JPH06242573A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To remarkably improve recoloring in spite of a rapid treatment, to remarkably prevent the thermal fading of a pigment and to prevent a color staining by treating the silver halide photographic sensitive material containing a specified cyan coupler in the bath containing the iron complex of a specified compd. and having bleaching property after color developing. CONSTITUTION:The silver halide color photographic sensitive material containing the cyan coupler expressed by formula I is color developed, then treated in the bath containing iron (tervalent) complex expressed by formula II and having bleaching property. In the formula I and II, Ra, is alkyl, cycloalkyl group, etc., R15 is acylamino group or the alkyl group having >=2C, Rc is hydrogen atom, halogen atom, etc., Za is hydrogen atom, halogen atom or the group which is climinated by the reaction with the oxide of an arom. prim. amine color developing agent, each of R1, R2, R3, R5, R6 and Re is hydrogen atom, aliphat. group, etc., W is a connecting group, each of M1, M2, M3 and M4 is hydrogen atom or a cation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular, recoloring is remarkably improved in spite of rapid processing, thermal fading of dye is remarkably prevented, and color contamination is caused. The present invention relates to a processing method in which is prevented.

[0002]

2. Description of the Related Art A color developing solution containing an aromatic primary amine color developing agent has been conventionally used for forming a color image, and now plays a central role in a color photographic image forming method. . However, the color developer has a problem that it is very easily oxidized by air or metal, and when a color image is formed using the oxidized developer, fog is increased and sensitivity and gradation are changed. It is well known that the desired photographic characteristics cannot be obtained because of the above. In particular, with the recent reduction in processing time, the change in photographic characteristics during continuous processing tends to be large, and in some cases a serious problem of color contamination may occur. Such problems are likely to occur especially when the desilvering process, the water washing process, etc. are shortened.

There are many possible causes of such changes in photographic characteristics and color contamination during continuous processing.
For example, A. The color developer deteriorates with time, the photographic characteristics fluctuate, and the oxide of the main agent adheres to the photosensitive material to cause color contamination. B. The color developing agent is brought into a bleaching solution or a bleach-fixing solution and is oxidized, causing fog or contamination. C. Light-sensitive material eluate accumulates in the color developer, which adheres to the light-sensitive material to cause color contamination. D. The dye or sensitizing dye contained in the photosensitive material was insufficiently washed out, and the photosensitive material was colored. E. The liquid used in the desilvering process and the subsequent stabilizing process deteriorates over time, causing color contamination. F. After processing, the bleaching agent remains on the light-sensitive material to cause color contamination. Among these, particularly for E and F, in order to improve color contamination, it depends largely on the kind of the bleaching agent, the stability of the rinse solution is improved, and even if the bleaching component remains, fog over time, etc. It is necessary not to be a cause of, and naturally, it will largely depend on the type of coupler used.

On the other hand, in recent years, there has been a strong demand in the industry for speeding up the processing, that is, for shortening the time required for the processing, and particularly for shortening the processing time of the desilvering process which accounts for almost half of the processing time. It has become a challenge. Among the desilvering processes, the bleaching process not only oxidizes silver, but also includes a so-called color restoration process in which a leuco ion dye is oxidized to form a cyan dye, but when the bleaching time is shortened, oxidation is sufficiently performed. This is not possible and causes a so-called color recovery failure, which causes a decrease in the maximum cyan density, and a solution to that problem is desired. Therefore, as a method of increasing the bleaching power, a method of adding various bleaching accelerators to a bleaching bath, a bleach-fixing bath or a prebath thereof has been proposed. As such a bleaching accelerator,
For example, ammonium bromide described in JP-A-51-87036, water-soluble iodide described in British Patent No. 926,569, and halide described in JP-B-53-11854 are known.

Further, in a bleaching solution or a bleach-fixing solution using an EDTA iron complex salt, when the bleaching process is carried out immediately after the step of containing a reducing agent such as a color developing solution, the reducing agent is bleached depending on the light-sensitive material. However, there is a problem that a cyan color recoloring failure is particularly likely to occur, and it is desired to solve such a problem. On the other hand, as a cyan coupler that suppresses fading, for example, Japanese Patent Publication No. Sho 49-11572.
And couplers described in JP-A-59-166956 and the like are known, and those which are expected to have an effect of improving the color-recovery property are included therein, but the effect is not sufficient. Not.

[0006]

However, even if the above-mentioned techniques are used alone, the problems of color contamination, thermal fading or color reversion can be solved to some extent, but still not sufficient effect. Not obtained. Accordingly, the present invention provides:
It is an object of the present invention to provide a processing method of a silver halide color photographic light-sensitive material which is remarkably improved. It is an object of the present invention to provide a method of processing a silver halide color photographic light-sensitive material which gives the above-mentioned improved effects by using a solution containing a bleaching agent which has an excellent effect in the above-mentioned processing. Is.

[0007]

Means for Solving the Problems The present inventor has conducted various studies on compounds used for bleaching agents, and has found that among the compounds that have never been used in the field of photography, they were excellent as bleaching agents. The substance which gives the effect was found, and on the basis of it, the processing method of the silver halide color photographic light-sensitive material which gave the excellent effect on the color contamination was completed. That is, the present invention has achieved the above object by the following means. (1) An iron (trivalent) complex of a compound represented by the following general formula (II) after color development of a silver halide color photographic light-sensitive material containing at least one cyan coupler represented by the following general formula (I). A method for processing a silver halide color photographic light-sensitive material, comprising processing in a bath having at least one of the above and having a bleaching ability. General formula (I)

[0008]

[Chemical 3]

(In the formula, R _a represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group.
_b represents an acylamino group or an alkyl group having 2 or more carbon atoms. R _c represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R _c may combine with R _b to form a ring. Z _a represents a hydrogen atom, a halogen atom, or a group capable of leaving in the reaction with an oxidized product of an aromatic primary amine color developing agent. ) General formula (II)

[0010]

[Chemical 4]

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group. W represents the following general formula (W). M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation General formula (W)-(W ₁ -Z) _n -W ₂ -General formula (W ), W ₁ represents an alkylene group or a single bond, W ₂ represents an alkylene group or —CO—, Z is a single bond, —O—, —S—, —CO—, or —N (R _w ).
-(R _w represents a hydrogen atom or an alkyl group which may be substituted). However, Z and W ₁ are not a single bond at the same time. n represents an integer of 1 to 3. (2) The silver halide color photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (II) has an optical isomer mainly composed of an [S, S] body. Processing method. (3) The silver halide color photographic light-sensitive material as described in the above item (1) or (2), wherein the processing time in the bath having the bleaching ability is 15 to 60 seconds. Processing method. (4) Any one of the above items (1) to (3), characterized in that the time of the washing and / or stabilizing step after the treatment in the bath having the bleaching ability is 10 seconds to 2 minutes. 2. A method for processing a silver halide color photographic light-sensitive material according to item 1.

