JPH07111573B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and particularly to provide a processing method excellent in desilvering property and image storability.

(Prior art) In the processing method of silver halide color photographic light-sensitive materials, the shortening of processing steps and processing time has spread the use of over-the-counter processing (minilabization) of color photographic light-sensitive materials in recent years, or shortened the delivery time of finished products at major laboratories. It is becoming a very important technical development issue.

In particular, the desilvering process of a color photographic light-sensitive material for photography (for example, a color negative film or a color reversal film) that contains a large amount of silver and at the same time contains iodine ions requires a bleaching load depending on the silver amount and a fixing load due to iodine ions. Large, bleach-fixing process, fixing-bleach-fixing process, bleach-
In most cases, it is processed in two baths or two or more solutions such as bleach-fixing process, and the desilvering time is very long, about 6 to 20 minutes, which is a major obstacle to shortening the processing time and the processing process. ing.

Various techniques have been conventionally proposed in order to shorten the desilvering process as described above. Among them, as a bleach-fixing technique, a technique using a diethylenetriaminepentaacetic acid iron (III) complex as a bleaching agent described in JP-A-59-149358,
No. 0-46327, the technique of using the aminopolycarboxylic acid in combination, WO (International Publication) 80/00624, the technique of using an alkyliminodiacetic acid iron complex as a bleaching agent, etc. are disclosed. Insufficient or insufficient stability of the bleach-fixing solution makes it unsatisfactory in practice.

Further, as a technique for using a cyclohexanediaminetetraacetic acid iron complex in a bleach-fixing solution, there are disclosed in JP-A-61-41145 and 61-4.
No. 7959, No. 61-50142, No. 61-118752, and Research Disclosure 24023, etc.,
The bleaching power was slightly higher than that of iron (III) ethylenediaminetetraacetate, and rather, the fixing was hindered, and the bleaching agent was insufficient in practical use.

Further, as a technique for incorporating a halogen ion into a bleach-fixing solution for the purpose of increasing the bleaching power, there is disclosed in JP-A-51-87036 and JP-A-
Although disclosed in JP-A 3-11854, addition of bromine ion requires a large amount of addition (NH ₄ Br 50 g to 100 g or so), on the other hand, the bleaching promoting effect is small, and addition of iodide ion causes fixation. It was not a satisfactory technique because it had the drawback of delaying

On the other hand, the magenta coupler represented by the general formula (II) is disclosed in JP-A-59-162548, JP-A-60-43659, JP-A-59-171956 and JP-A-6-162598.
It is known from 0-172982, 60-33552 and US Pat. No. 3,061,432, and various studies have been conducted because of its excellent hue.

However, it has been found that the magenta coupler represented by the general formula (II) has a serious drawback that bleaching fog is likely to occur during continuous treatment and magenta stain is likely to occur with time after treatment. .

Regarding the generation of magenta stain after the treatment, the conventional anti-fading technology and anti-stain technology (as anti-fading technology, for example, U.S. Patent Nos. 2,360,290, 2,418,613, 2,2,
675,314, 2,701,197, 2,704,713, 2,728,6
No. 59, No. 2,732,300, No. 2,735,765, No. 2,710,801
No. 2,816,028, British Patent 1,363,921, JP-A-58-
Hydroquinone derivatives described in 24141, US Patent
Gallic acid derivatives described in 3,457,079 and 3,069,262, etc., U.S. Patents 2,735,765, 3,698,909, and Japanese Patent Publication No. 49
-20977, p-alkoxyphenols described in 52-6623, U.S. Patents 3,432,300, 3,573,050,
No. 3,574,627, No. 3,764,337, JP-A-52-35633,
Techniques such as p-oxyphenol derivatives described in JP-A Nos. 52-147434 and 52-152225, and bisphenols described in US Pat. No. 3,700,455. As stain prevention technology,
JP-A-49-11330, JP-A-50-57223, JP-A-56-85747,
And the technology of Japanese Examined Patent Publication No. 56-8346) cannot be used to obtain a sufficient effect.

As described above, it has been desired to develop a technique for overcoming the drawbacks of the magenta coupler represented by the general color (II).

(Means for Solving Problems) As a result of various studies, the present inventors have found that the object of the present invention can be effectively achieved by using the following means. That is, after color development, at least one metal complex of aminopolycarboxylic acid represented by the following general color (I) is contained and thiosulfate is added in an amount of 0.3-2.
A processing method for a silver halide color photographic light-sensitive material, which comprises processing with a bleach-fixing solution containing mol / l and iodine ions in an amount of 5 × 10 ^{-4 to} 0.05 mol / l.

General formula (I) In the formula, X represents a substituent, and n represents 0 or an integer of 1-10. M represents a hydrogen atom, an ammonium salt, an alkali metal or an alkaline earth salt. M may represent 1 / a of the a-valent polyvalent cation.

Particularly, in the bleach-fixing solution represented by the general formula (I), which uses the aminopolycarboxylic acid metal complex as a bleaching agent, the desilvering rate was remarkably improved when the desilvering treatment was carried out in the presence of a specific amount of iodine ion. It is also noteworthy that the fixing delay does not occur in spite of the presence of iodine ions.

Further, the above desilvering promoting effect is extremely effective in a light-sensitive material containing iodo ions in a silver halide emulsion, and is particularly effective in a light-sensitive material having a relatively large coating amount of silver. It was completely unpredictable from the prior art. It is also a surprising fact that when the magenta coupler of the general formula (II) is used and the magenta coupler is used, the disadvantage of the coupler, that is, the generation of magenta stain, is eliminated at the same time. This effect is obtained by treating with a bleach-fixing solution containing an aminopolycarboxylic acid metal complex represented by the general formula (I) as a bleaching agent, so that the color developing agent contained in the light-sensitive material can be washed out in a bleach-fixing solution. It is presumed that bleaching fog and image storability were improved as a result.

The details of the compound represented by formula (I) are described below.

