JP2660579B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly, to a method in which a used bleach-fix solution is reused as a replenisher during continuous processing to reduce the amount of waste liquid. And a processing method that reduces running costs.

(Prior Art) In a processing method of a silver halide color photographic light-sensitive material, a used processing solution is generally discarded as an overflow solution.

However, these used processing liquids collected and treated as waste liquids have a large pollution load value, which is not preferable in terms of environmental conservation, and the collection and delivery costs for the recovery cannot be ignored. Therefore, if the used processing solution (overflow solution) can be used and reused as a replenisher, the above-mentioned problem can be solved, and the active ingredient remaining in the overflow solution can be reused. As a result, the amount of chemicals used is smaller than in the case where a replenisher is newly prepared, and the cost can be further reduced. Therefore, in order to make it possible to reuse the used processing solution, as a regeneration process, the fluctuation caused during the process is corrected, that is, in general, the accumulated components that affect the photographic performance are removed and consumed. There have been many studies on so-called regeneration techniques, in which the deficient components are added and used again as a replenisher.

Various studies have been made on such a recycling technique for a bleach-fix solution used for processing a color photographic light-sensitive material.

The bleach-fix solution generally contains chemicals having at least three functions: an aminopolycarboxylate (III) complex as a bleaching agent, a thiosulfate as a fixing agent, and a sulfite as a preservative. . The overflow solution of the bleach-fixing solution further contains silver ions generated by the desilvering action and a color developer component brought in from the previous bath. At the same time, iron (II) aminopolycarboxylate produced by oxidizing silver to silver ions is contained.

As mentioned above, regeneration technology generally requires removal of harmful accumulated components and addition of missing components.However, in particular, how to effectively remove accumulated components is a problem. Various reproduction methods have been proposed by removing or reducing silver ions generated by the desilvering action.

The method of contact with metallic iron (steel wool) is Radi
ography 29 , 256-259 (1963), and JP-A-48-3624. In this method, silver ions can be recovered as metallic silver by contact with metallic iron and the silver ion concentration can be reduced, but at the same time, metallic iron is eluted as strongly reducing iron (II) ions, so the oxidation of the bleach-fix solution As the power decreases, the metal iron dissolves as the regeneration is repeated, and the iron ion concentration fluctuates greatly, making stable concentration management difficult. This problem is more likely to occur as the silver ion concentration is reduced.

Further, methods for reducing and recovering silver ions by electrolysis are described in JP-B-53-40491, JP-A-51-19535 and JP-A-51-19535.
No. 36136 and U.S. Pat. No. 4,014,764.
In this case, too, the iron (III) complex is simultaneously
I) Since the solution is reduced to a complex or the sulfite ion is oxidized to a sulfate ion at the anode, the degree of fatigue of the solution becomes remarkable and the stability of the solution decreases. This problem becomes more prominent as the current is increased, the silver recovery is increased, and the silver ion concentration in the bleach-fix solution is reduced.

In addition, a technology for adsorbing and removing a silver complex using an ion exchange resin is disclosed in J. Appl. Photogr. Eng. 6: 14-18 (1980), S.
MPTE J. 93 : 800-807 (1984). However, in this method, it is necessary to release the adsorbed silver complex from the resin and regenerate the resin, so that the operation is complicated, the amount of waste liquid is large, and the running cost is not satisfactory.

As described above, the technology of removing or reducing unnecessary components from the used processing solution and reusing the same is generally difficult in final control of the component ratio or analysis thereof, and the operation is complicated, and the regeneration equipment is large. Disadvantage.

In JP-B-56-33697 and JP-A-50-145231, silver is not actively removed, but if necessary, the amount of equilibrium accumulation of silver ions is relatively reduced by dilution or the like. ,
A technique for regenerating the overflow liquid has been disclosed. This method is a simple and inexpensive method because it can be reused without a special silver recovery device.

(Problems to be Solved by the Invention) However, simply using this method causes a delay in desilvering due to accumulation of silver halide eluted from the light-sensitive material, particularly silver bromide eluted in a large amount and accumulation of sulfate. Further, it has been found that there is a problem in the stability of the running performance because undesired stains are easily generated due to the accumulation of the developing solution components, and poor recoloring is likely to occur.

This is because, especially when the bleach-fix solution is reused, the accumulation of halogen ions and silver ions, the accumulation of iron (II) aminopolycarboxylate, the accumulation of developer components, or the oxidation of sulfite ions. As a result, the accumulation of sulfate and the like occur, and these act in a complicated manner or in unison, resulting in delay in desilvering, leuco-formation of cyan dye (resulting in poor recoloration), deterioration of image storability, especially cyan dye. This is considered to cause thermal discoloration. This is even more pronounced in rapid processing.

Therefore, although it is generally difficult to develop a technique for regenerating the overflow solution, it is particularly difficult to regenerate the bleach-fix solution because the contained or accumulated components interact in a complicated manner.

On the other hand, U.S. Pat.No. 3,615,508 and JP-A-50-140128
The use of ammonium ion as a cation in the bleach-fix solution improves the desilvering performance.
No. 271352 describes that the use of ammonium ion as a cation in a low replenishing amount of a bleach-fix replenisher can prevent the generation of magenta stain. However, in a regenerating system in which a used bleach-fix solution is repeatedly used many times, as described above, the effects of various accumulated components are larger than expected, and in general, the technology relating to the bleach-fix solution cannot be simply applied as it is. Further, in the reproduction system, the above technique does not suggest any solution to the problems of recoloring failure and deterioration of image storability (particularly, thermal fading of a cyan dye), which are new problems.