According to the present invention, the silver halide color photographic light-sensitive material containing at least one cyan coupler represented by the above-mentioned general formula (I) is used as an iron compound of the compound represented by the above-mentioned general formula (II) ( By combining the (trivalent) complex so as to be treated in a bath having a bleaching ability containing at least one kind, it is possible to obtain remarkably excellent effects in each of color stain, thermal fading and recolorability. Hereinafter, the present invention will be described in more detail. First, general formula (I)
Regarding the cyan coupler represented by, the structural formula of the general formula and the definition of each group are as described above, and the general formula (I) will be described in detail. In the general formula (I), the alkyl group of R _a, preferably an alkyl group having 1 to 32 carbon atoms, such as methyl, butyl, tridecyl, cyclohexyl, an allyl group, and an aryl group Examples of the heterocyclic group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a 2-pyridyl group. When R _a is an amino group, a phenyl-substituted amino group which may have a substituent is particularly preferable.

R _a is an alkyl group, an aryl group,
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 Groups, etc.), carboxy groups, alkyl or arylcarbonyl groups (eg, methoxycarbonyl groups, phenoxycarbonyl groups, etc.), acyloxy groups (eg, acetyl groups, benzoyloxy groups, etc.), sulfamoyl groups (eg, N-ethylsulfamoyl). Group, N-octadecylsulfamoyl group, etc.),
A carbamoyl group (for example, an N-ethylcarbamoyl group,
N-methyl-dodecylcarbamoyl group etc.), sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group etc.), acylamino group (eg acetylamino group, benzamide group, ethoxycarbonylamino group, phenylaminocarbonylamino group) Such),
It may be substituted with a substituent selected from an imide group (eg, succinimide group, dantoynyl group, etc.), a sulfonyl group (eg, methanesulfonyl group, etc.), a hydroxy group, a cyano group, a nitro group and a halogen atom.

In the general formula (I), Z _a represents a hydrogen atom, a halogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. The halogen atom and the removable group are collectively referred to as a coupling leaving group. Examples thereof include halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (eg, dodecyloxy group, methoxycarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy Group (for example, 4-chlorophenoxy group, 4-methoxyphenoxy group, etc.), acyloxy group (for example, 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 (eg, ethoxycarbonyloxy group) Group, benzyloxycarbonyloxy group etc.), aryloxycarbonyloxy group (eg phenoxycarbonyloxy group etc.), aliphatic or aromatic thio group (eg phenylthio group, tetrazolylthio etc.), imide group (eg succinimide group, Hydantoyl group), N-heterocycle (eg, 1-pyrazolyl group, 1-benztriazolyl group, etc.), and aromatic azo group (eg, phenylazo group). These leaving groups may include photographically useful groups.

In the general formula (I), R _b represents an acylamino group or an alkyl group having 2 or more carbon atoms (eg, ethyl group, propyl group, tert-butyl group).
R _c is a hydrogen atom, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, etc.) or an alkoxy group (eg, methoxy group, ethoxy group). Group). R _c may combine with R _b to form a ring.
Next, specific examples of the cyan coupler represented by the general formula (I) are shown, but the cyan coupler is not limited thereto.

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

The cyan coupler represented by the above general formula (I) is disclosed in JP-A-59-166956 and JP-B-49-11.
It can be synthesized based on the method described in No. 572 or the like. The content of the cyan coupler is not particularly limited, but preferably 1 × 10 ^-6 to 1 per 1 m ² of the light-sensitive material.
× 10 ^-2 mol, more preferably ^{1x10 -5} to ^{1x10 -3}
It is a mole.

Next, in the treatment method of the present invention, the compound represented by the general formula (II) is used as an iron (trivalent) complex in a bath having a bleaching ability.
The compound represented by will be described. This compound is one of the features of the present invention. The compound represented by the general formula (II) will be described in more detail. R ₁ , R ₂ ,
The aliphatic group represented by R ₃ , R ₄ , R ₅ and R ₆ is a straight chain,
It is a branched or cyclic alkyl group, alkenyl group or alkynyl group, preferably having 1 to 10 carbon atoms. The aliphatic group is more preferably an alkyl group, further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. R ₁ , R ₂ , R ₃ ,
The aromatic group represented by R ₄ , R ₅ and R ₆ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is more preferable.

The aliphatic group and aromatic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may have a substituent, for example, an alkyl group (eg methyl, ethyl). ), Aralkyl groups (eg phenylmethyl), alkenyl groups (eg allyl), alkynyl groups, alkoxy groups (eg methoxy, ethoxy), aryl groups (eg phenyl, p).
-Methylphenyl), amino group (eg dimethylamino), acylamino group (eg acetylamino), sulfonylamino group (eg methanesulfonylamino), ureido group, urethane group, aryloxy group (eg phenyloxy), sulfamoyl (eg methyl Sulfamoyl), carbamoyl group (eg carbamoyl, methylcarbamoyl), alkylthio group (eg methylthio), arylthio group (eg phenylthio), sulfonyl group (eg methanesulfonyl), sulfinyl group (eg methanesulfinyl), hydroxy group, halogen atom (Eg chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group (eg phenyloxycarbonyl), acyl group (eg Cetyl, benzoyl), an alkoxycarbonyl group (eg methoxycarbonyl), an acyloxy group (eg acetoxy), a carbonamido group, a sulfonamide group, a nitro group, a hydroxamic acid group and the like, and if possible, a dissociation product or salt thereof. May be When the above substituent has a carbon atom, it preferably has 1 to 4 carbon atoms. R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ and R ₆ are preferably a hydrogen atom or a hydroxy group, more preferably a hydrogen atom.

The linking group represented by W is represented by the following general formula (W). Formula _{(W) - (W 1 -Z} ) n -W 2 - W 1 represents an alkyl group or a single bond. The alkylene group represented by W ₁ is preferably a linear or branched alkylene group having 1 to 8 carbon atoms (for example, a methylene group, an ethylene group,
A propylene group) and a cycloalkylene group having 5 to 10 carbon atoms (for example, a 1,2-cyclohexylene group). W ₂ represents an alkylene group or -CO-. The alkylene group represented by W ₂ has the same meaning as the alkylene group represented by W ₁ .
The alkylene groups represented by W ₁ and W ₂ may be the same or different from each other, or may have a substituent.
As the substituent, those mentioned as the substituent for R ₁ are applicable, but an alkyl group, a hydroxy group or a carboxy group is preferable. W ₁ and W ₂ are more preferably an alkylene group having 1 to 3 carbon atoms, and a methylene group or an ethylene group is particularly preferable. Z is a single bond, -O-, -S-,
_{-CO -, - N (R W} ) - represents a. R _W represents a hydrogen atom or an optionally substituted alkyl group. R as a substituent
_Although those mentioned as the substituent of ₁ can be applied, it is preferably a carboxy group, a phosphono group, a sulfo group, a hydroxy group or an amino group. Z is preferably a single bond. n is preferably 1 or 2, and more preferably 1. Specific examples of W include the following.

[0026]

[Chemical 11]

[0027]

[Chemical 12]

Examples of the cation represented by M ₁ , M ₂ , M ₃ and M ₄ include alkali metals (eg lithium, sodium, potassium), ammonium (eg ammonium, tetraethylammonium) and pyridinium. it can.

