DE3878745T2 - COLOR PHOTOGRAPHIC SILVER HALOGENIDE MATERIALS. - Google Patents

Description

The invention relates to color photographic silver halide materials.

In general, silver halide color photographic materials are basically processed by a color development process and a desilvering process. The exposed silver halide is reduced by a color developing agent to form silver during the color development process and at the same time the oxidized form of the color developing agent reacts with a color forming agent (coupler) to give a color image. The silver thus formed is then oxidized by a bleaching agent and then converted into a soluble silver complex by the action of a fixing agent, whereby the silver is dissolved and removed in the desilvering process.

In recent years, there has been a strong demand in the industry for faster processing, i.e. for shorter processing times and in particular for shortening the desilvering process, which accounts for about half of the processing time.

Disclosures concerning couplers releasing a bleach accelerating compound have been described in Research Disclosure Nos. 24241 and 11449 and in Japanese Patent Application (OPI) No. 201247/86 as a way to increase the bleaching power. It is known that the desilvering properties can be improved by using silver halide color photographic materials containing these couplers releasing a bleach accelerating compound.

However, photosensitive materials containing these couplers releasing a bleach accelerating compound have the disadvantage of a predicted deterioration of the cyan image back-staining properties, if they are processed quickly in the desilvering process.

On the other hand, there are various known cyan image-forming couplers which are effective to improve the back-coloring properties of the cyan image (e.g., ureidophenol type cyan couplers described in U.S. Patent 4,333,999 and Japanese Patent Application (OPI) Nos. 207593/82, 204544/82, 11863/83, the 5-amidonaphthol cyan couplers described in Japanese Patent Application (OPI) Nos. 237448/85, 145557/86 and 153640/86, and in addition, the diacylaminophenol type cyan couplers used in the color paper field), and a 2-ureidophenol type cyan coupler having a 4-cyanophenyl group, a type of cyan image-forming coupler effective for back-staining properties is used in the examples of Japanese Patent Application (OPI) No. 201247/86, which relates to the aforementioned couplers releasing a bleach-accelerating compound.

However, it has been found that there is a disadvantage that a satisfactory minimum density cannot be obtained when 2-ureidophenol type cyan couplers are used as cyan image-forming couplers. This disadvantage is particularly evident when high-speed processing is used. Therefore, this does not help to solve the problem of shortening the desilvering process. In addition, diacylaminophenol type cyan couplers also undesirably tend to have a high level of residual color and an increased minimum image density similar to that observed with the ureido type.

This invention is intended to solve the above-described problems encountered in silver halide color photographic materials containing compounds releasing a bleaching accelerating agent.

Accordingly, it is the object of the invention to provide color photographic silver halide materials which are superior in terms of desilvering speed, and which have good color-recovery properties and minimal image densities.

It has been found that the above-mentioned object of the invention can be achieved by means of a silver halide color photographic material comprising a support having at least one silver halide emulsion layer thereon, wherein the material (1) contains at least one kind of cyan dye-forming coupler represented by the general formula (A)

wherein R₁ represents a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amidine group, a guanidine group or a group represented by

R₂ represents a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an amino group, a cyano group, a nitro group, an aliphatic group, an aromatic group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, an acyl group, an acyloxy group, an aliphatic oxy group, an aromatic oxy group, an aliphatic sulfonyl group, an aromatic sulfonyl group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, a sulfamoylamino group, a heterocyclic group or an imido group, l' represents an integer of 0 to 3, R₃ represents a hydrogen atom or R₆U, and T represents a hydrogen atom or a group which can be eliminated by a coupling reaction with the oxidized product of an aromatic primary amine developing agent, wherein R₄ and R₅ each independently represent an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an aliphatic oxy group or an aromatic oxy group, and R₆ represents a hydrogen atom or a group which can be eliminated by a coupling reaction with the oxidized product of an aromatic primary amine developing agent. a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group,

-SO₂OR₇ or an imido group and U represents NR₉, -CO-, -SO₂-, -SO- or a single bond, wherein R₇ represents an aliphatic group, an aromatic group or a heterocyclic group, R₈ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R₇ and R₁₀ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an aliphatic sulfonyl group or an aromatic sulfonyl group when l' is 2 or 3, R₂- groups may be the same or different and may be linked together to form a ring, and R₃, or R₃ and T, may be linked together to form rings, further dimers or oligomers or polymers which may also be formed with each other via divalent groups or groups having a valence greater than 2 for each of R₁, R₂, R₃ or T, characterized in that the material further contains (2) at least one kind of compound which reacts with the oxidized product of a primary aromatic amine developing agent to release a bleach accelerator.

In this invention, it has surprisingly been found that when a light-sensitive material containing a compound which reacts with the oxidized product of a primary aromatic amine-based color developing agent and releases a bleaching accelerating agent (hereinafter "bleaching accelerating agent-releasing compound") is rapidly processed, not only the back-coloring properties are improved but also the minimum density obtained is effectively suppressed by adding the specific cyan image-forming coupler represented by the general formula (A) to the light-sensitive material.