Accordingly, it is an object of the present invention to provide a silver halide color which is less likely to cause poor recoloring and deterioration in image storability even after repeated use of such a bleach-fix solution (reuse of a used processing solution as a replenisher). An object of the present invention is to provide a method for processing a photographic light-sensitive material.

(Means for Solving the Problems) An object of the present invention is to provide a processing method in which a silver halide color photographic material is subjected to bleach-fixing after color development, followed by washing and / or stabilization. (C) containing at least one cyan coupler represented by formula (C), and adding a regenerating agent to the used bleach-fixing solution used in the bleach-fixing process and reusing it as a regenerating bleach-fixing replenisher;
Further, it has been found that the problem can be solved by a method for processing a silver halide color photographic light-sensitive material, characterized in that at least 80 mol% of cations composed of alkali metal ions and ammonium ions of the regenerant are ammonium ions. .

General formula (C) (In the formula, Ra represents an alkyl group, a cycloalkyl group, an aryl group, an amino group, or a heterocyclic group. Rb represents an acylamino group or an alkyl group having 2 or more carbon atoms. Rc represents a hydrogen atom, a halogen atom, an alkyl group. Rc may be bonded to Rb to form a ring.
Za represents a hydrogen atom, a halogen atom or a group which can be eliminated in the reaction with an oxidized form of an aromatic primary amine color developing agent.

That is, in the present invention, in the processing of a color photographic light-sensitive material, when recycling the used processing solution in the bleach-fixing process, metal ions (sodium ion, potassium ion, etc.) usually used in the bleach-fixing solution are used in the replenisher. It has been found that, when contained in a large amount, the metal ions are remarkably accumulated in the bleach-fix solution as the material is reused and used, which causes unexpected problems (defective recoloring, poor image preservability, etc.) as described above. Based on
Surprisingly, the above problems can be effectively solved by using a replenisher in which the cation in the regenerated bleach replenisher is a specific amount of ammonium ion.

Further, without actively removing or reducing unnecessary accumulated components (for example, silver ions) from the used processing solution (overflow solution), only the deficient components are added as a so-called regenerating agent, and the replenishing solution as a replenishing solution is used. It has been found that even with repeated use, a sufficiently good desilvering property is achieved and the above problem does not occur. Further, it was found that the silver halide color photographic light-sensitive material contains at least one cyan coupler represented by the general formula (C), whereby the above-described color reproducibility and image storability are dramatically improved. .

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof.
These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions are pH buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole agent, a benzothiazole compound or a mercapto compound. If necessary, such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and 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 amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Viscosity imparting agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, 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, N ', N'-tetramethylenephosphonic acid, ethylenediamine Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

However, in the present invention, the color developer preferably does not substantially contain benzyl alcohol. Here, "substantially not containing benzyl alcohol" means that the color developing solution 1
It means that the amount of benzyl alcohol in the medium is 2 ml or less, and it is more preferable that the benzyl alcohol is not contained at all.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes 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 pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 or less per square meter of the light-sensitive material, and the bromide ion concentration and chloride ion concentration in the replenisher should be reduced. To 500 ml or less, and even 150 ml or less. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The photographic emulsion layer of the color developing solution is usually bleached. The bleaching process in the present invention may be performed simultaneously with the fixing process (bleach-fixing process).

Further, in the processing method of bleach-fixing after bleaching, the purpose is to further process in a continuous bleach-fixing bath of two tanks, to perform fixing before bleach-fixing, or to perform bleaching after bleach-fixing. Depending on the color development, bleaching is preferably performed immediately after color development.

Examples of the bleaching agent include iron (III) and cobalt (II
Compounds of polyvalent metals such as I), chromium (VI) and copper (II), and peracids are used. Typical bleaching agents are organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Aminopolycarboxylic acids such as 1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid and malic acid; persulfates and the like can be used. Among these, iron aminopolycarboxylate (II) such as iron (III) complex salt of ethylenediaminetetraacetate and iron (III) complex of diethylenetriaminepentaacetate
I) Complex salts, persulfates and hydrogen peroxide are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, aminopolycarboxylic acid iron (III) complex salts are particularly useful. The pH of the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8. However, in order to speed up the processing, the processing can be carried out at a lower pH. ~ 6.5 is preferred.

A bleaching accelerator can be used in the bleach-fixing solution, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-95630, Research Disclosure No. 17,129 (1978) A compound having a mercapto group or a disulfide bond described in, for example, July); a thiazolidine derivative described in JP-A-50-140129;
Thiourea derivatives described in U.S. Pat. No. 3,706,561; iodide salts described in JP-A-58-16235; West German patent 2,748,430
No. 45-88
Polyamine compounds described in No. 36; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, and
Compounds described in 53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative of the bleach-fixing solution, a sulfite, a bisulfite, a sulfinic acid or a carbonyl bisulfite adduct is preferable.

Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

In the present invention, a used bleach-fix solution (overflow solution) contains a regenerating agent and is reused as a replenisher for regenerated bleach-fix.