In the present invention, specific examples of the compound represented by the above general formula (II) are shown below, but the present invention is not limited thereto.

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

The compounds represented by the general formula (II) of the present invention are disclosed in JP-A-63-199295 and JP-A-3-17.
It can be synthesized according to the description in Japanese Patent No. 3857 or the like. As described in these documents, the compound represented by the general formula (II) of the present invention includes optical isomers ([R, R], [S, S], [S, R] , [R, S])
(However, depending on the compound, the [S, R] form and the [R, S] form may be structurally the same.) For example, the exemplary compound (II-1) of the compound represented by the general formula (II) of the present invention includes three optical isomers ([R, R],
[S, S], [S, R] = [R, S]) exist, and these can be synthesized individually or as a mixture. It goes without saying that the present invention includes these individual optical isomers and mixtures thereof. Optical isomers [R, R], [S, S], [S,
R] and [R, S] are each mixed by about 25%. In addition, among the optical isomers, [S, S] in terms of improving the color reversion property, thermal fading or color contamination which is the object of the present invention.
It is preferable to selectively use the isomer, and from this point, it is preferable to use an optical isomer mainly consisting of the [S, S] isomer, and the amino acid in the L isomer is used as a raw material like the exemplified compound (II-1). Compounds synthesized as are preferred. Further, in order to selectively obtain the [S, S] -form, a method of synthesizing the L-form amino acid corresponding to the product as a raw material as described above, or a mixture of optical isomers by a conventional method using a commercially available column is used. Examples of the method of separation include the following. A synthetic method is preferable, and this method is also preferable in terms of cost.

Further, the [S, S] form is a compound which is easily biodegradable when discharged into the environment and is also preferable in terms of environmental pollution. Here, the meaning of “selective” or “predominantly” means that a larger amount is present than other optical isomers, and for example, 50% or more is the [S, S] isomer. Preferably, 70% or more of the mixture of optical isomers is [S, S].
It means a body, and more preferably 90% or more is a [S, S] body. Most are, for example, 1
00% may be [S, S] body. These compounds are described by Springer and Copecca in Chem. Zves
ti. 20 (6): 414-422 (1966) and the method described in JP-A-3-173857. Further, the selective synthesis method of [S, S] form is described by UMEZAWA et al.
L OF ANTIBIOTICS, Volume 37, Volume 4
No., page 426 (APR. 1984) and the like.

The iron (trivalent) complex of the compound represented by the general formula (II) of the present invention contains trivalent iron ions in the general formula (II).
It can be prepared by mixing with the compound of. When used as a bleaching agent, it may be isolated and used as a chelating agent iron (trivalent) complex. In this case, it can be isolated, for example, as an ammonium salt, a sodium salt, or a potassium salt. The amount of these iron (trivalent) complexes used is 0.02 per liter of a bleaching bath.
The amount is about mol to 1.0 mol, preferably about 0.04 mol to 0.5 mol. Further, it is preferable that the free form is present in excess of about 10 to 20% in addition to the iron (trivalent) complex. II-1, II-2, II-3 in the compound of the general formula (II),
The compounds of II-15, II-16 and II-17 are particularly preferable. The bleaching bath in the present invention may be either a bleaching bath or a bleach-fixing bath. Therefore, the iron (trivalent) complex of the compound represented by the general formula (II) is added and contained in the bleaching solution or the bleach-fixing solution.

The compound represented by the general formula (II) used in the present invention is used as a builder in the field of detergent (JP-A-63-199295, JP-A-3-173857).
Although it is a known substance, it is included in polyaminocarboxylic acid as a superordinate concept, but has never been used in photographic processing and is a novel substance in this field. Compared with the EDTA iron (trivalent) complex that has been generally used as a bleaching agent,
It works extremely well.

The silver halide color photographic light-sensitive material which can be processed by the processing method of the present invention may be any light-sensitive material such as so-called color negative or color paper, but it is particularly suitable for color paper. . Regarding the silver halide color photographic light-sensitive material containing at least one cyan coupler represented by formula (I), the constitution other than the above cyan coupler will be described. Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) used in these light-sensitive materials, and processing methods and processing additives applied to process the light-sensitive material. As the above, those described in the following patent publications, particularly European Patent EP 0,355,660A2 (Patent No. 1-107011) are preferably used. The places where the photographic components are described in the following patent publications are shown as a list.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

Of these photographic constituents, the cyan coupler must include the coupler represented by formula (I), but other couplers that can be used in combination are described in JP-A-2-33144. In addition to the diphenylimidazole type cyan coupler of European Patent EP 0,33
3-Hydroxypyridine cyan couplers described in No. 3,185A2 (among others, a 4-equivalent coupler of the coupler (42) listed as a specific example has a chlorine-releasing group.
Equivalent ones, couplers (6) and (9) are particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (among others, coupler examples 3 and 8 listed as specific examples). , 34 are particularly preferable).

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide and the like can be used, but especially for the purpose of the present invention. Is preferably high silver chloride. An emulsion composed of such high silver chloride has a silver chloride content of 90% which does not substantially contain silver iodide.
It is preferable to use a silver chlorobromide or silver chloride emulsion in an amount of mol% or more, further 95% or more, and particularly 98% or more. Here, the term "substantially free of silver iodide" means 1 mol% or less of silver iodide, particularly 0.5 mol% or less, and may be zero. The silver halide emulsion is preferably a monodisperse emulsion, particularly a coefficient of variation of 0.2% or less, particularly 0.1%. The effect of the present invention is particularly exhibited when developing a color light-sensitive material using such a high silver chloride emulsion.

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is added to the photosensitive colloid layer for the purpose of improving the sharpness of an image, etc., in EP No. 0,337,490A2, Nos. 27-37.
A dye decolorizable by treatment (among others, an oxonol dye) described on page 76 is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more,
It is preferable that the water-resistant resin layer of the support contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a divalent to tetravalent alcohol (eg, trimethylolethane). In addition, the light-sensitive material according to the present invention includes a coupler and a European patent EP 0,277,
It is preferred to use a color image keeping improving compound as described in 589A2. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, a compound (F) and / or a compound which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing. Further, in the light-sensitive material according to the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, JP-A-63-271 is used.
It is preferable to add an antifungal agent as described in No. 247.

As the support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to further improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferably set in the range of 5 to 0.8. The light-sensitive material used in the present invention has a coating silver amount of 1 g / m ²
The following is preferable, 0.4 to 0.8 g / m ² is more preferable, and 0.5 to 0.7 g / m ² is particularly preferable. Further, the dry thickness of the photographic constituent layer (excluding the support from the light-sensitive material and mainly composed of the light-sensitive emulsion layer, the intermediate layer, etc.) is preferably 4 to 14 μm, more preferably 5 to 12 μm, and 6 ˜11 μm is particularly preferred.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, upon exposure, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved.