In the formula, X represents a substituent and may be the same or different when n ≧ 2. Specifically, a halogen atom, an alkyl group, a hydroxy group, a carboxy group, a sulfonic acid, a phosphonic acid, a nitro group, an amino group, a mercapto group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a hetero group. Ring oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group , An alkoxycarbonylamino group, an aryloxycarbonylamino group,
It represents a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group and the like. Two or more kinds of these substituents may be used.

n represents an integer of 0-10. Preferably n = 0, 1, 2
Is. Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

Some of these compounds are commercially available,
It can also be synthesized according to the method described in R. Pribil, V. Vesely, Talanta, 10, 1287 (1963) and the like.

The metal complex salt of the compound of the general formula (I) means iron as a metal,
Copper, cobalt and nickel complex salts are mentioned, and iron (III) complex is particularly preferable. These metal complexes may be used by mixing the compound of the general formula (I) with metal ions and isolating them as a metal complex in advance, or by mixing them at the time of use. Further, it is particularly preferable that the molar concentration of the compound of the general formula (I) is higher than the molar concentration of metal ions, and a mixing ratio of about 1.05; 1 or 1.2: 1 is optimal.

The amount of the metal complex salt of the general formula (I) used is 0.025 to 1 mol, preferably 0.05 to 0.5 mol, per 1 bleach-fixing solution.

As the bleaching agent of the bleach-fixing solution of the present invention, other organometallic complex (preferably iron (III) complex salt) may be used in combination. The preferred organometallic complex to be used in combination is the iron (III) complex of aminopolycarboxylic acid shown below.

Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Triethylenetetraminehexaacetic acid Nitrilotriacetic acid Methyliminodiacetic acid 1,3-Propylenediaminetetraacetic acid Glucolic etherdiaminetetraacetic acid Iodine ions in the bleach-fixing solution of the present invention are 5 × 10 ^{−4 to} 0.05
mol / l Preferably, the content is 2 × 10 ^{−3 to} 0.02 mol / l.

Here, the bleaching power of 5 × 10 ⁻⁴ or less decreases, and the bleaching power of 0.05 or more unfavorably results in a slow fixing speed. These iodine ions may be added with an organic or inorganic compound which releases iodine ions. Further, during continuous processing, the silver halide color photographic light-sensitive material is fixed so that the iodine ions are eluted and the above concentration is obtained. May be.

Here, even if iodine ions are eluted in the batch process usually performed, the amount is 5 × 10 ⁻⁵ mol / l or less.

Typical compounds to be added include potassium iodide, ammonium iodide and sodium iodide.

The fixing agents used in the bleach-fixing solution according to the present invention include known fixing agents, that is, thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid, 3,6-dithia-1,8- It is a thioether compound such as octanediol and a water-soluble silver halide dissolving agent such as thioureas.
A mixture of two or more species can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per 1 is preferably 0.3 to 2 mol, more preferably 0.5 to 1.5 mol.

Further, various bleaching accelerators can be used if necessary.

For example, U.S. Pat. No. 3,893,858, German Patent No.
No. 1,290,812, JP-A-53-95630, and Chisearch Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide bond, and JP-B-45-8506 and JP-A-SHO No. 52-20832, No. 53-327
Thiourea compounds described in U.S. Pat. No. 35, US Pat. No. 3,706,561 and the like, or halides such as bromine ions are preferred because of their excellent bleaching power.

If necessary, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate,
Phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and other inorganic acids having one or more pH buffering agents, organic acids and their alkali metal or ammonium salts, or ammonium nitrate, guanidine, etc. Agents and the like can be added.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

The bleach-fixing solution according to the present invention contains a sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), a bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as a preservative. ), Metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like. These compounds are preferably contained in an amount of about 0.02 to 0.50 mol / l in terms of sulfite ion, more preferably 0.04 to
It is 0.40 mol / l.

As a preservative, sulfite is generally added, but in addition, sulfinic acids, ascorbic acid, carbonyl bisulfite adduct, carbonyl compound or the like may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like may be added if necessary.

The pH of the bleach-fixing solution of the present invention is 3-10, preferably 4-8,
It is more preferably 5 to 7. Replenishment amount is 1m ²
100 ml to 2500 ml, preferably 250 ml to 1500 ml, and particularly preferably 300 ml to 500 ml.

The most preferable embodiment is to reduce the replenishment amount, for example, 1000 ml / m ² or less, and mainly supply iodine ions by elution from the light-sensitive material. Particularly, a high iodine-containing light-sensitive material, for example, AgI = 5 to 15 mol% is suitable for the above embodiment.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N, N-diethylaniline. Methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or a development inhibitor or a fog. Generally, it contains an inhibitor and the like. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as aminos, dye forming couplers, competitive couplers, fogging agents such as sodium boron hydride. , 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, Representative examples are N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts.

When the reversing process is performed, black and white development is usually performed before color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The replenishment amount of these color developing solution and black-and-white developing solution depends on the color photographic light-sensitive material to be processed, but it is generally less than 3 liters per square meter of light-sensitive material, and 500 ml can be obtained by reducing the bromide ion concentration in the replenishing solution. It can also be: When the replenishment amount is reduced, it is preferable to prevent the evaporation of liquid and air oxidation by reducing the opening area of the processing tank. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution. The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture a
nd Television Engineers, Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In processing the color light-sensitive material of the present invention, as a solution to such a problem,
The method of reducing calcium and magnesium ions described in Japanese Patent Application No. 61-131,632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9.
And preferably 5-8. The temperature of washing water and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15-45 ° C, and preferably 30 at 25-40 ° C.
A range of seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No.
All known methods described in -8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat. Salt complex, JP-A-5
The urethane compound described in 3-135,628 can be mentioned.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
3-Prazolidones may be incorporated. Typical compounds are JP-A Nos. 56-64,339, 57-144,547, and 58.
-115,438 etc. are described.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath.

Next, the silver halide color photographic light-sensitive material of the present invention will be described in detail.

The silver halide in the silver halide emulsion layer of the present invention preferably contains silver halide grains containing at least 0.5 mol% silver iodide. From the viewpoint of the sensitivity of the light-sensitive material, the photographic characteristics and the desilvering property in the bleach-fixing solution, it is preferably 0.5 to 25 mol%, more preferably 2 to 20 mol%, and especially 5 to 15 mol%.
In the present invention, an iodomol content exceeding 25 mol% is not preferable because the desilvering rate is delayed.