The regenerating replenisher is prepared by a method known in the art, such as disclosed in JP-A-48-3624 and U.S. Pat.
No. 313, steel wool method, U.S. Pat.No. 4,014,764
No. 4,036,715, JP-B-53-40491 and JP-A-61-61.
-232452, the electrolysis method described in JP-B-56-33697, or the dilution method described in JP-B-56-33697. May be used as a regeneration replenisher. In particular, a silver ion removing method by an electrolytic method is preferable in that the effect of the present invention is easily achieved, and a method of adjusting a regeneration replenisher simply by adding a regenerating agent without performing a method of removing or reducing silver ions or the like is preferred. It is preferable in terms of simplicity.

The regenerating agent is added to the overflow solution for the purpose of supplementing the components consumed in the bleach-fixing process in principle.

The regenerating agent used in the present invention includes, in principle, bleach-fixing agents and preservatives of the same type as used in the bleach-fixing solution, and further, if necessary, a bleaching accelerator, a rehalogenating agent, a pH buffering agent, and the like. And a small amount of an acid.

In the present invention, particularly in the case of reusing without performing the accumulation removing means, the effect of the accumulation of the developer component due to the carry-in from the previous bath is likely to occur. In the present invention, these effects were unexpectedly suppressed, but in order to further reduce these effects, it is preferable to add a small amount of an acid as a regenerating agent component to the overflow liquid.

As the acid, any of an organic acid and an inorganic acid can be used, and in particular, addition of hydrochloric acid, nitric acid, and acetic acid is preferable for obtaining the effects of the present invention. The addition amount is the regeneration replenisher 1
The amount is preferably 1 g to 30 g, and most preferably, the pH of the regeneration replenisher is adjusted to 4.0 to 6.0 by adding an acid.

For the same reason as described above, the content of the bleaching agent as a regenerating agent component is preferably 0.1 g to 50 g, more preferably 1 g to 30 g per replenisher (overflow liquid).

Similarly, the addition amount of the fixing agent is 2 g to 50 g /, more preferably
It is preferably from 5 g to 30 g /, and the added amount of the preservative is preferably from 5 g to 50 g /, more preferably from 10 g to 30 g /.

In the present invention, in order to increase the amount of ammonium ions as cations present in the bleach-fixing regenerant,
The bleach-fixing regenerant is characterized in that, among the cation components composed of alkali metal ions and ammonium ions, those having an ammonium ion content of 80 mol% or more, preferably 95 to 100 mol%, and most preferably 100 mol% are used. Therefore, it is preferable to use each component of the regenerating agent, for example, an ammonium salt such as a bleaching agent, a bleaching accelerator, a rehalogenating agent, a pH buffer, a fixing agent, a preservative, and the like. It is necessary to adjust so as to be 80 mol% or more of the above. Here, in order to achieve the above ratio, it is particularly preferable to use ammonium iron (III) aminopolycarboxylate, ammonium thiosulfate, ammonium sulfite, ammonium bisulfite, aqueous ammonia or the like.

The regenerant is usually stored in a tank or the like with a used bleach-fix solution (overflow solution), and is added to the overflow solution when a certain amount of the solution is stored, and is adjusted as a replenisher. The overflow liquid can be reused any number of times. If necessary, the accumulated component can be removed using a known method as described above after a certain period of time.

The replenishment rate of these replenisher in the bleach-fixing process, thus the overflow liquid amount, the photosensitive material 1 m ² per 30ml~500m
1, particularly preferably from 60 ml to 250 ml.

Since the effect of the present invention becomes more remarkable as the processing speed increases, the temperature of the bleach-fix processing solution is 20 ° C. to 50 ° C., and further 30 ° C.
~ 40 ° C, treatment time 20 seconds ~ 3 minutes, 30 seconds ~ 1
Minutes.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, a method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131632/1986 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. It is also possible to use bactericides described in "Sterilization, Sterilization and Antifungal Techniques of Microorganisms" edited by the Society of Sanitary Engineers, and "Encyclopedia of Antifungal and Antifungal Agents" edited by the Japan Society of Antifungals and Fungi.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the light-sensitive material, applications, etc., but in the present invention, the temperature is 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 minutes.
A range of 30 seconds to 2 minutes at 4040 ° C. is selected.

Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization treatment, JP-A-57-8543, 58-14834, 60
All known methods described in -220345 can be used.

In some cases, a stabilization process may be performed after the water washing process. For example, the stabilization process is used as a final bath of a color photographic material for photography. Examples include a stabilizing bath containing formalin and a surfactant. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a 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 speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. Salt complexes and urethane compounds described in JP-A-53-135628 can be exemplified.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547, and JP-A-58-144547.
No. 15438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

The method of the present invention can be applied to any processing step using a color developer. For example, it can be applied to processing of color paper, color reversal paper, color positive film, color negative film, color reversal film, color direct positive photosensitive material, and the like. In particular, application to color paper, color reversal paper, and autopositive paper is preferable.

The silver halide emulsion of the light-sensitive material used in the present invention,
Any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride can be used.