Next, the processing method of the present invention will be described. The color developing solution used in the development processing of the light-sensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Although aminophenol compounds are also useful, p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 4-amino-N-ethyl-N. -Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N- [delta] -hydroxybutylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. 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. It is common to include agents or antifoggants. If necessary, various preservatives such as hydroxylamine, N, N-di (sulfoethyl) hydroxylamine, diethylhydroxylamine, sulfite, hydrazines, phenylsemicarbazides, triethanolamine, catecholdisulfonic acids, ethylene glycol, etc. , Organic solvents such as 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,
Various chelating agents represented by viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, 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, N ', N'-tetramethylenephosphonic acid, ethylenediamine Add di (o-hydroxyphenylacetic acid) and their salts. The pH of these color developing solutions is generally 9-12.

The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally 1 liter or less per square meter of the light-sensitive material. By reducing the bromide ion concentration in the replenishing solution, It can be 300 ml or less. Preferably 30 ml to 150 ml
/ M ² . When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution. The photographic emulsion layer after color development is usually subsequently bleached in a bath having a bleaching ability. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used.
Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, as described above, it is necessary to use the iron (trivalent) complex of the compound represented by the general formula (II), but other bleaching agents may be used together if necessary. Typical bleaching agents that can be used together are ferricyanide; dichromate; iron (3
Valent) or cobalt (trivalent) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Aminopolycarboxylic acids such as 1,3-diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like You can do it.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent No. 1,290,812, Japanese Patent Publication No. 53-95,630,
Research Disclosure No. Compounds having a mercapto group or a disulfide bond described in JP-A No. 17,129 (July 1978); JP-A-50-140,
Thiazolidine derivatives described in U.S. Pat. No. 129; US Pat.
Thiourea derivatives described in JP 706561 A;
No. 16,235, the iodide salt; West German Patent No. 2,7.
Polyoxyethylene compounds described in 48,430;
Polyamine compounds described in JP-B-45-8836; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95,6.
The compounds described in No. 30 are preferable. Further, the compounds described in US 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 light-sensitive material for photography. The treatment time of the bath having a bleaching ability is preferably 15 seconds to 60 seconds for the purpose of speeding up. More preferably, it is 20 seconds to 50 seconds. When the length is short, desilvering failure occurs, and when the length is long, the effect of the present invention cannot be sufficiently obtained. The replenishing amount is 1 liter or less per square meter of the light-sensitive material, preferably 300 ml or less, and most preferably 3 liters.
It is 0 to 150 ml. For the purpose of improving the stability and crystallization of the replenisher, the bleaching agent component and the fixing component may be separated and replenished.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. The use of thiosulfates is common, and ammonium thiosulfate is particularly preferable. Is the most widely used. As a bleach-fixing solution or a preservative for the fixing solution, sulfite, bisulfite, benzenesulfonic acid or carbonyl bisulfite adduct is preferable. 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 Soc.
society of Motion Picture and Television Engineers Volume 64, P. It can be determined by the method described in 248-253 (May 1955 issue).

According to the multi-stage countercurrent system described in the above-mentioned document,
Although the amount of water to be washed can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and the resulting suspended matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, antibacterial agents and antifungal agents described below can be added. The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be set variously depending on the characteristics and intended use of the light-sensitive material.
It is preferable to select a range of 20 seconds to 1 minute and 30 seconds at -40 ° C. Further, the light-sensitive material of the present invention, instead of the above water washing,
It is also possible to treat directly with the stabilizing solution. In such a stabilization treatment, all known methods described in JP-A-57-8,543, JP-A-58-14,834 and JP-A-60-220,345 can be used.

It is preferable that the washing water and the stabilizing solution contain various kinds of surfactants in order to prevent unevenness of water droplets when the processed light-sensitive material is dried. As these surfactants, polyethylene glycol type nonionic surfactants,
Polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant, alkylnaphthalene sulfonate type anionic surfactant, quaternary ammonium salt Type cationic surfactants, amine salt type cationic surfactants, amino salt type amphoteric surfactants, betaine type amphoteric surfactants are preferred, but it is preferable to use nonionic surfactants, especially alkylphenol ethylene oxide addition. The thing is preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Further, it is preferable that the washing water and the stabilizing solution contain various antibacterial agents and fungicides in order to prevent the generation of water stains and the mold generated in the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents are shown in JP-A Nos. 57-157244 and 58-105145, which are thiazolylbenzimidazole compounds, and JP-A-57-8542. Such isothiazolone compounds, chlorophenol compounds represented by trichlorophenol, bromophenol compounds, organotin and organozinc compounds, acid amide compounds,
Diazine and triazine compounds, thiourea compounds,
Benzotriazole compounds, alkyl guanidine compounds, quaternary ammonium salts such as benzalkonium chloride, antibiotics such as penicillin, Journal Antibacterial &
Antifungus Agent (J. Antibact. Ant
Ifung. Agents) vol 1. No. 5, p.207 to 223 (1983), general-purpose antifungal agents and the like can be mentioned. You may use these 2 or more types together. Further, various bactericides described in JP-A-48-83820 can also be used.

Further, it is preferable that the washing water and the stabilizing solution contain various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid and diethylenetriamine-N, N, N ', N'-tetramethylene. Examples thereof include organic phosphonic acids such as phosphonic acid, and hydrolysis products of maleic anhydride polymers described in European Patent 345172A1.

In the stabilizing solution, compounds that stabilize the dye image, such as formalin, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylol compounds such as dimethylolurea and N-methylolpyrazole, and organic compounds are used. Acids, pH buffers, etc. are included. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include hexamethylenetetramine and N-methylolpyrazole.
N-methylolazoles described in 318644, N,
Azolylmethylamines described in JP-A-4-313753 such as N'-bis (1,2,4-triazol-1-yl) piperazine are preferable. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners,
It is also preferable to contain a hardening agent, an alkanolamine described in U.S. Pat. No. 4,786,583, and a preservative that can be contained in the fixing solution or the bleach-fixing solution. Among these, the sulfinic acid compounds described in JP-A-1-231510 (for example, benzenesulfinic acid, toluenesulfinic acid, or salts thereof such as sodium and potassium) are preferable, and the addition amount of these is a stabilizing solution. 1
1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol per liter is preferable, and 3 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol is particularly preferable.

The amount of replenishment in the washing and / or stabilizing step of the present invention is preferably small. The amount of replenisher is 0.1 to 50 with respect to the carry-in amount of the pre-bath per unit area of the light-sensitive material.
It is preferably double, and more preferably 3 to 30 times. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C. to 42 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and 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. Further, the developing solution used for developing the black-and-white light-sensitive material in the present invention is described in JP-A-63-81337, page 66, line 7 to page 68.

[0062]

In the present invention, a silver halide color photographic light-sensitive material containing at least one cyan coupler represented by the general formula (I) and an iron (trivalent) complex of the compound represented by the general formula (II) are used. By treating with a bath having at least one bleaching ability and having a bleaching ability, color contamination and thermal fading are reduced as compared with the case of combining the cyan coupler with a conventional bleaching agent of an iron (trivalent) complex such as EDTA. , The color recovery property is improved. The compound represented by the general formula (II) used in the present invention belongs to a polyaminocarboxylic acid as a superordinate concept,
It is a novel processing agent which has never been used in conventional photographic processing, and when the iron (trivalent) complex is used as a bleaching agent in the present invention, it is mixed with the use of the cyan coupler represented by the general formula (I). And has an extremely excellent effect. Furthermore, in the present invention, when a compound represented by the general formula (II) whose optical isomer is mainly composed of [S, S] form is used, a more excellent effect is exhibited.