The coated silver amount of the silver halide of the present invention is from 1 g in terms of desilvering property.
Preferably 8 g / m ^2, more preferably from 1.5g~7g / m ^2.
Here, if it exceeds 8 g / m ² , desilvering property is not preferable.

Further, the smaller the particle size distribution of the silver halide grains of the silver halide emulsion used in the present invention, the more preferred is so-called monodisperse silver halide grains.

The photographic emulsion used in the present invention is Research Disclosure (RD) vol.170 Item No.17643 (I, II, III).
It can be prepared using the method described in Section (December 1978).

In the present invention, silver iodide-containing planographic silver halide grains are preferably used. The planographic silver halide grains preferably have a grain size of 5 times or more the grain thickness. It is more preferably 5 to 50 times, and most preferably 7 to 20 times. The planographic silver halide grains are disclosed in JP-A Nos. 58-113930 and 58-1085.
It can be prepared by a general preparation method described in No. 32 or the like, and in the present invention, those in the above range are preferable in terms of bleaching fog and desilvering property.

The "monodisperse silver halide grains" preferably used in the present invention means that the shape of each silver halide grain looks uniform when the emulsion is observed by an electron micrograph, and the grain size is uniform, and The ratio S / of the standard deviation S of the particle size distribution to the average particle size is preferably 0.22 or less, more preferably 0.15 or less. Here, the standard deviation S of the particle size distribution is calculated according to the following equation.

Further, the average grain size referred to here is the diameter of spherical silver halide grains, or the diameter of a cubic image or grains of a shape other than spherical when the projected image is converted into a circular image of the same area. Is the average value of, and when its particle size is ri and its number is ni, then is defined by the following equation.

The above particle diameter can be measured by various methods generally used in the technical field for the above purpose. A typical method is Loveland's "Particle Size Analysis Table" ASTM Symposium on
Wright Microscopy, 1955, pp. 94-122 or "The Theory of Photographic Process" by Mies and James,
The third edition, published by Macmillan, Inc. (1966), Chapter 2. This particle size can be measured using the projected area of the particle or a diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The relationship between particle size distributions is described in "The Empirical Relationship between Sensitometric and Particle Size Distributions in Photographic Emulsions", The Photographic Journal, Volume LXXIX, (1949), pages 330-338, Triperi and Smith. This can be determined in the manner described.

The silver halide grains used in the silver halide emulsion of the present invention may be those prepared by any of the acid method, the neutral method and the ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the opposite pot are controlled, and the amount of silver ions corresponding to the growth rate of silver halide grains as described in JP-A-54-48521, for example. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure Vol. 176, No. 17643 (December 1978) and Vol. 187, N.
No. 18716 (November 1979), and the corresponding places are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the locations described in the table below are shown.

Various color couplers can be used in the present invention. Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and closed or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17643 (1978).
December 1987), section VII-D and the patent cited in 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a balance group or is polymerized to be diffusion resistant. The amount of coated silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted by a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. A coupler in which the color-forming dye has a suitable diffusibility, a colorless coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator can also be used.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and U.S. Pat.Nos. 3,408,194 and 3,447,9 are used.
No. 28, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow coupler or Japanese Patent Publication No. 55-10739, U.S. Patent No. 4,401,752, No. 4,326,
No. 024, RD18053 (April 1979), British Patent No. 1,425,020
Representative examples thereof include nitrogen atom-releasing yellow couplers described in West German Application Publication Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness, especially the light fastness, of the color forming dye, while the α-benzoyl acetanilide type coupler can obtain a high coloring density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

In the present invention, the above-mentioned pyrazoloazole coupler represented by the general formula (II) is used as a magenta coupler,
Most preferable in terms of photographic characteristics.

The magenta coupler represented by formula (II) will be described in detail below.

General formula (II) In the formula, R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Za, Zb and Zc represent methine, substituted methine, = N- or -NH-, and Za
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. Furthermore, the case where R ₁ or X forms a dimer or higher multimer is also included. In addition, when Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or higher multimer.

In the general formula (II), the multimer means one having two or more groups represented by the general formula (II) in one molecule, and a bis form and a polymer coupler are also included in this. Here, the polymer coupler is a monomer having a portion represented by the general formula (II) (preferably one having a vinyl group,
Hereinafter, a homopolymer composed of only a vinyl monomer) may be used, or a copolymer may be prepared together with a non-color forming ethylene-like monomer that does not couple with an oxidation product of an aromatic primary amine developing agent.

The compound represented by the general formula (II) is a 5-membered ring-5-membered ring fused nitrogen heterocyclic type coupler, and its coloring mother nucleus shows isoelectronic aromaticity with naphthalene, and is generally called azapentalene. It has a structure. Among the couplers represented by formula (II), preferred compounds are 1H-imidazo [1,2-b] pyrazoles, 1H-pyrazolo [1,5-b] pyrazoles, 1H-pyrazolo [5,1-c ] [1,2,4] Triazoles, 1H-pyrazolo [1,5-b] [1,2,4] triazoles, 1H-pyrazolo [1,5-d] tetrazole and 1
H-pyrazolo [1,5-a] benzimidazoles,
General formula (IIa) (IIb) (IIc) (IId) (IIe)
Of these, particularly preferred compounds represented by (IIf) and (IIf) are (IIa), (IIc) and (IId).

The substituents R ₂ , R ₃ and R ₄ in formulas (IIa) to (IIf) are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group or an aryloxy group. , Heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocycle Represents a thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and X represents a hydrogen atom, a halogen. atom,
It represents a carboxy group or a group capable of coupling off with a group bonded to a carbon at a coupling position via an oxygen atom, a nitrogen atom or a sulfur atom.