When rapid processing or low replenishment processing is performed, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and a silver chloride content of 80 to 100 mol% is more preferable. Particularly preferred. In addition, high sensitivity is required, and at the time of manufacture,
When fogging during storage and / or processing is required to be particularly low, a silver chlorobromide emulsion or a silver bromide emulsion containing 50 mol% or more of silver bromide is preferable, and 70 mol% is more preferable.
The above is preferred. When the amount of silver bromide is 90 mol% or more, rapid processing becomes difficult, but if means for promoting development such as a silver halide solution, a capsera agent, or a means for causing a developing accelerator such as a developer to act during processing is used, Development can be accelerated to some extent without being limited by the content of silver bromide, which is preferable in some cases. In any case, it is not preferable to contain a large amount of silver iodide, and it is sufficient if it is 3 mol% or less. These silver halide emulsions are preferably used mainly for photosensitive materials for printing such as color paper.

Silver bromoiodide and silver chloroiodobromide are preferred for color light-sensitive materials for photography (such as negative films and reversal films), and the silver iodide content is preferably 3 to 15 mol%.

The silver halide grains used in the present invention may have different phases (core / shell grains) in the interior and surface layers, may have a multi-phase structure having a bonding structure, or may consist of a uniform phase throughout the grains. Is also good. They may be mixed.

Average grain size of silver halide grains used in the present invention (in the case of spherical or nearly spherical grains, the grain diameter is used; in the case of cubic grains, the ridge length is used as the grain size, and the average is based on the projected area. Is also expressed in terms of sphere.) Is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm or more. Although the grain size distribution may be narrow or wide, the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size (variation) is within 20%, particularly preferably 15%. % Of the so-called monodispersed silver halide emulsion is preferably used in the present invention. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in an emulsion layer having substantially the same color sensitivity (the monodispersity is defined as (Preferably those having a variation rate) can be mixed in the same layer or multi-layer coated in another layer. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used as a mixture or as a mixture.

The shape of the silver halide grains used in the present invention is regular such as cubic, octahedral, rhombodecahedral, and tetradecahedral.
It may have a crystalline form or coexist with them, may have an irregular crystalline form such as a sphere, or may have a complex form of these crystalline forms. Tabular grains may be used. In particular, an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more, occupy 50% or more of the total projected area of the grains may be used. An emulsion comprising a mixture of these various crystal forms may be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside a grain.

The photographic emulsion used in the present invention can be prepared by the method described in Research Disclosure (RD) vol. 176, Item No. 17643 (I, II, III) (December 1978).

The silver coating amount of the silver halide color photographic light-sensitive material of the present invention is particularly preferably 0.80 g / m ² or less from the viewpoint of the effect of the present invention, and most preferably 0.40 to 0.60 g / m ² .

The emulsion used in the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure Vol. 176, No. 17643 (December 1978) and Vol.
No. 18716 (November 1979), and the relevant locations 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 their locations are shown in the table below.

Various color couplers can be used in the present invention. Here, the color coupler refers to a compound capable of forming a dye by a coupling reaction with an oxidized aromatic primary amine developing agent. Typical examples of useful color couplers include:
There are naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are described in Research Disclosure (RD) 17643 (197
(December 8), and in the patents cited in Section VII-D and 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is diffusion-resistant by being polymerized. A two-equivalent color coupler in which the coupling active position is substituted with a leaving group can reduce the amount of coated silver than a four-equivalent color coupler of a hydrogen atom. Couplers in which the color-forming dye has an appropriate diffusibility, colorless couplers, or DIR couplers which release a development inhibitor or a coupler which releases a development accelerator upon coupling reaction can also be used.

Typical examples of the yellow coupler that can be used in the present invention include oil-protected acylacetamide couplers. Specific examples thereof are described in U.S. Pat.
No. 210, No. 2,875,057 and No. 3,265,506. In the present invention, the use of a two-equivalent yellow coupler is preferred, and U.S. Patent Nos. 3,408,194 and 3,44
7,928, 3,933,501 and 4,022,620, etc., described as oxygen couplers yellow couplers or JP-B-55-10739, U.S. Pat.No. 4,401,752,
No. 326,024, RD18053 (April 1979), UK Patent No. 1,425,
No. 020, West German Application No. 2,219,917, No. 2,261,361
Nos. 2,329,587 and 2,261,361, 2,32
A typical example is a nitrogen atom-elimination type yellow coupler described in JP-A-9,587 and JP-A-2,433,812. α-pivaloylacetanilide-based couplers are excellent in the fastness of color-forming dyes, especially in light fastness.
Benzoylacetanilide-based couplers provide high color density.

Examples of magenta couplers that can be used in the present invention include oil-protected, indazolone-based or cyanoacetyl-based, preferably 5-pyrazolone-based and pyrazoloazole-based couplers such as pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamine group or an acylamino group, from the viewpoint of the hue and color density of the coloring dye. Representative examples thereof are U.S. Patent 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 coupler, a nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or an arylthio group described in U.S. Pat. No. 4,351,897 is preferable. Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 can obtain a high color density.