[0063]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these. Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to form a layer structure shown below. A multi-layer color photographic paper A was prepared. The coating liquid was prepared as follows.

Preparation of fifth layer coating solution Cyan coupler (ExC) 32.0 g, color image stabilizer (C
pd-2) 3.0 g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g and color image stabilizer (Cpd-).
8) 5.0 g, ethyl acetate 50.0 cc and solvent (S
14.0 g of olv-6) was added and dissolved, and this solution was added to 500 cc of a 20% gelatin aqueous solution containing 8 cc of sodium dodecylbenzenesulfonate, and then emulsified and dispersed by an ultrasonic homogenizer to prepare an emulsified dispersion. on the other hand,
Silver chlorobromide emulsion (cubic, 1: 4 of large size emulsion of average grain size 0.58 μm and small size emulsion of 0.45 μm)
Mixture (Ag molar ratio). Coefficients of variation of grain size distribution are 0.09 and 0.11, respectively, and each size emulsion is AgBr
0.6 mol% was locally contained in a part of the particle surface) was prepared. The red-sensitive sensitizing dye E shown below was added to this emulsion in an amount of 0.9 × 10 ^-4 per mol of silver for a large-sized emulsion.
Mol, and 1.1 × 10 ⁻⁴ mol was added to the small size emulsion. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below.

The coating solutions for the first to fourth layers, the sixth layer and the seventh layer were prepared in the same manner as the fifth layer coating solution. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. In addition, the total amount of Cpd-10 and Cpd-11 in each layer is 2
It was added to a 5.0 mg / m ² and 50.0 mg / m ^2.
The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. [Blue-sensitive emulsion layer] Sensitizing dye A

[0066]

[Chemical 18]

And sensitizing dye B

[0068]

[Chemical 19]

(2.0 × 10 ⁻⁴ mol for large size emulsion and 2.5 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) [Green-sensitive emulsion] Layer] Sensitizing dye C

[0070]

[Chemical 20]

(Per mol of silver halide, 4.0 × 10 ^-4 mol for large size emulsion, 5.6 × 10 ^-4 mol for small size emulsion) and sensitizing dye D

[0072]

[Chemical 21]

(1 mol of silver halide: 7.0 × 10 ^-5 mol for large size emulsion, 1.0 × 10 ^-5 mol for small size emulsion) [Red-sensitive emulsion layer] Sensitizing dye E

[0074]

[Chemical formula 22]

(0.9 × 10 ⁻⁴ mol for large size emulsion and 1.1 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) Further, the following compounds were halogenated. 2.6 × 10 ⁻³ mol was added per mol of silver halide.

[0076]

[Chemical formula 23]

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, at 8.5 × 10 ⁻ per mol of silver halide. ⁵ mol, 7.7 × 10 ^-4
Mol, 2.5 × 10 ⁻⁴ mol. Further, 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 mol, respectively, per mol of silver halide. × 10 ^-4
Mol added. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0078]

[Chemical formula 24]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)]

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large size emulsion with average grain size 0.88 μm and small size emulsion with 0.70 μm (silver mole ratio)) Coefficients of variation of grain size distribution are 0.08 and 0.10 respectively, and each size emulsion contains 0.3% mol of silver bromide locally on a part of grain surface) 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06

Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion with average grain size 0.55 μm and small size emulsion with 0.39 μm (Ag mole ratio)) Coefficients of variation of grain size distribution are 0.10 and 0.08, respectively, and 0.8 mol% of AgBr is locally contained in a part of grain surface in each size emulsion.) 0.12 Gelatin 1.24 Magenta coupler ( ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40

Fourth Layer (UV Absorbing Layer) Gelatin 1.58 UV Absorbing Agent (UV-1) 0.47 Color Mixing Preventing Agent (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion having average grain size 0.58 μm and small size emulsion 0.45 μm (Ag mole ratio)) The coefficient of variation of the grain size distribution is 0.09 and 0.11, and in each size emulsion 0.6 mol% of AgBr was locally contained in a part of the grain surface.) 0.23 Gelatin 1.34 Cyan coupler ( ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14

Sixth Layer (UV Absorbing Layer) Gelatin 0.53 UV Absorbing Agent (UV-1) 0.16 Color Mixing Preventing Agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh Layer ( Protective Layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.17 Liquid paraffin 0.33 Chemical formulas and the like of the compounds used in each of the above layers are shown below.

[0086]

[Chemical 25]

[0087]

[Chemical formula 26]

[0088]

[Chemical 27]

[0089]

[Chemical 28]

[0090]

[Chemical 29]

[0091]

[Chemical 30]

[0092]

[Chemical 31]

[0093]

[Chemical 32]

The light-sensitive material thus obtained was designated as Sample 1-A. Next, the cyan coupler ExC was changed as follows to prepare samples 1-B, 1-C, 1-D, and 1-E. Sample 1-B Cyan coupler below

[0095]

[Chemical 33]

Sample 1-C Cyan Coupler C-1 Sample 1-D Cyan Coupler C-2 Sample 1-E Cyan Coupler C-9 A running test of the treatment was performed on each of the above samples. During the running test, the above light-sensitive material was imagewise exposed using an automatic printer FAP3500 (manufactured by Fuji Photo Film Co., Ltd.), and continuously processed (running until the bleach-fix solution was replenished twice by using the following processing steps and processing solutions). Test). However, the composition of the bleach-fixing solution was subjected to a running test for each level in which a compound forming an iron (trivalent) complex as a bleaching agent was changed as shown in Tables 6 to 7.

Processing process Temperature Time Replenishment amount Tank capacity (sec) (ml / m ² ) (liter) Color development 38.5 ℃ 45 60 17 Bleach fixing 30-35 ℃ 30 40 17 Rinse 30-35 ℃ 20-8 Rinse 30 ~ 35 ° C 20-8 Rinse 30-35 ° C 20-8 Rinse 30-35 ° C 30 160 8 Rinsing was a 4-tank countercurrent system of →→→. The composition of each processing liquid is as follows.