The case where R ₂ , R ₃ , R ₄ or X becomes a divalent group to form a bis form is also included. When the moieties represented by formulas (IIa) to (IIf) are present in the vinyl monomer, R ₂ , R ₃
Alternatively, R ₄ represents a simple bond or a linking group, and the moiety represented by the general formulas (IIa) to (IIf) is bonded to the vinyl group via this.

More specifically, R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, propyl group, i-propyl group, t
-Butyl group, trifluoromethyl group, tridecyl group, 3
-(2,4-di-t-amylphenoxy) propyl group, 2
-Dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl group (e.g., phenyl group, 4-t-butylphenyl group, 2,4-di group) -T-amylphenyl group, 4-tetradecanamidophenyl group,
Etc.), a heterocyclic group (for example, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group,
Etc.), cyano group, alkoxy group (eg, methoxy group,
Ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-phenoxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (for example, phenoxy group, 2-methylphenoxy group, 4-t
-Butylphenoxy group, etc.), heterocyclic oxy group (eg, 2-benzimidazolyloxy group, etc.), acyloxy group (eg, acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (eg, N- Phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (eg, trimethylsilyloxy group, etc.), sulfonyloxy group (eg, dodecylsulfonyloxy group, etc.), acylamino group (eg, acetamide group, benzamide) Group, tetradecanamide group, α- (2,4-di-t-amylphenoxy) butyramide group, γ- (3-t-butyl-4-hydroxyphenoxy) butyramide group, α- {4- (4-hydroxyphenyl) Sulfonyl) phenoxy} decanamide group, etc.), anilino group ( In example, a phenyl group, 2
-Chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5- {α- (3-t- Butyl-4-hydroxyphenoxy) dodecanamide} anilino group, etc.), ureido group (eg, phenylureido group, N-butyl-N′-)
Methylureido group, methylureido group, N, N-dibutylureido group, etc.), imide group (for example, N-succinimido group, 3-benzylhydantoinyl group, 4- (2-ethylhexanoylamino) phthalimide group, Etc.), a sulfamoylamino group (eg, N, N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), a carbamoylamino group (eg,
Carbamoylamino group, N, N-dimethylcarbamoylamino group, etc.), alkylthio group (for example, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3
-(4-t-butylphenoxy) propylthio group,
Etc.), an arylthio group (for example, a phenylthio group, 2-
Butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc., heterocyclic thio group (for example, 2-benzothiazolylthio group) Base,
Etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (eg, phenoxycarbonylamino group, 2,4-di-t
ert-butylphenoxycarbonylamino group, etc.), sulfonamide group (eg, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5) -T-butylbenzenesulfonamide group, etc.), carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group, N-methyl-N-dodecyl group Carbamoyl group, N
-{3- (2,4-di-tert-amylphenoxy) propyl} carbamoyl group, etc., acyl group (e.g., acetyl group, (2,4-di-tert-amylphenoxy) acetyl group, benzoyl group, Etc.), a sulfamoyl group (for example,
N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group, N- (2-dodecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group Group, etc.), sulfonyl group (for example, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, trienesulfonyl group,
Etc.), a sulfinyl group (eg, octansulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group,
Etc.) and an aryloxycarbonyl group (eg, a phenyloxycarbonyl group, a 3-pentadecylphenyloxy-carbonyl group, etc.).

X is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a carboxyl group, or a group linked by an oxygen atom (for example, an acetoxy group, a propanoyloxy group, a benzoyloxy group, 2,4- Dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyrvinyloxy group, cinnamoyloxy group, phenoxy group,
4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-
Naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.),
Groups linked by nitrogen atoms (eg, benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3,4,5,6, -pentafluorobenzamide group, octanesulfonamide group, p -Cyanophenylureido group, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, 1-benzyl-ethoxy-3-hydantoinyl group, 2N-1,1-dioxo-3
(2H) -oxo-1,2-benzisothiazolyl group, 2-
Oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2,4-triazol-1-yl group, 5- or 6-bromo-benzotriazole-1- Group, 5-methyl-1,2,3,4-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoinyl group, 1-benzyl-5-hexadecyloxy-3-hydantoinyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group,
4-pivaloylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo group, etc.), a group linked by an ion atom (for example, phenylthio group, 2-carboxyphenylthio group, 2-butoxy-5-group). t-octylphenylthio group, 4-methanesulfonamidophenylthio group, 2,5-dibutoxyphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 4-dodecyloxyphenylthio group, 2- (2-hexanesulfonylethyl) -5-tert-octylphenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2 , 3,4,5
-Tetrazolylthio group, 2-benzothiazolylthio group,
2-dodecylthio group, 2-dodecylthio-5-thiophenylthio group, 2-phenyl-3-dodecyl-1,2,4-triazolyl-5-thio group and the like).

When R ₂ , R ₃ , R ₄ or X is a divalent group to form a bis derivative, the divalent group can be described in more detail. A substituted or unsubstituted alkylene group (eg, methylene group, ethylene group, 1,10-decylene _{group, -CH 2 CH 2 -O-CH} 2 CH 2 -,
Etc.), a substituted or unsubstituted phenylene group (eg 1,4
-Phenylene group, 1,3-phenylene group, -NHCO-R ₅ -CONH- group (R ₅ is. A substituted or unsubstituted alkylene group or a phenylene group) and the like.

The linking group represented by R ₂ , R ₃ or R ₄ when the compounds represented by the general formulas (IIa) to (IIf) are present in the vinyl monomer is an alkylene group (a substituted or unsubstituted alkylene group , For example, methylene group, ethylene group, 1,10-decylene group, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc., phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group A 1,3-phenylene group, -NHCO-, -CONH-, -O-, -OCO-, and aralkylene groups (e.g., Etc.) and groups that are established by combining those selected from the above.

The vinyl group in the vinyl monomer has the general formula (IIa)
To (IIf) are also included. A preferable substituent is a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid, α-is a non-color-forming ethylene-like monomer that does not cull with an oxidation product of an aromatic primary amine developer.
Chloroacrylic acid, α-alacrylic acid (eg, methacrylic acid, etc.) and esters or amides derived from these acrylic acids (eg, acrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methacrylamide, Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxymethacrylate), methylenedibisacrylamide, vinyl ester (eg vinyl acetate, vinyl propionate, etc. And vinyl laurate),
Acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl Ethyl ether), maleic acid, maleic anhydride, maleic acid ester, N-vinyl-2-
Pyrrolidone, N-vinyl pyridine, and 2- and 4
-Vinyl pyridine and the like. It also includes the case where two or more non-color-forming ethylenically unsaturated monomers used here are used together.

