetate diammonium salt 10 ethylene diamine tetraacetate iron [m] complex salt 75 ta Sodium sulfite 10 polythiosulfate ammonium 90 ta Water
1. Prebath with 28% sodium hydroxide aqueous solution, pH 6.3 (Na2B407, 10 days 20)
20 ta shelf acid 40 evening water and 1 evening pH
8.2 Previous General (B) Glacial acetic acid
30.0 liters of sodium hydroxide 2.4 liters of water
1zo pH
41 ago Case {C) Shelf sand (Na2&07,10
Day 20) 20 multi-shelf acid
40 evening water and 11 evening pH
8.
2 ago Yutana Sand 2
0 Evening Shelf Acid 40 Evening CQC Day 2CH Sunset 5 Ta Water
pH at 1
Before 8.2 Bath leg shelf acid
40 Yutana Sand
20 evening Exemplary compound 01
5. End 1 with Yusui.
8.2 ago Yu {F} Glacial acetic acid
30 I sodium hydroxide
2.4 Exemplary Compound 4}
10 ta water for 1 evening
H 4
．． Before 0 General (G) Sodium bicarbonate
2 Sodium carbonate 12.
0 ta Exemplary Compound 6} 5 Yumizu de 1 SoPH
Before 9.7 General (H) 0 Sodium sulfite 6.0 ta Glacial acetic acid
12.0'sodium acetate
10.0 Sodium tathiosulfate
120.0 ta Sodium hydroxide
2.02 Exemplary Compound '7}
5 t water and 1 PH
4.6 separate
Case (1) Exemplary compound 7} 10
1 PH at Yusui
7.9 Processing is 3800 for prefixing and bleach-fixing, and 29.50 for other processing.
I went with 0. The time taken to complete the bleach-fixing of the film in each treatment was measured, and the neutral density of the film when the bleach-fixing treatment was carried out for 3 minutes was measured to compare the bleach-fixing performance with the use of pre-heating. The results are shown in Table 3 below. The bleach-fixing completion time is the time required for all of the silver salts in the unexposed and exposed areas to be removed from the desilvering system (the so-called clearing time), and the neutral density is the sum of the dye and residual silver. . This is the optical density due to white light. Table 3 As is clear from Table 3, when a conventional bleach-fixing solution containing no compound of the present invention is used, bleach-fixing is incomplete with the commonly known bleach-fixing solution for Kafu vapor processing. On the other hand, when treated with a sample containing the compound of the present invention, bleach-fixing was completed in a surprisingly short time even with a bleach-fixing solution with weak oxidizing power, and the neutral density was comparable to that of samples treated separately with standard treatment. It can be seen from the facts that bleach-fixing is carried out without any problem. Furthermore, the dye images obtained by bleach-fixing with a pre-bath treatment containing the compound of the present invention have a higher color density and color than dye images obtained by standard processing using a red blood salt bleaching solution. It was confirmed that there was no inferiority in photographic properties such as balance, and the storage stability of the dye was also good. After the pre-bath treatment, a bleach-fixing treatment was performed via a water washing treatment, and the same results as shown in Table 3 were obtained in all cases. Example 4 A sample was prepared by sequentially coating the following layers on a support made of cellulose acetate film from the support side. Layer 1: Antihalation layer. Layer 2: Gelatin middle layer. Layer 3: 1- as a cyan coupler dissolved in tri-o-cresyl phosphate and dispersed in an aqueous gelatin solution.
Hydroxy-N- {6-(2,4-t-aminophenoxy)butyl}-2
Red-sensitive silver halide gelatin emulsion layer containing naphthamide at a ratio of 1.4 parts/power. Layer 4: Gelatin middle layer. Layer 5: Magenta coupler and 1-(2,4,
6-Trichlorophenyl)-3-{[Q-(2,4-di-t-amylphenoxy)-acetamide]penzamide}-5-pyrazolone and 1-(2,4,6-trichlorophenyl)- 3-{1 [Q-
(2,4-di-t-amylphenoxy)acetamide]
penzamide}-4-(4-methoxyphenylazo)-
A green-sensitive silver halide gelatin emulsion layer containing 5-pyrazolone at a ratio of 1.8%. Layer 6: Gelatin middle layer. Layer 7: Filter layer containing yellow colloidal silver. Layer 8 Nobi-(4-nitrophenoxy)-Q-pivalyl-5-[r-(2,4-di-t-amylphenoxy)butyramide} as a yellow coupler dissolved in dibutyl phthalate and dispersed in an aqueous gelatin solution. A sound-sensitive silver halide gelatin emulsion layer containing 2-chloroacetanilide at a rate of 2.4 m/m. Layer 9: Gelatin protective layer. This sample was exposed to a certain amount of light using a tungsten light source with the color temperature adjusted to 490 pK using a filter, and then subjected to the following treatments. Processing process Processing time Color development 3 minutes before bath 2 minutes bleaching 1 minute to 2 minutes washing 2 minutes fixing 8 minutes washing 2 minutes stabilizing 1 minute drying Each process was performed at 37.600, color development and fixing. The same treatment solution used in Example 2 was used for the test and stability, and the same treatment solution used in Example 3 was used for Maekoya, but the following bleaching solution was used. Bleach solution formulation Ammonium ethylenediaminetetraacetate lv Iron diaminetetraacetate [m] Mirror salt 50 Ammonium bromide 509 Water
1 evening with ammonium hydroxide PH6.3
The bleaching completion time of the film in each treatment was measured and shown in Table 4. The bleaching completion time refers to the bleaching treatment time required for the amount of residual silver to become zero after completion of fixing, and the bleaching acceleration effect of the former was compared. Table 4 As is clear from Table 4, when the preparation not containing the compound of the present invention was used, the bleaching treatment was incomplete during the normal treatment time. On the other hand, it can be seen that when a precursor containing the compound of the present invention is used for treatment, sufficient treatment is possible in a short time even with a bleaching solution having weak oxidizing power. This allows the treatment solution to be diluted, which is advantageous in terms of pollution control and rapid processing. In addition, it was confirmed that the dye images obtained by pre-wetting treatment containing the compound of the present invention, followed by bleaching and fixing treatments, had no problems in photographic properties such as color density and color balance, and the storage stability of the dyes was also good. .

Claims (1)

[Scope of Claims] 1. After developing the exposed silver halide color photographic light-sensitive material, it contains a compound represented by the following general formula:
1. A method for processing a silver halide color photographic light-sensitive material, which comprises carrying out photographic processing using a processing solution having bleaching ability containing a metal complex salt of an organic acid or a processing solution directly preceding the processing solution. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are hydrogen atoms, hydroxyl groups or lower alkyl groups, A is an n-valent heterocyclic residue, m is 1 to
The integer of 5 and n represent an integer of 1 to 4. ]