The compounds used according to the invention are described in more detail below.

The aliphatic groups are straight-chain, branched or cyclic alkyl groups, alkenyl groups or alkynyl groups, and they can be substituted or unsubstituted groups.

The aromatic groups are substituted or unsubstituted aryl groups, and they may have condensed rings.

The heterocyclic groups are substituted or unsubstituted heterocyclic groups of single ring or condensed ring type.

Current examples of aliphatic groups include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a cyclopentyl group, a t-pentyl group, a cyclohexyl group, an n-octyl group, a 2-ethylhexyl group, an n-decyl group, an n-dodecyl group, a n-tetradecyl group, an n-hexadecyl group, an n-octadecyl group, a 2-hexyldecyl group, an adamantyl group, a trifluoromethyl group, a carboxymethyl group, a methoxyethyl group, a vinyl group, an allyl group, a hydroxyethyl group, a heptafluoropropyl group, a benzyl group, a phenethyl group, a phenoxyethyl group, a methylsulfonylethyl group, a Methanesulfonamidoethyl group, a 3-(2-ethylhexyloxy)propyl group, a 3-n-decyloxypropyl group, a 3-n-dodecyloxypropyl group, a 3-n-tetradecyloxypropyl group, an oleyl group, a propargyl group, an ethynyl group, a 3-(2,4-di-t-pentylphenoxy)propyl group, a 4-(2,4-di-t-pentylphenoxy)butyl group, a 1-(2,4-di-t-pentylphenoxy)propyl group, a 1-(2,4-di-t-pentylphenoxy)pentyl group, a 1-(3-tetradecylphenoxy)propyl group and a 2-n-dodecylthioethyl group.

Current examples of aromatic groups include a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a 4-chlorophenyl group, a 4-nitrophenyl group, a 4-cyanophenyl group, a 4-hydroxyphenyl group, a 3-hydroxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-diphenylyl group, p-diphenylyl group, a pentafluorophenyl group, a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a 4-methoxyphenyl group, a 4-t-butylphenyl group, a 4-t-octylphenyl group, a 4-carboxyphenyl group, a 4-methanesulfonamidophenyl group, a 4-(4-hydroxyphenylsulfonyl)phenyl group, a 2-n-tetradecyloxyphenyl group. a 4-n-tetradecyloxyphenyl group, a 2-chloro-5-n-dodecyloxyphenyl group, a 3-n-pentadecylphenyl group, a 2-chlorophenyl group, a 4-methoxycarbonylphenyl group, a 4-methylsulfonylphenyl group and a 2,4-di-t-pentylphenyl group.

Current examples of heterocyclic groups include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-furyl group, a 2-thienyl group, a 3-thienyl group, a 4-quinolyl group, a 2-imidazolyl group, a 2-benzimidazolyl group, a 4-pyrazolyl group, a 2-benzoxazolyl group, a 2-benzothiazolyl group, a 1- imidazolyl group, a 1-pyrazolyl group, a 5-tetrazolyl group, a 1,3,4-thiadiazol-2-yl group, a 2-prolyl group, a 3-triazolyl group, a 4-oxazolyl group, a 4-thiazolyl group, a 2-pyrimidyl group, a 1,3,5-triazin-2-yl group, a 1,3,4-oxadiazol-2-yl group, a 5-pyrazolyl group, a 4-pyrimidyl group, a 2-pyrazyl group, a succinimido group, a phthalimido group, a morpholino group, a pyrrolidino group, a piperidino group, an imidazolidin-2,4-dion-3-yl group, an imidazolidin-2,4-dion-1-yl group and an oxazolidin-2,4-dion-3-yl group.

The individual substituent groups in the general formula (A) are described in detail below.

R₁ in the general formula (A) represents a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amidine group, a guanidine group, or a group represented by Here, R₄ and R₅ represent each individually an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms, an amino group having 0 to 30 carbon atoms (e.g. an amino group, a methylamino group, a dimethylamino group, an n-butylamino group, an anilino group, an N-(2-n-tetradecyloxyphenyl)amino group, a pyrrolidino group, a morpholino group, a piperidino group, a 2-ethylhexylamino group, an n-dodecylamino group, an N-methyl-N-dodecylamino group, a 3-dodecyloxypropylamino group, a 3-(2,4-di-t-pentylphenoxy)propylamino group or a 4-(2,4-di-t-pentylphenoxy)butylamino group), an aliphatic Oxy group having 1 to 30 carbon atoms (e.g., a methoxy group, an ethoxy group, a butoxy group, a methoxyethoxy group, an n-dodecyloxy group, or a 3-(2,4-di-t-pentylphenoxy)propoxy group) or an aromatic oxy group having 6 to 30 carbon atoms (e.g., a phenoxy group, a 4-n-dodecyloxyphenoxy group, or a 4-methoxycarbonylphenoxy group). R₄ and R₅ may be bonded to each other to form a ring. When R₁ is a halogen atom, it is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. When R₁ is a phenyl group, it is a phenyl group. is an amidine group or a guanidine group, the total number of carbon atoms is 1 to 30, and these groups may be substituted with aliphatic groups, aromatic groups, hydroxyl groups, aliphatic oxy groups, acyl groups, aliphatic sulfonyl groups, aromatic sulfonyl groups, acyloxy groups, aliphatic sulfonyloxy groups or aromatic sulfonyloxy groups, and two nitrogen atoms may be bonded to each other to form a heterocyclic ring such as an imidazole or a benzimidazole, etc.