Examples of compounds of the couplers represented by the general formulas (IIa) to (IIf), synthetic methods, and the like are described in the following documents.

The compound of the general formula (IIa) is disclosed in JP-A-59-162548, the compound of the general formula (IIb) is disclosed in JP-A-60-43659, and the compound of the general formula (IIc) is disclosed in JP-B-47-27411. And the general formula (II
The compounds of d) are disclosed in JP-A-59-171956 and JP-A-60-172982.
Etc., the compound of the general formula (IIe) is described in JP-A-60-33552, and the compound of the general formula (IIf) is described in US Pat. No. 3,061,432.
Etc., respectively.

Further, JP-A-58-42045, 59-214854 and 59-17755.
3, 59-177544 and 59-177557, the highly chromogenic ballast group is represented by the above general formulas (IIa) to (IIf).
It applies to any of the compounds of.

Specific examples of the pyrazoloazole-based coupler used in the present invention are shown below, but the invention is not limited thereto.

These couplers are generally used in an amount of 2 × 10 ⁻³ to 5 × 10 ⁻¹ mol, preferably 1 × 10 ⁻² mol per mol of silver in the emulsion layer.
Mol to 5 × 10 ^-1 mol.

The above couplers and the like can be used in combination in two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound in two or more different layers.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan couplers, U.S. Pat.Nos. 2,772,162 and 1
3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and 2,5-diacylamino-substituted phenol couplers and U.S. Pat. Third 3,446,622
Nos. 4,333,999, 4,451,559 and 4,42
Nos. 7,767 and the like include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No. 2,1.
Specific examples of magenta couplers are described in 25,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound can be used in two or more different layers. Can also be introduced.

To introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 are used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (for example,
Acetyl citrate tributyl), benzoic acid esters (eg octyl benzoate), alkyl amides (eg diethyl lauryl amide), fatty acid ester acids (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate) ), Or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. After being dissolved in, it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and 0.003 to 0.3 mol for the cyan coupler. It is 0.002 to 0.3 mol.

The photographic light-sensitive material used in the present invention is applied to a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper or a rigid support such as glass. For details on the support and coating method, see Research Disclosure Vol. 176 Item 17643 XV (P.27) XVI
It is described in Item I (P.28) (December 1978 issue).

As the color light-sensitive material, a color light-sensitive material for photographing (negative film, reversal film, etc.) is preferable.

Representative examples of preferred embodiments of the present invention are shown below. However, it is not limited to the following.

(1) The method for processing a silver halide color photographic light-sensitive material according to claim (1), wherein the amount of silver coated on the silver halide color photographic light-sensitive material is 1 g to 8 g / m ^2. .

(2) The silver halide color photographic light-sensitive material is iodine-free.
A silver halide color photographic light-sensitive material according to claim (2), which is a color light-sensitive material for photography having at least one layer containing a silver iodobromide emulsion of 5 mol% or more. Processing method.

(Examples) Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention. However, the present invention is not limited to the following examples.

Example 1 On a subbed cellulose triacetate film support,
A sample, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