Pyrazoloazole-based couplers include U.S. Pat.
Pyrazolobenzimidazoles described in US Pat. No. 369,879, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure 24220 (June 1984). Pyrazolotetrazole described and Research Disclosure 24
230 (June 1984). The imidazo [1,2-b] pyrazoles described in EP 119,741 are preferred from the viewpoint of low yellow side absorption and light fastness of the coloring dye, and EP 119,8
Pyrazolo [1,5-b] [1,2,4] triazole described in No. 60 is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol couplers and phenol couplers, and naphthol couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212 and 4,146,396, Nos. 4,228,233 and 4,296,200
The representative examples are the oxygen-equivalent double-equivalent naphthol couplers described in the above publication. Specific examples of phenol couplers are described in U.S. Pat.Nos. 2,369,929 and 2,80
Nos. 1,171, 2,772,162, and 2,895,826. Cyan couplers which are robust to humidity and temperature are preferably used in the present invention, and typical examples thereof include phenols having an alkyl group at the meta-position of the phenol nucleus or higher, as described in U.S. Pat.No. 3,772,002. Cyan coupler, U.S. Pat.Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729 and JP-A-59-166956, and 2,5-diacylamino-substituted phenolic couplers described in U.S. Pat.
No. 2, No. 4,333,999, No. 4,451,559 and No. 4,4
And phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and the like. Furthermore, it has been found that when the cyan coupler in the light-sensitive material to be processed in the present invention is represented by the following general formula (C), the effect of the present invention is further improved. In particular, it has been found that there is a remarkable effect on the thermal fading property of the cyan dye formed in such a reproducing method.

 The general formula (C) will be described in detail below.

General formula (C) (In the formula, Ra represents an alkyl group, a cycloalkyl group, an aryl group, an amino group, or a heterocyclic group. Rb represents an acylamino group or an alkyl group having 2 or more carbon atoms. Rc represents a hydrogen atom, a halogen atom, an alkyl group. Rc may be bonded to Rb to form a ring, and Za is eliminable in the reaction with a hydrogen atom, a halogen atom or an oxidized form of an aromatic primary amine color developing agent. In formula (C), the alkyl group represented by Ra is preferably an alkyl group having 1 to 32 carbon atoms, such as a methyl group, a butyl group, a tridecyl group, a cyclohexyl group, and an allyl group. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a 2-pyridyl group and a 2-furyl group.

When Ra is an amino group, a phenyl-substituted amino group which may have a substituent is particularly preferable.

Ra further represents an alkyl group, an aryl group, an alkyl or aryloxy group (for example, methoxy group, dodecyloxy group, methoxyethoxy group, phenyloxy group, 2,4
-Di-tert-amylphenoxy group, 3-tert-butyl-
4-hydroxyphenyloxy group, naphthyloxy group, etc.), carboxy group, alkyl group or arylcarbonyl group (eg, acetyl group, tetradecanoyl group, benzoyl group, etc.), alkyl or aryloxycarbonyl group (eg, methoxycarbonyl group) Phenoxycarbonyl group), acyloxy group (eg, acetyl group, benzoyloxy group, etc.), sulfamoyl group (eg, N-ethylsulfamoyl group, N-octadecylsulfamoyl group, etc.), carbamoyl group (eg, N -Ethylcarbamoyl group, N-methyl-dodecylcarbamoyl group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), acylamino group (eg, acetylamino group, benzamide group, ethoxy Ruboniruamino group, phenylaminocarbonyl amino group), an imido group (e.g.,
It may be substituted with a substituent selected from a succinimide group, a hydantoinyl group, a sulfonyl group (eg, a methanesulfonyl group), a hydroxy group, a cyano group, a nitro group, and a halogen atom.

In the general formula (C), Za represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), and an alkoxy group (for example, a dodecyloxy group, Methoxycarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (eg, 4-chlorophenoxy group, 4-methoxyphenoxy group, etc.), acyloxy group (eg, acetoxy group, tetradecanoyloxy group) , Benzoyloxy group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (eg, dichloroacetylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group Si group (eg, ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group, etc.), aliphatic or aromatic thio group (eg, phenylthio group, tetrazolylthio group, etc.) , An imide group (eg, succinimide group, hydantoinyl group, etc.), an N-heterocycle (eg, 1-pyrazolyl group, 1-benzotriazolyl group, etc.), an aromatic azo group (eg, phenylazo group, etc.). . These leaving groups may include photographically useful groups.

Ra or Rb of the general formula (C) may form a dimer or a multimer thereof.

Specific examples of the cyan coupler represented by the general formula (C) are shown below, but the present invention is not limited thereto.

The cyan coupler represented by the general formula (C) can be synthesized based on the description in JP-A-59-16669, JP-B-49-11572 and the like.

The content of the present cyan coupler is not particularly limited, but is preferably 1 × 10 ^-4 to 1 × 10 ^-2 mol, more preferably 1 × 10 ^-5 to 1 × 10 ^-3 mol, per m ² of the light-sensitive material. .

In the present invention, the granularity can also be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusing couplers are described in U.S. Pat.No. 4,366,237 and British Patent No. 2,125,570 as specific examples of magenta couplers, and European Patent No. 96,570 and West German Application Publication No.
No. 3,234,533 describes specific examples of yellow, magenta or cyan couplers.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,282.

Various couplers used in the present invention can be used in combination of two or more in the same layer of the photosensitive layer, or different two or more layers of the same compound in order to satisfy the characteristics required for the photosensitive material. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Further, the steps and effects of the latex dispersion method as one of the polymer dispersion methods and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) No. 2,541,274.
No. 2,541,230, etc., a dispersion method using an organic solvent-soluble polymer is described in the specification of PCT Application No. JP87 / 00492.