[Color Developer] Tank Solution Replenisher Water 800 ml 800 ml EDTA.2Na 3 g 3 g Catechol-3,5-disulfonate sodium 0.3 g 0.3 g Triethanolamine 8.0 g 8.0 g Potassium bromide 0.03 g -Sodium chloride 6.0 g-N, N-di (sulfoethyl) hydroxylamine 5.0 g 8.0 g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g Sodium sulfite 0.2 g 0.2 g N -Ethyl-N- (β-methanesulfonamidoethyl) 3-methyl-4-aminoaniline sulfate 5.0 g 12.0 g Water was added to 1000 ml 1000 ml pH (25 ° C) 10.05 11.15

[Bleach-fixing tank liquid] Water 800 ml Ammonium thiosulfate (50% by weight) 120 ml Ammonium sulfite 17 g Iron (trivalent) complex 0.15 mol Complex forming compound 0.01 mol Glacial acetic acid 8 g Water is added to 1000 ml pH (25 %) 5.00

[Bleach-fixing replenisher] Water 500 ml Ammonium thiosulfate (50% by weight) 250 ml Ammonium sulfite 35 g Iron (trivalent) complex (ammonium salt) 0.35 mol Complex forming compound 0.01 mol Glacial acetic acid 25 g Water was added. 1,000 ml pH (25 ° C) 4.50 [rinse solution] (tank solution and replenisher are the same) Ion-exchanged water (3 ppm each for calcium and magnesium)
Less than)

In each running test, a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 320
Gradient exposure of the sensitometric filter was performed (0 ° K) (exposure at this time was performed at an exposure amount of 250 CMS with an exposure time of 0.1 second). The sample thus exposed was subjected to development processing, and the processed sample was subjected to density measurement by a self-recording densitometer to determine the minimum density change (ΔD _Bmin ) of yellow in the unexposed portion at the start and end. Next, the maximum density part is a color negative bleaching solution CN-16X N ₂
It was dipped in Bleach (manufactured by Fuji Photo Film Co., Ltd.) for 4 minutes, washed with water and dried, and the cyan density was measured again. At this time, the rate of increase in the maximum cyan density (degree of color restoration failure) was determined as the color development rate P (%). P (%) = (cyan concentration after treatment / cyan concentration after rebleaching) × 100 (%) At the same time, the treated sample was stored at 80 ° C./70% RH for 20 days, and the amount of decrease in the maximum cyan concentration was decreased. (Fade, ΔD _Rmax )
I asked. The results are shown in Tables 6-7. According to the present invention, an increase in yellow stain (contamination) on a white background was small and good, and at the same time, good results were obtained with small cyan fading and color restoration defects. In particular, mainly as optical isomers [S,
S] ^-compound II-1 ^** or II-2 ^** was used. In Nos. 1-8 and 1-9, cyan fading and color restoration defects are further improved. Compound II-1 used here
^** or II-2 ^** [S, S], [R, S] = [S,
The ratio of R] and [R, R] was about 1: 2: 1.

[0102]

[Table 6]

[0103]

[Table 7]

Example 2 Experiment No. 2 of Example 1 Under the conditions of 1-1, 1-4 and 1-8, the bleach-fixing time was 10 seconds, 15 seconds, 30 seconds, 4
Tables 8 to 11 show the results when the same experiment as in Example 1 was conducted with 5 seconds, 60 seconds, and 90 seconds. According to the invention,
Particularly, when the bleach-fixing time was 15 seconds to 60 seconds, good results were exhibited with less color contamination and less fading of the cyan dye.

[0105]

[Table 8]

[0106]

[Table 9]

[0107]

[Table 10]

[0108]

[Table 11]

Example 3 An example of processing of a silver halide color light-sensitive material used as a color negative will be shown. An example of the method for preparing the emulsion in the light-sensitive material used in this example is shown below. (1 liquid) Gelatin 30 g NaCl 12 g Water 1000 cc (2 liquid) AgNO ₃ 20 g NH ₄ NO ₃ 0.5 g Water added 300 cc (3 liquid) KI 1.17 g NaCl 9.49 g Water added 300 cc (4 liquid) AgNO ₃ 80g NH ₄ NO ₃ 1g water to make 600cc (5 solution) was added KI 2.35g NaCl 39.97g water 600g

An example of emulsion preparation is shown below for silver iodochloride emulsion A-1. (A-1) Emulsion (1st solution) was kept at 55 ° C., 1.5 g of Compound A was added, and (2nd solution) and (3rd solution) were simultaneously added in the same amount over 5 minutes. Next, (4th liquid) and (5th liquid) were simultaneously added in the same amount in 30 minutes by accelerating addition so that the final addition amount was double the initial addition amount to obtain a silver iodochloride emulsion. . During the grain formation of the emulsion, it was added while controlling with dilute sulfuric acid in order to keep the pH of the reactor constant. In addition, (4 solution) and (5 solution) 30
During the latter 10 minutes, a solution prepared by adding 320 cc of methanol to the spectral sensitizing dye ExS-6 in an amount of 0.018 mol per mol of silver halide was added at a constant rate during the latter 10 minutes. Two minutes after the completion of the addition, the temperature was lowered to desalt. A gelatin aqueous solution for dispersion was added to adjust the pH to 6.4 and pA.
The g was adjusted to 7.5. The grains of the obtained silver iodochloride emulsion were tabular, and the average aspect ratio was 7, the average grain size and the average grain thickness were 1.35 and 0.18 μm, respectively.
Compound B was added to this emulsion in an amount of 12 mg per mol of silver halide.
And diphenylthiourea, chloroauric acid and potassium thiocyanide were added at 58 ° C. in an amount of 5 × 10 ⁻⁶ mol, 3.7 × 10 ⁻⁵ mol and 4 × 10 ⁻³ mol, respectively, per mol of silver halide, Optimal chemical sensitization was applied. After this, treatment with activated carbon was carried out, followed by filtration with a microfilter. Further, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene and 1- (3-methylcarbamoylaminophenyl) -2-mercaptotetrazole were added to prepare (A-1) emulsion.

[0111]

[Chemical 34]

Optimum chemical sensitization of the emulsion prepared above means that the sensitivity obtained by subjecting the emulsion to exposure of 1/100 second and processing under constant processing conditions gives the highest sensitivity. Chemical sensitization.

Using these various emulsions prepared as described above, a multilayer silver halide color photographic light-sensitive material 101 comprising each layer having the following composition was prepared on an undercoated polyethylene terephthalate support. . The amount coated amount (Composition of photosensitive layer) is represented in units 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. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative. UV: UV absorber, Solv: High boiling organic solvent, Ex
S: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd; Additive

[0114] The first layer (antihalation layer) Black colloidal silver 0.18 Gelatin ^{1.02 UV-1 4.4 × 10 -2} UV-2 8.8 × 10 -2 UV-3 10.0 × 10 - ² Solv-2 0.10 Second layer (intermediate layer) Gelatin 1.21

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodochloride emulsion (AgI 0.5 mol%, internal high AgI type with core-shell ratio 1: 2, spherical equivalent diameter 0.45 μm, variation coefficient of spherical equivalent diameter) 15%, cubic grains) coated silver amount 0.50 silver iodochloride emulsion (AgI 1 mol%, internal high AgI type with core-shell ratio 1: 2, sphere equivalent diameter 0.62 μm, variation coefficient of sphere equivalent diameter 12%, plate Particles, diameter / thickness ratio 2.0) amount of coated silver 0.40 gelatin 3.20 ExS-1 5.16 × 10 ⁻³ ExS-2 2.84 × 10 ⁻³ ExS-7 3.80 × 10 ^{− 4} ExS-3 4.6 × 10 ⁻⁴ ExC-1 0.84 ExC-2 3.6 × 10 ⁻² ExC-3 5.0 × 10 ⁻² Solv-1 0.38 Solv-2 0.76