1st layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.3 Coupler C-1 0.06 UV absorber UV-1 0.1 Same as above UV-2 0.2 Dispersion oil Oil-1 0.01 Same as above Oil-2 0.01 Second layer (intermediate layer) Fine particles Silver bromide (average grain size 0.07μ) 0.15 Gelatin 1.0 Coupler C-2 0.02 Dispersion oil Oil-1 0.1 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 mol%, diameter / Thickness ratio 2.5, average particle size 0.3μ, internal high AgI type) Silver 0.4 Gelatin 0.6 Sensitizing dye I 1.0 × 10 ^-4 Sensitizing dye II 3.0 × 10 ^-4 Sensitizing dye III 1 × 10 ^-5 Coupler C- 3 0.06 Coupler C-4 0.06 Coupler C-8 0.04 Coupler C-2 0.03 Dispersed oil Oil-1 0.03 Same as above Oil-3 0.012 4th layer (2nd red-sensitive emulsion layer) Silver iodobromide emulsion (5 mol of silver iodide) %, diameter / thickness ratio of 4.0, an average particle diameter of 0.7 .mu.m, internal high AgI type) 0.7 sensitizing silver dye I 1 × 10 ^-4 sensitizing dye II 3 × 10 sensitized ^-4 dye III 1 ^10-5 Coupler C-3 0.24 Coupler C-4 0.24 Coupler C-8 0.04 Coupler C-2 0.04 dispersion oil Oil-1 0.15 Same as above Oil-3 0.02 Fifth Layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (Silver iodide 10 mol%, diameter / thickness ratio 1.3, average grain size 0.8 μ, internal high AgI type) Silver 1.0 Gelatin 1.0 Sensitizing dye I 1 × 10 ⁻⁴ Sensitizing dye II 3 × 10 ⁻⁴ Sensitizing Dye III 1 × 10 ^-5 Coupler C-6 0.05 Coupler C-7 0.1 Dispersion oil Oil-1 0.01 Same as above Oil-2 0.05 Sixth layer (intermediate layer) Gelatin 1.0 Compound Cpd-A 0.03 Dispersion oil Oil-1 0.05 Seventh Layer (first green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide 2 mol%, diameter / thickness ratio 2.5, average grain size 0.3 μ, internal high AgI type) Silver 0.3 Sensitizing dye IV 5 × 10 ^{− 4} Sensitizing dye VI 0.3 × 10 ^-4 Sensitizing dye V 2 × 10 ^-4 Gelatin 1.0 Coupler C-9 0.2 Coupler C-5 0.03 Coupler C-1 0.03 Compound Cpd-C 0.012 Dispersion oil Oil-1 0. 5 8th layer (2nd green sensitive emulsion layer) Silver iodobromide emulsion (4 mol% silver iodide, diameter / thickness ratio 4.0, average grain size 0.6μ, internal high AgI type) Silver 0.4 Sensitizing dye IV 5 × 10 ^-4 Sensitizing Dye V 2 × 10 ^-4 Sensitizing Dye VI 0.3 × 10 ^-4 Coupler C-9 0.25 Coupler C-1 0.03 Coupler C-10 0.015 Coupler C-5 0.01 Compound Cpd-C 0.012 Dispersion Oil Oil -1 0.2 9th layer (3rd green emulsion layer) Silver iodobromide emulsion (6 mol% silver iodide, diameter / thickness ratio 1.2, average grain size 1.0μ, internal high AgI type) Silver 0.85 Gelatin 1.0 increase Sensitizing dye VII 3.5 × 10 ^-4 Sensitizing dye VIII 1.4 × 10 ^-4 Coupler C-13 0.01 Coupler C-12 0.03 Coupler C-9 0.20 Coupler C-1 0.02 Coupler C-15 0.02 Dispersed oil Oil-1 0.20 Same as above Oil -0.05 0.05 10th layer (yellow filter layer) Gelatin 1.2 Yellow colloidal silver 0.08 Compound Cpd-B 0.1 Dispersion oil Oil-1 0.3 11th layer (1st blue sensitive emulsion layer) Monodisperse iodine odor Silver halide emulsion (silver iodide 4 mol%, diameter / thickness ratio of 1.5, an average particle diameter of 0.5 [mu], internal high AgI type) silver 0.4 Gelatin 1.0 Sensitizing dye IX 2 × 10 ^-4 coupler C-14 0.9 Coupler C-5 0.07 Dispersion oil Oil-1 0.2 12th layer (2nd blue sensitive emulsion layer) Silver iodobromide emulsion (10 mol% silver iodide, diameter / thickness ratio 4.5, average grain size 1.3μ, internal high AgI type) Silver 0.4 Gelatin 0.6 Sensitizing dye IX 1 × 10 ^-4 Coupler C-14 0.25 Dispersion oil Oil-1 0.07 13th layer (first protective layer) Gelatin 0.8 UV absorber UV-1 0.1 Same as above UV-2 0.2 Dispersion oil Oil- 1 0.01 Dispersion oil Oil-2 0.01 14th layer (2nd protective layer) Fine silver bromide (average particle size 0.07μ) 0.5 Gelatin 0.45 Polymethylmethacrylate particles (diameter 1.5μ) 0.2 Hardener H-1 0.4 p -Hydroxybenzoic acid n-butyl 0.012 Formaldehyde scavenger S-0.5 Formaldehyde scavenger S-2 0.5 In addition to the above components, a surfactant was added to each layer as a coating aid.

The chemical structural formulas or names of the compounds used in this example are shown below: Oil-1 Tricresyl phosphate Oil-2 Dibutyl phthalate Oil-3 Bis (2-ethylhexyl) phthalate 20 CMS of the color photographic light-sensitive material obtained as described above
After being exposed to light at 1, the following processing steps were performed. However, the composition of the bleach-fix solution was changed as shown in Table 1.

 Process Treatment time Treatment temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching and fixing 4 minutes 00 seconds 38 ℃ Washing with water (1) 20 seconds 35 ℃ Washing with water (2) 20 seconds 35 ℃ Stability 20 seconds 35 ℃ Drying 50 seconds 65 ℃ Next The composition of the treatment liquid is described in.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N-β-hydroxyethyl amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 l pH 10.05 (bleach-fixing solution) (unit: g) Aminopolycarboxylic acid iron (III) ・ NH ₄ (Table 1 0.25mol Ammonium dihydrate Aminopolycarboxylic acid disodium salt 0.01mol Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0ml Acetic acid (98%) 5.0ml KI See Table 1 1.0l pH 6.0 Washing solution) Tap water is used as an H-type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amber Light IR-400) was passed through a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / l or less, followed by 20 mg / l sodium diisocyanurate dichloride and 0.15 g / l sodium sulfate. Was added.

The pH of this solution is in the range 6.5-7.5.

(Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added to 1.0 l pH 5.8-8.0 Above After the processing in the processing step, the residual silver amount was analyzed by exposure X-ray, and the results are shown in Table 1.

In Table 1, the desilvering promoting effect is small when aminopolycarboxylic acids other than the present invention are used and iodo ions are used in combination. The effect and residual silver amount were reduced.

(No. 9, 10, 11, 12, 13, 15, 16, 17, 18, 19, 20) Example 2 On a subbed cellulose triacetate film support,
A sample A, which is a multi-layer color light-sensitive material composed of each layer having the composition shown below, was prepared.