Examples of the organic solvent used in the above-described oil-in-water dispersion method include alkyl phthalates (such as dibutyl phthalate and dioctyl phthalate) and phosphates (such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctyl butyl phosphate). Fate), citrate (eg, acetyl tributyl citrate), benzoate (eg, octyl benzoate), alkyl amide (eg, diethyl lauryl amide), fatty acid esters (eg, dibutoxyethyl succinate, diethyl azelate), trimesine Acid esters (eg, tributyl trimesate) and the like, or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, ethyl acetate;
A lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate and the like may be used in combination.

Typical amounts of color coupler used range from 0.001 to 1 mole per mole of photosensitive silver halide,
Preferably 0.01 to 0.5 mol for a yellow coupler,
The amount is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

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

In the present invention, a reflective support is preferably used. "Reflective support" enhances reflectivity to sharpen a dye image formed in a silver halide emulsion layer. Such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as calcium carbonate and calcium sulfate, and those coated with a hydrophobic resin dispersedly containing a light reflecting substance as a support.

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

Example 1 A multilayer color photographic paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY), color image stabilizer (Cpd-
1) Ethyl acetate 2 in 4.4 g and 0.7 g of color image stabilizer (Cpd-7)
7.2 cc and a solvent (Solv-1) 8.2 g were added and dissolved, and this solution was added with 10% sodium dodecylbenzenesulfonate 8 cc.
Was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (average grain ratio) of 0.88 μm and 0.70 μm) (silver molar ratio) The coefficient of variation of the particle size distribution is 0.08 and 0.10, and each emulsion is silver bromide
The following blue-sensitive sensitizing dyes are added to the large-sized emulsion in an amount of 2.0 × 10 ⁻⁴ mol per mol of silver, and the small-sized emulsion is added to the small-sized emulsion. , Each of which was subjected to sulfur sensitization after addition of 2.5 × 10 ^-4 mol. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

Blue-sensitive emulsion layer (Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, and each for small-size emulsion
2.5 × 10 ^-4 mol) Green-sensitive emulsion layer (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mol) Red-sensitive emulsion layer (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 mol, respectively, per mol of silver halide. ×
10 ^-4 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating layer (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent ( Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm average and 0.39 μm emulsion (Ag mole) The coefficient of variation of the grain size distribution is 0.10 and 0.08, and each emulsion has AgBr0.
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv) -5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 µm and 0.45 µm in average grain size, Ag molar ratio) Variation in grain size distribution The coefficients are 0.09 and 0.11, AgBr0 for each emulsion.
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree
17%) 0.17 Liquid paraffin 0.03 (ExY) yellow coupler 1: 1 mixture (molar ratio) with (ExM) magenta coupler 1: 1 mixture (molar ratio) with (ExC) cyan coupler 2: 4: 4 mixture by weight of each (Cpd-1) color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixing inhibitor (Cpd-6) color image stabilizer 2: 4: 4 mixture (weight ratio) (Cpd-7) color image stabilizer (Cpd-8) Color image stabilizer (Cpd-9) Color image stabilizer (UV-1) UV absorber 4: 2: 4 mixture (weight ratio) (Solv-1) solvent (Solv-2) solvent 2: 1 mixture (volume ratio) with (Solv-4) solvent (Solv-5) solvent (Solv-6) solvent First, the sample was given an imagewise exposure. The exposed sample was subjected to continuous processing (running test) using a paper processor.

Bleach quantitative solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Iron (III) ethylenediaminetetraacetate 60g Disodium ethylenediaminetetraacetate 5g Add water 1000ml pH (25 ℃) 5.40 Rinse solution (tank solution and replenisher are the same) Ion exchange water (Calcium and magnesium are 3ppm each)
The bleach-fix solution used for the overflow solution was used as a replenisher by adding a regenerating agent having the following formulation at the time when the tank capacity was doubled (34). However, the following five types of regenerants A to E having different ammonium ion mol% were used. All the formulations were indicated by the amount added per overflow liquid.

Regenerating agent A: 55% ammonium ion sodium thiosulfate (anhydrous) 20 g Ammonium sulfite 10 g Iron (III) ammonium ethylenediaminetetraacetate · 2H ₂ O 15 g Ethylenediaminetetraacetic acid 2 g Add glacial acetic acid to pH 5.40 Regenerating agent B: Ammonium regenerant and the ion 63% ammonium thiosulfate (70W / V%) 27ml sodium sulfite 10.9g ethylenediaminetetraacetic acid iron (III) ammonium · 2H ₂ O 15 g ethylenediamine pH5.40 added tetraacetate 2g glacial acetic acid C: ammonium ions 80 % Ammonium thiosulfate (70 W / V% 27 ml Ammonium sulfite 4.6 g Sodium sulfite 5.8 g Ammonium iron (III) ethylenediaminetetraacetate ・ 2H ₂ O 15 g Ethylenediaminetetraacetic acid 2 g Add glacial acetic acid to pH 5.40 Regenerant D: ammonium ion 92% Ammonium thiosulfate (70W / V%) 27ml Ammonium sulfite 10g Ethylene dia Emissions tetraacetate iron (III) sodium · 2H ₂ O15g ethylenediaminetetraacetate 2g glacial acetic acid is added pH5.40 to regenerant E: Ammonium ions 100% Ammonium thiosulfate (70W / V%) 27ml ammonium sulfite 10g Ethylenediaminetetraacetic acid iron (III) Ammonium ・ 2H ₂ O1
5 g of ethylenediaminetetraacetic acid and 2 g of glacial acetic acid were added to adjust the pH to 5.40. When the above-mentioned regenerating operation was repeated 20 times, the photosensitive material was subjected to wedge-shaped exposure and processed.