Fourth Layer (High Sensitivity Red Sensitive Emulsion Layer) Silver iodochloride emulsion (AgI 5.0 mol%, internal high AgI type with core-shell ratio 1: 2, sphere equivalent diameter 1.00 μm, variation coefficient of sphere equivalent diameter) 25%, plate-like particles, diameter / thickness ratio of 6.0) Coating amount of silver 0.45 Gelatin 0.69 ExS-1 0.13 × 10 ⁻³ ExS-2 0.70 × 10 ⁻³ ExS-7 0. 92 x 10 ^-4 ExS-3 0.12 x 10 ^-4 ExC-1 2.90 x 10 ^-2 ExC-3 6.20 x 10 ^-2 ExC-4 6.60 x 10 ^-2 Solv-1 0. 18

Fifth layer (intermediate layer) Gelatin 0.52 Cpd-8 3.20 × 10 ⁻² Polyethyl acrylate latex 0.24 Solv-1 5.0 × 10 ⁻² Solv-2 2.1 × 10 ^{− 2}

Sixth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodochloride emulsion (AgI 6.0 mol%, internal high AgI type with core-shell ratio of 1: 2, sphere equivalent diameter 0.60 μm, sphere equivalent diameter variation coefficient) 25%, plate-like particles, diameter / thickness ratio 7.0) Coating amount of silver 0.50 Gelatin 1.00 ExS-5 2.21 × 10 ⁻³ ExS-4 2.19 × 10 ⁻³ ExS-8 2. 32 × 10 ⁻³ ExM-5 0.48 ExM-10 3.1 × 10 ⁻² ExM-6 0.15 ExM-7 2.0 × 10 ⁻² Solv-1 0.40

Seventh Layer (High Sensitivity Green Sensitive Emulsion Layer) Silver iodochloride emulsion (AgI 1.0 mol%, sphere equivalent diameter 0.93 μm, variation coefficient of sphere equivalent diameter 43%, plate-like grain, diameter / thickness ratio) 3.0) Silver coating amount 0.40 Gelatin 0.70 ExS-5 1.06 × 10 ⁻³ ExS-4 1.05 × 10 ⁻³ ExS-8 1.11 × 10 ⁻³ ExM-13 0.5 × 10 ^-2 ExM-14 0.9 × 10 ^-2 ExM-15 1.7 × 10 ^-2 ExM-6 2.4 × 10 ^-2 Cpd-8 1.4 × 10 ^-2 Solv-1 0.21 Solv-2 3.0 × 10 ^-2

Eighth Layer (Yellow Filter Layer) Yellow Colloidal Silver 0.10 Gelatin 0.63 Cpd-8 0.13 Solv-1 0.21 Solv-2 8.6 × 10 ^-2 Polyethylacrylate Latex 0.31

Ninth Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodochloride emulsion (AgI 0.8 mol%, internal high AgI type with core-shell ratio 1: 2, sphere equivalent diameter 0.98 μm, variation coefficient of sphere equivalent diameter) 43%, plate-like particles, diameter / thickness ratio 3.0) amount of coated silver 0.20 gelatin 0.95 ExS-6 2.0 × 10 ⁻⁴ ExY-11 0.97 ExY-12 6.9 × 10 ^{− 2} Cpd-8 1.2 × 10 ^-2 Solv-1 0.32

10th layer (intermediate layer) Gelatin 0.30 ExY-12 0.15 Solv-1 0.26

Eleventh layer (high-sensitivity blue-sensitive emulsion layer) Silver iodochloride emulsion (A-1) Coating silver amount 0.60 Gelatin 1.05 ExS-6 1.0 × 10 ⁻⁴ ExY-11 0.23 Cpd -8 2.7 x 10 ^-3 Solv-1 7.7 x 10 ^-2 polyethyl acrylate latex 0.48

Twelfth Layer (Intermediate Layer) Fine grain silver iodobromide emulsion (AgI 1.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Coating silver amount 0.26 Gelatin 0.40 UV-40. 11 UV-5 0.17 Solv-5 1.9 × 10 ^-2 Polyethyl acrylate latex 8.7 × 10 ^-2

Thirteenth layer (protective layer) Gelatin 0.25 B-1 (diameter 1.5 μm) 3.0 × 10 ^-2 B-2 (diameter 1.5 μm) 3.6 × 10 ^-2 B-31 .8 × 10 ^-2 W-4 1.8 × 10 ^-2 Cpd-5 0.20 H-1 0.24

In addition to the above, the samples thus prepared include
1,2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm the same), and 2-
Phenoxyethanol (about 10,000 ppm) was added. Furthermore, B-4, B-5, F-1, F-2, F
-3, F-4, F-5, F-6, F-7, F-8, F-
9, F-10, F-11, F-12, F-13 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained. In addition to the above components, surfactants W-1, W-2, and W-3 were added to each layer as coating aids and emulsion dispersants. The compounds used and the like are shown below.

[0127]

[Chemical 35]

[0128]

[Chemical 36]

[0129]

[Chemical 37]

[0130]

[Chemical 38]

[0131]

[Chemical Formula 39]

[0132]

[Chemical 40]

[0133]

[Chemical 41]

[0134]

[Chemical 42]

[0135]

[Chemical 43]

[0136]

[Chemical 44]

[0137]

[Chemical formula 45]

[0138]

[Chemical formula 46]

The dry film thickness of Sample 101 is 15 μm,
The swelling speed T1 / 2 was 8 seconds. The total coated silver amount was 3.69 g / m ² . Further, the cyan coupler ExC-1 of the sample 101 was changed to an equimolar coupler shown below to prepare samples 102 to 104. Sample 102

[0140]

[Chemical 47]

Sample 103 C-20 Sample 104 C-26 Sample 101 was cut to a width of 35 mm and photographed with a camera. The composition of the bleach-fixing solution was 2 m ² per day for 15 days as shown in Tables 12 to 13. Was changed and each was processed. (Running processing) Each processing was carried out as follows using a modified machine of an automatic processor FP-560B manufactured by Fuji Photo Film Co., Ltd.