The amount (photosensitive layer composition) coating layer was expressed by the unit of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.3 ExM-9 0.06 UV-1 0.03 UV-2 0.06 UV-3 0.06 Solv-1 0.15 Solv-2 0.15 Solv-3 0.05 Second layer (intermediate layer) Gelatin 1.0 UV-1 0.03 ExC-4 0.02 ExF-1 0.004 Solv-1 0.1 Solv-2 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.5)
μ, coefficient of variation of equivalent spherical diameter 20%, plate-like particles, diameter / thickness ratio
3.0) Coating silver amount 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 15%, spherical particles, diameter / thickness ratio
1.0) Silver coating amount 0.6 Gelatin 1.0 ExS-1 4 × 10 ^-4 ExS-2 5 × 10 ^-5 ExC-1 0.05 ExC-2 0.50 ExC-3 0.03 ExC-4 0.12 ExC-5 0.01 4th layer (high sensitivity) Red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 1: 1 internal high A)
gI type, equivalent sphere diameter 0.7μ, variation coefficient of equivalent sphere diameter 15%, plate-shaped particles, diameter / thickness ratio 5.0) Coating silver amount 0.7 Gelatin 1.0 ExS-1 3 × 10 ^-4 ExS-2 2.3 × 10 ^-5 ExC-6 0.11 ExC-7 0.05 ExC-4 0.05 Solv-1 0.05 Solv-3 0.05 Fifth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.1 Solv-1 0.05 Sixth layer (low-sensitivity green-sensitive emulsion layer) Odor Silver halide emulsion (AgI 4 mol%, core shell ratio 1: 1 internal high A
gI type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Coating silver amount 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of equivalent spherical diameter 25%, spherical particles, diameter / thickness ratio
1.0) Silver coating amount 0.20 Gelatin 1.0 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.4 ExM-9 0.07 ExM-10 0.02 ExY-11 0.03 Solv- 1 0.3 Solv-4 0.05 7th layer (high-sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio 1: 3, internal high A)
gI type, sphere equivalent diameter 0.7μ, variation coefficient of sphere equivalent diameter 20%, plate-like particles, diameter / thickness ratio 5.0) Coating silver amount 0.8 Gelatin 0.5 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.1 ExM-9 0.02 ExY-11 0.03 ExC-2 0.03 ExM-14 0.01 Solv-1 0.2 Solv-4 0.01 Eighth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.05 Solv -1 0.02 9th layer (donor layer having a multilayer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 2 mol%, core-shell ratio 2: 1, internal high A)
gI type, equivalent sphere diameter 1.0μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 6.0) Silver coating amount 0.35 Silver iodobromide emulsion (AgI 2 mol%, core shell ratio 1: 1) A
gI type, equivalent sphere diameter 0.4μ, variation coefficient of equivalent sphere diameter 20%, plate-shaped particles, diameter / thickness ratio 6.0) Coating silver amount 0.20 Gelatin 0.5 ExS-3 8 × 10 ^-4 ExY-13 0.11 ExM-12 0.03 ExM-14 0.10 Solv-1 0.20 10th layer (yellow filter layer) Yellow colloidal silver 0.05 Gelatin 0.5 Cpd-2 0.13 Solv-1 0.13 Cpd-1 0.10 11th layer (low sensitivity blue sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, sphere equivalent diameter 0.7
μ, coefficient of variation of spherical equivalent diameter 15%, plate-like particles, diameter / thickness ratio
7.0) Coating silver amount 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 25%, plate-shaped particles, diameter / thickness ratio
7.0) Coating silver amount 0.15 Gelatin 1.6 ExS-6 2 × 10 ^-4 ExC-16 0.05 ExC-2 0.10 ExC-3 0.02 ExY-13 0.07 ExY-15 1.0 Solv-1 0.20 12th layer (high-sensitivity blue-sensitive emulsion layer) ) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, spherical equivalent diameter 1.
0μ, coefficient of variation of equivalent sphere diameter 25%, multiple twinned plate-like particles, diameter / thickness ratio 2.0) Coating silver amount 0.5 Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-15 0.20 ExY-13 0.01 Solv-1 0.10 13th layer (1st protective layer) Gelatin 0.8 UV-4 0.1 UV-5 0.15 Solv-1 0.01 Solv-2 0.01 14th layer (2nd protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, Equivalent sphere diameter 0.07μ) 0.5 Gelatin 0.45 Polymethylmethacrylate particles Diameter 1.5μ 0.2 H-1 0.4 Cpd-5 0.5 Cpd-6 0.5 In addition to the above components in each layer, emulsion stabilizer Cpd-3 (0.0
4 g / m ² ) Surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate Next, in Sample A, the magenta coupler ExM-8 was changed to the following magenta coupler in an equimolar ratio to obtain Samples B, C, and
It was set to D and E.

Sample C M-30 Sample D M-45 Sample E M-61 Next, sample A was imagewise exposed and continuously processed (running test) until the replenishment amount of each color developer was replenished in the following processing steps. Was done. However, the composition of the bleach-fixing solution is the second
Changes were made as shown in the table, and each was performed.

Next, the composition of each treatment liquid will be described.

(Bleach-fixing solution) mother liquor replenisher common aminopolycarboxylic acid iron (III) ammonium 0.3 mol aminopolycarboxylic acid 0.03 mol potassium iodide 2 × 10 ^-3 mol sodium sulfite 12.0 g ammonium thiosulfate aqueous solution (70%) 260.0 ml acetic acid ( 98%) 5.0ml Add water 1.0l pH 6.0 (Stable solution) Common to mother liquor and replenisher 5-chloro-2-methyl-4-isothiazolin-3-one 6.0mg Formalin (37%) 0.5g Polyoxyethylene- p-Monononyl phenyl ether (average degree of polymerization: 10) 0.3 g Ethylenediaminetetraacetic acid disodium salt 0.05 g Water was added to 1.0 l pH 5.0-8.0 In each running equilibrium solution obtained, sample A,
B, C, D and E were processed through a wedge wedge after exposure with 20 CMS. For the Dmax (maximum density part) of the processed light-sensitive material, the amount of residual silver was measured by fluorescent X-ray. Dmin
For the (minimum density part), the magenta density was measured with a Macbeth densitometer, and the magenta density was measured after one week at 80 ° C. The results are shown in Table 2.

In Table 2, when the bleach-fixing treatment is carried out with the aminopolycarboxylic acid iron silver body of the present invention, the desilvering property is remarkably improved, and the magenta coupler of the general formula (II) is used. Good results were obtained with a decrease in post magenta stain increase.

Example 3 In the same manner as in Example 2, except that potassium iodide in the bleach-fixing solution was not added, a running process was carried out until the tank was replenished up to 3 times the dissolved amount in the tank. In the aminopolycarboxylic acid of the present invention, Example 2 was obtained due to elution and accumulation (KI of about 1.7 g / l).
Excellent results were obtained as well.

Example 4 On a subbed cellulose triacetate film support,
Multi-layer color light-sensitive material F was prepared by applying each layer having the following composition in multiple layers.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount in g / m ² unit, and for silver halide, the coating amount in terms of silver.
However, regarding the sensitizing dye, silver halide /
The coating amount per mol is shown in mol.

The coefficient of variation described for the silver iodobromide emulsion is the coefficient of variation relating to the grain size. Further, the dispersion solvent means a high boiling point organic solvent for dispersing the hydrophobic diffusion resistant compound in the same layer.