After measuring the processed photosensitive material,
It was immersed in Fuji Film Co., Ltd. CN-16N ₂ (bleach solution) at 25 ° C. for 4 minutes and the density was measured again. The density before the reprocessing at the point where the cyan density reached 2.2 was indicated by the color development rate.

Further, after the processed photographic material was aged at 80 ° C. for 2 months, the density decrease (light fading) at the point of cyan density 2.0 was measured.

 The results are shown in Table 1.

According to the present invention, both poor color reproduction and fading of cyan are improved. In particular, 90% or more of ammonium ion is preferable.

Furthermore, it was found that the above values hardly changed even if the reproduction operation was repeated 30 times and 40 times. This is presumably because the composition of the regeneration replenisher is almost in equilibrium.

Example 2 Samples 1 to 6 were prepared in the same manner as in the light-sensitive material of Example 1 except that the cyan coupler was changed in an equimolar amount as shown below.
It was created.

Sample 1 (same as in Example 1) (Mixing ratio of 2: 4: 4 by weight) Sample 2 Compound of the above (C-1) Sample 3 And the compound of (C-9) (1: 1 by weight) Sample 4 And the compound of the above (C-10) (1: 1 by weight ratio) Sample 5 Sample 6 Each of the samples obtained as described above was treated with the running liquids of the regeneration formulations B and E of Example 1 after the wedge-shaped exposure, respectively, and the cyan coloring ratio and cyan fading were measured in the same manner.
The results are shown in Table 2.

The use of the regenerating prescription E of the present invention significantly improves the cyan coloring ratio (defective recoloring) and cyan fading (Nos. 7 to 1).
2). Particularly when the preferred cyan coupler represented by the general formula (C) is used, better results are obtained. (N
o.7,8,9,10).

Example 3 A multilayer color photographic paper (sample 7) having the following layer constitution was produced on a paper support having both surfaces laminated with polyethylene and the surface thereof subjected to a corona discharge treatment. The coating solution was prepared as follows.

Preparation of first layer coating solution 60.0 g of yellow coupler (ExY) and anti-fading agent (Cp
d-1) In 28.0 g, 150 cc of ethyl acetate and a solvent (Solv-
3) Add 1.0 cc and 3.0 cc of a solvent (Solv-4) to dissolve the solution, and add this solution containing sodium dodecylbenzenesulfonate to 10
% Gelatin aqueous solution, and dispersed with an ultrasonic homogenizer. The resulting dispersion was treated with 420 g of a silver chlorobromide emulsion (0.7 mol% of silver bromide) containing the following blue-sensitive sensitizing dye.
To prepare a first layer coating solution.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1,2-
Bis (vinylsulfonyl) ethane was used.

The following were used as spectral sensitizing dyes for each layer.

Blue-sensitive emulsion layer; anhydro-5,5'-dichloro-3,3'-
Disulfoethyl thiacyanine hydroxide Green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide Red-sensitive emulsion layer; 3,3'-diethyl- 5-methoxy-9,11-
Neopentylthiadicarbocyanine iodide The followings were used as stabilizers for each emulsion layer.

Further, the following substances were used as the irradiation preventing dye.