The processing steps and processing liquid compositions are shown below. (Processing step) Process processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 23 ml 17 liters Bleach 30 seconds 38.0 ° C 5 ml 5 liters Bleach fixing 30 seconds 38.0 ° C-5 liters Fixed 30 seconds 38.0 ° C 16 ml 5 liters Water wash 20 seconds 38.0 ° C 34 ml 3.5 liters Stability (1) 15 seconds 38.0 ° C −3 liters Stability (2) 15 seconds 38.0 ° C 20 ml 3 liters Dry 1 minute 00 seconds 60 ° C * The replenishment amount is per 35 m width of the photosensitive material and 1.1 m (equivalent to 24 Ex. 1). The stabilizing solution is a countercurrent system from (2) to (1), and the overflow solution of washing water is all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching step, the amount of bleaching solution brought into the bleach-fixing step, the amount of bleach-fixing solution brought into the fixing step and the amount of fixing solution brought into the washing step were as follows. 2.5 ml, 2.0 ml, 2.0 ml per meter,
It was 2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.1 Carbonic acid Potassium 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N- (β-hydroxyl Ethyl) Amino] aniline sulfate 4.5 6.0 Water was added to 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.15 (bleaching solution) Tank solution (g ) Replenisher (g) Compound iron (trivalent) complex / ammonium salt 0.35 mol 0.50 mol Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 0 60 Water was added 1.0 liter 1.0 liter pH (adjusted with ammonia water) 4.0 4.0 (bleach-fixing tank liquid) 15:85 (volume ratio) of the above bleaching tank liquid and the following fixing tank liquid Mixture. (PH 7.0)

(Fixer) Tank liquid (g) Replenisher (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 mg / l) 300 ml 860 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water was added 1.0 l 1 0.0 liter pH (adjusted with ammonia water and acetic acid) 7.4 7.45 (wash water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Hurst Co.).
And an OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through the column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by isocyanuric dichloride. Sodium acid 20mg / liter and sodium sulfate 150mg /
1 liter was added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing Solution) Tank Solution and Replenishing Solution Common Unit (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetic acid Salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5 Above Samples 101, 102, 103, and 104 exposed through a wedge-shaped wedge were treated with each running solution and running start solution in the same manner as in Example 1, and the following evaluations were performed.

(Evaluation of Color Contamination) In the unexposed area, the difference (increase) in yellow density between the running start solution and the running solution was measured. (ΔD _{B min} ) (Evaluation of storability of color image) The density of the sample treated with the running solution was measured, and the sample was allowed to stand at 60 ° C./70% RH for 4 weeks. The density reduction amount at the point was calculated. (ΔD _{R 1.5} ) (Evaluation of recolorability) The density of the sample treated with the running liquid was measured, and the recoloring rate P of cyan was measured in the same manner as in Example 1
(%) Was calculated. The results are shown in Tables 12 to 13. According to the present invention, the iron (trivalent) complex of ethylenediaminetetraacetic acid that has been conventionally used in the treatment using the bleaching agent comprising the iron (trivalent) complex of the compound represented by the general formula (I) of the present invention. Is more effective than the case of using as a bleaching agent. In addition, No.
3-4 to No. According to 3-9, when not only the bleaching agent but also the cyan coupler is the one of the present invention, it has an excellent effect. In particular, in Experiment No. 2 using compounds II-1 ^** and II-2 ^** mainly composed of [S, S] isomers as optical isomers. 3-
In Nos. 8 and 3-9, the above three effects can be obtained more remarkably.

[0147]

[Table 12]

[0148]

[Table 13]

Example 4 Using Sample 1-C of Example 1, a running test was carried out until the bleaching solution was replenished three times in the following processing steps.
However, as shown in Table 14, the composition of the bleaching solution was subjected to a running test for each level in which a compound forming an iron (trivalent) complex as a bleaching agent was changed. Process time Temperature Replenishment amount Tank capacity (° C) (ml / m ² ) (liter) Color development 45 seconds 38 80 10 Bleaching 45 seconds 38 200 10 Water washing 45 seconds 30 1000 10 Fixed 60 seconds 38 200 15 Water washing 90 Second 30 10000 20 Dry 60 seconds 70-90

The composition of each processing solution used is as follows. (Color developer) Tank liquid Replenisher Water 600 ml 600 ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 2.0 g 2.0 g Triethanolamine 14.0 g 14.0 g Lithium sulfate 1.0 g 1.0 g Diethylhydroxylamine 3.0 g 4.0 g Sodium chloride 3.0 g -N-ethyl-N (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.0 g 8.5 g Optical brightener (Ciba Geigy Company, UVI TEX-CK) 1.5 g 3.0 g potassium carbonate 27 g 27 g Water was added to the above 1000 ml 1000 ml KOH pH 10.0 10.0

(Bleach) Water 600 ml 600 ml Iron (trivalent) complex 0.08 mol 0.08 mol Complex forming compound 0.01 mol 0.01 mol Ammonium bromide 50 g 65 g Nitric acid 5 g 8 g Water is added to the above 1000 ml 1000 ml pH 5.0 4.5

(Fixer) Water 600 ml 600 ml Sodium thiosulfate 100 g 110 g Sodium sulfite 15 g 20 g EDTA2Na 2 g 3 g Water was added to the above 1000 ml 1000 ml pH 7.0 7.3 In each running test, in the same manner as in Example 1,
At the end of the running, sensitometry was performed to determine the change in the minimum density of yellow, the fading of cyan, and the degree of color restoration failure. The measurement results are shown in Table 14.

[0153]

[Table 14]

In the present invention, color contamination and cyan fading were small, and good color recovery was obtained.

According to the processing method of the silver halide color photographic light-sensitive material of the present invention, the recoloring rate is remarkably high and the recoloring is improved, thermal fading of the dye is remarkably prevented, and color contamination is prevented. Has the remarkable effect of Moreover, these effects can be obtained despite rapid processing. In particular,
When the compound represented by the general formula (II) whose optical isomer is mainly composed of the [S, S] form, the above three effects are more remarkably obtained. Also,
In the present invention, even when compared with the case of treatment with an iron (trivalent) complex such as ethylenediaminetetraacetic acid, which is a typical bleaching agent that has been used conventionally, it has a remarkably excellent effect on the above-mentioned color reversion property.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07C 233/25 7106-4H 233/56 7106-4H 235/24 7106-4H 237/12 7106-4H 275/32 323/25 323/52

Claims (4)

[Claims] 1. A silver halide color photographic light-sensitive material containing at least one cyan coupler represented by the following general formula (I) is color-developed, and then iron (trivalent) of a compound represented by the following general formula (II) is developed. ) A processing method of a silver halide color photographic light-sensitive material, which comprises processing in a bath having a bleaching ability containing at least one complex. General formula (I) (In the formula, R _a represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R _b represents an acylamino group or an alkyl group having 2 or more carbon atoms. R _c represents a hydrogen atom or a halogen atom. Represents an alkyl group or an alkoxy group, R _c may combine with R _b to form a ring, and Z _a represents a hydrogen atom, a halogen atom or an aromatic first group.
A group capable of splitting off upon reaction with an oxidant of a primary amine color developing agent is shown. ) General formula (II): (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group. W is represented by the following general formula (W). Represents a linking group.
M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. Formula _{(W) - (W 1 -Z} ) n -W 2 - In the general formula (W), W ₁ represents an alkylene group or a single bond. W ₂ represents an alkylene group or -CO-. Z is a single bond, -O-, -S-, -CO-, or -N ( _Rw ).
-(R _w represents a hydrogen atom or an alkyl group which may be substituted). However, Z and W ₁ are not a single bond at the same time. n represents an integer of 1 to 3. ) 2. The compound represented by the general formula (II) is
2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the optical isomer is mainly composed of [S, S] body. 3. The processing of a silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the processing time in the bath having the bleaching ability is 15 to 60 seconds. Method. 4. The washing and / or stabilizing step after the treatment in the bath having the bleaching ability is performed for 10 seconds to 2 minutes, according to any one of claims 1 to 3.
5. A method for processing a silver halide color photographic light-sensitive material as described in the above item.