1st layer (antihalation layer) Black colloidal silver 0.16 Gelatin 1.0 UV absorber UV-1 0.1 UV absorber UV-2 0.1 UV absorber UV-3 0.1 Dispersing solvent Oil-1 0.02 Second layer (intermediate layer) Fine particle odor Silver halide (average grain size 0.07μ) 0.15 Gelatin 1.0 Third layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (6.2 mol% silver iodide, average grain size 0.3)
μ, coefficient of variation 19%) 1.36 Gelatin 0.9 Sensitizing dye S-A 2.0 × 10 ^-4 Sensitizing dye S-B 1.0 × 10 ^-4 Sensitizing dye S-C 0.3 × 10 ^-4 Coupler Cp-1 0.5 Coupler CC -1 0.2 Coupler DIR-1 0.02 Coupler DIR-2 0.01 Dispersing solvent Oil-1 0.1 Dispersing solvent Oil-2 0.1 Fourth layer (second red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 6.3 mol% , Average particle 0.7
μ, variation coefficient 18%) 1.7 Gelatin 1.0 Sensitizing dye S-A 3 × 10 ^-4 Sensitizing dye S-B 1.5 × 10 ^-4 Sensitizing dye S-C 0.45 × 10 ^-4 Coupler Cp-2 0.15 Coupler Cp -3 0.05 Coupler CC-1 0.03 Coupler DIR-1 0.01 Dispersion solvent Oil-2 0.1 Fifth layer (intermediate layer) Gelatin 1.0 Compound Cpd-A 0.05 Dispersion solvent Oil-2 0.01 Sixth layer (first green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 7.2 mol%, average grain 0.3
μ, coefficient of variation 19%) 0.4 Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.5
μ) 0.8 Gelatin 1.0 Sensitizing dye S-D 1 × 10 ^-4 Sensitizing dye S-E 4 × 10 ^-4 Sensitizing dye S-F 1 × 10 ^-4 Coupler Cp-4 0.4 Coupler Cp-5 0.4 Coupler CC -2 0.1 Coupler CC-3 0.05 Coupler DIR-3 0.05 Dispersing solvent Oil-2 0.05 Seventh layer (second green sensitive layer) Polydisperse silver iodobromide emulsion (6.3 mol% silver iodide, average grain size 0.8)
μ, coefficient of variation 15%) 1.14 Gelatin 0.9 Sensitizing dye S-D 0.7 × 10 ^-4 Sensitizing dye S-E 2.8 × 10 ^-4 Sensitizing dye S-F 0.7 × 10 ^-4 Coupler Cp-5 0.15 Coupler CC -2 0.05 Coupler DIR-3 0.01 Dispersing solvent Oil-1 0.08 Dispersing solvent Oil-3 0.03 8th layer (yellow filter layer) Yellow colloidal silver 0.12 Gelatin 0.8 Compound CpdA 0.2 Dispersing solvent Oil-1 0.1 9th layer (1st blue) Emulsion-sensitive layer) Monodispersed silver iodobromide emulsion (4.8 mol% silver iodide, average grain size 0.3)
μ, coefficient of variation 20%) 0.50 Gelatin 2.0 Sensitizing dye S-G 1 × 10 ^-4 Sensitizing dye S-H 1 × 10 ^-4 Coupler Cp-6 0.4 Coupler Cp-7 0.5 Coupler DIR-1 0.05 Dispersion oil Oil -3 0.9 10th layer (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (7.3 mol% silver iodide, average grain size 1.5)
μ, variation coefficient 14%) 0.54 Gelatin 0.5 Sensitizing dye S-G 5 × 10 ^-5 Sensitizing dye S-H 5 × 10 ^-5 Coupler Cp-6 0.1 Coupler Cp-7 0.1 Coupler DIR-1 0.02 Dispersing solvent Oil -3 0.01 11th layer (1st protective layer) Gelatin 0.5 UV absorber UV-1 0.1 UV absorber UV-2 0.1 UV absorber UV-3 0.1 UV absorber UV-4 0.1 Dispersion solvent Oil-4 0.01 12th Layer (second protective layer) Fine grain silver bromide emulsion (average particle size 0.07μ) 0.18 Gelatin 0.5 Polymethylmethacrylate particles (diameter 1.5μ) 0.2 Formaldehyde deactivator Cpd-B 0.5 Others, surfactant W-1, hard Membrane agent H-1 was added.

Similarly to the sample F, samples G, H, and I were prepared in which the coated silver amount was varied as shown in the table below. (Unit is g / m ² ) Samples F, G, H, and I prepared as described above were cut to a width of 35 mm, exposed to 10 CMS, and then exposed to Example 1, No. 1, 2, 8, and 11.
And the amount of residual silver was measured. The results are shown in Table 3.

According to the present invention, the desilvering property of a light-sensitive material having a coated silver amount of 8 g / m ² or less, particularly 7 g / m ² or less is excellent.

Claims (2)

[Claims] 1. After color development, at least one metal complex of aminopolycarboxylic acid represented by the following general formula (I) is contained and 0.3 to 2 mol / l of thiosulfate and 5 × of iodide ion are contained. A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a bleach-fixing solution containing 10 ^{-4 to} 0.05 mol / l. General formula (I) (In the formula, X represents a substituent, n represents 0 or an integer of 1 to 10. M represents a hydrogen atom, an ammonium salt, an alkali metal or an alkaline earth metal. M represents an a-valent polyvalent cation. You may express 1 / a.) 2. The silver halide color photographic light-sensitive material contains at least one pyrazoloazole-based magenta coupler represented by the following general formula (II). A method for processing a silver halide color photographic light-sensitive material as described above. General formula (II) (In the formula, R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developer. Za, Zb and Zc.
Represents methine, substituted methine, = N- or -NH-,
One of the Za-Zb bond and the Zb-Zc bond is a double bond,
The other is a single bond. When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. In addition, R ₁
Alternatively, the case where X forms a dimer or higher multimer is also included.
In addition, when Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or higher multimer. )