[3-carboxy-5-hydroxy-4- (3- (3-
Carboxy-5-oxo-1- (2,5-bisulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl] benzene-2,5-disulfonate-disodium salt N, N '-(4,8-dihydroxy-9,10-dioxo-3,7-
Disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt [3-cyano-5-hydroxy-4- (3- (3-cyano-5-oxo-1- (4 -Sulfonatophenyl)-
2-pyrazolin-4-ylidene) -1-bentanyl)-
[1-Pyrazolyl] benzene-4-sulfonate-sodium salt (layer constitution) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Paper support laminated on both sides with polyethylene and corona discharge treated on the surface First layer (blue-sensitive layer) Silver chlorobromide emulsion (AgBr 0.7 mol%, cubic, average particle size 0.9 μm) 0.29 Gelatin 1.80 Yellow coupler (ExY) 0.60 Anti-fading agent (Cpd-1) 0.28 Solvent (Solv-3) 0.01 Solvent (Solv-4) 0.03 Second layer (color mixture prevention layer) Gelatin 0.80 Color mixture inhibitor (Cpd-2) 0.055 Solvent ( Solv-1) 0.03 Solvent (Solv-2) 0.15 Third layer (green sensitive layer) Silver chlorobromide emulsion described above (AgBr 0.7 mol%, cubic, average particle size 0.45 μm) 0.25 Gelatin 1.86 Magenta coupler (ExM) 0.27 Anti-fading agent (Cpd-3) 0.17 Anti-fading agent (Cpd-4) 0.10 Solvent (Solv-1) 0.2 Solvent (Solv-2) 0.03 Fourth layer (color mixture prevention layer) Gelatin 1.70 Color mixture inhibitor (Cpd-2) ) 0.065 UV absorber (UV-1) 0.45 UV absorber (UV-2) 0.23 Solvent Solv-1) 0.05 Solvent (Solv-2) 0.05 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion described above (AgBr 4 mol%, cubic, average particle size 0.5 μm) 0.25 Gelatin 1.80 Cyan coupler (ExC-1) 0.26 Cyan coupler (ExC-2) 0.12 Anti-fading agent (Cpd-1) 0.20 Solvent (Solv-1) 0.16 Solvent (Solv-2) 0.09 Color development accelerator (Cpd-5) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.70 UV absorber (UV-1) 0.26 UV absorber (UV-2) 0.07 Solvent (Solv-1) 0.30 Solvent (Solv-2) 0.09 Seventh layer (protective layer) Gelatin 1.07 (Cpd-1) Anti-fading agent (Cpd-2) Color-mixing inhibitor 2,5-di-tert-octylhydroquinone (Cpd-3) Anti-fading agent 7,7'-dihydroxy-4,4,4 ', 4'-tetramethyl-2,
2'-spirochroman (Cpd-4) anti-fading agent N- (4-dodecyloxyphenyl) -morpholine (Cpd-5) color-developing agent p- (p-toluenesulfonamido) phenyl-dodecane (Solv-1) solvent di (2-ethylhexyl) phthalate (Solv-2) solvent dibutyl phthalate (Solv-3) solvent di (i-nonyl) phthalate (Solv-4) solvent N, N-diethylcarbonamide-methoxy-2,4-di-t
-Amylbenzene (UV-1) UV absorber 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole (UV-2) UV absorber 2- (2-hydroxy-3,5-) Di-tert-butylphenyl) benzotriazole (ExY) yellow coupler (ExM) Magenta coupler (ExC) Cyan coupler After the imagewise exposure of the sample 7, the continuous processing was performed in the following processing steps.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Glacial acetic acid 9g Add water 1000ml pH (25 ℃) 5.40 Stabilizer (tank solution and replenisher are the same) 1-hydroxyethylidene-1,1-diphosphonic acid (60wt
%) 1.5 g Nitrilotrimethylene phosphonic acid (40 wt%) 1.5 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.01 g Fluorescent brightener 0.5 g Ammonia Water (28%) 1.5 ml water was added and 1000 ml pH (25 ° C.) 7.0 The bleach-fixer was regenerated by the following method. That is, when the overflow liquid has accumulated 10
After recovering a certain amount of silver using the electrolytic silver recovery apparatus shown in FIGS. 1 and 2 of No. 491, each of the following regenerating agents F and G was added and used as a replenisher for regeneration. Each overflow was collected and the regeneration was repeated.

Regenerant F: (indicated by the amount added per overflow solution) Ammonium thiosulfate (70% w / v) 15 ml Sodium sulfite 12 g Iron (III) ethylenediaminetetraacetate · 2H ₂ O 12 g Ethylenediaminetetraacetic acid 2 g Add glacial acetic acid pH 5.40 (ammonium ion 48%) Regenerant G: (indicated by the amount added per overflow solution) Ammonium thiosulfate (70% w / v) 15 ml ammonium sulfite 11.0 g iron (III) ammonium ethylenediaminetetraacetate · 2H ₂ O 12 g Ethylene diamitetraacetic acid 2 g Glacial acetic acid was added to adjust the pH to 5.40 (ammonium ion 100%) Silver recovery was performed by operating both electrolytic silver recovery devices at a voltage between both electrodes of 20 V and a flow rate of 200 ml / hr. did.

When the above reproduction was performed 20 times, the sample was subjected to wedge-shaped exposure, and the color development rate of cyan and the fading of cyan were evaluated in the same manner as in Example 1. The results are shown in Table 3.

According to the present invention, the cyan coloring ratio and cyan fading are improved.

(Effects of the Invention) According to the present invention, even if the bleach-fix solution is reused (the used processing solution is reused as a replenisher) and processed repeatedly, poor recoloring and deterioration of image storability do not easily occur. Thus, a silver halide color photographic light-sensitive material having excellent image quality can be obtained.

Claims (1)

(57) [Claims] 1. A processing method in which a silver halide color photographic light-sensitive material is subjected to bleach-fixing after color development, followed by washing and / or stabilization, wherein the light-sensitive material is represented by the following general formula (C): Wherein the bleach-fixing solution used in the bleach-fixing process contains a regenerating agent and is reused as a regenerated bleach-fixing replenisher;
And a method for processing a silver halide color photographic light-sensitive material, wherein 80 mol% or more of cations comprising alkali metal ions and ammonium ions of the regenerant are ammonium ions. General formula (C) (In the formula, Ra represents an alkyl group, a cycloalkyl group, an aryl group, an amino group, or a heterocyclic group. Rb represents an acylamino group or an alkyl group having 2 or more carbon atoms. Rc represents a hydrogen atom, a halogen atom, or an alkyl group. Rc may be bonded to Rb to form a ring.
Za represents a hydrogen atom, a halogen atom or a group which can be eliminated in the reaction with an oxidized form of an aromatic primary amine color developing agent. )