R₂ in the general formula (A) represents a halogen atom (a fluorine atom, a chlorine atom, an ero atom or an iodine atom), a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, an amino group, which has 0 to 30 carbon atoms (eg an amino group, a methylamino group, a dimethylamino group, a pyrrolidino group or an anilino group), an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a carbonamido group having 1 to 30 carbon atoms (eg a formamido group, an acetamido group, a trifluoroacetamido group or a benzamido group), a sulfonamido group having 1 to 30 carbon atoms (eg a methanesulfonamido group, a trifluoromethanesulfonamido group, an n-butanesulfonamido group or a p-toluenesulfonamido group), a carbamoyl group having 1 to 30 carbon atoms (eg a carbamoyl group, an N,N-dimethylcarbamoyl group, an N-methylcarbamoyl group, a pyrrolidinocarbamoyl group or an Nn-hexadecylcarbamoyl group), a sulfamoyl group having 0 to 30 carbon atoms (eg a sulfamoyl group, an N-methylsulfamoyl group, an N,N-dimethylsulfamoyl group, a morpholinosulfonyl group or an Nn-dodecylsulfamoyl group), a ureido group having 1 to 30 carbon atoms (eg a ureido group, a 3-methylureido group, a 3-phenylureido group or a 3,3-dimethylureido group), an acyl group having 1 to 30 carbon atoms (eg an acetyl group, a pivaloyl group, a benzoyl group or a dodecanoyl group), an acyloxy group having 1 to 30 carbon atoms (eg an acetoxy group or a benzoyloxy group), an aliphatic oxy group having 1 to 30 carbon atoms, a aromatic oxy group having 6 to 30 carbon atoms, an aliphatic thio group having 1 to 30 carbon atoms, an aromatic thio group having 6 to 30 carbon atoms, an aliphatic sulfonyl group having 1 to 30 carbon atoms, an aromatic sulfonyl group having 6 to 30 carbon atoms, an aliphatic sulfinyl group having 1 to 30 carbon atoms, an aromatic sulfinyl group having 6 to 30 carbon atoms, an aliphatic oxycarbonyl group having 2 to 30 carbon atoms, an aromatic oxycarbonyl group having 7 to 30 carbon atoms, an aliphatic Oxycarbonylamino group having 2 to 30 carbon atoms, an aromatic oxycarbonylamino group having 7 to 30 carbon atoms, a sulfamoylamino group having 0 to 30 carbon atoms (eg, a sulfamoylamino group, a 3,3-dimethylsulfamoylamino group or a piperidinosulfonylamino group), a heterocyclic group having 1 to 30 carbon atoms, or an imido group having 4 to 30 carbon atoms (eg, a succinimido group, a maleimido group, a phthalimido group, a diglycolimido group or a 4-nitrophthalimido group).

R₃ in the general formula (A) represents a hydrogen atom or R₆U. Here, R₆ represents a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms,

or an imido group having 4 to 30 carbon atoms (e.g., a succinimido group, a maleimido group, a phthalimido group, or a diacetylamino group), and U represents >NR9, -CO-, -SO2-, -SO-, or a single bond, and R7 represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 1 to 30 carbon atoms, R8 represents a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 1 to 30 carbon atoms, and R9 and R10 each independently represent a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms (e.g., an acetyl group, a trifluoroacetyl group, a benzoyl group, or a p-chlorobenzoyl group), or a sulfonyl group having 1 to 30 carbon atoms (e.g., a methylsulfonyl group, an n-butylsulfonyl group, a phenylsulfonyl group, or a p-nitrophenylsulfonyl group). R�9 and R₁₀ may be bonded together to form a ring.

T in the general formula (A) represents a hydrogen atom or a group which can be eliminated by a coupling reaction with the oxidized product of a primary aromatic amine developing agent. Here, examples of the latter groups include halogen atoms (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a sulfo group, a thiocyanato group, an iso-thiocyanato group, a selenocyanato group, aliphatic oxy groups having 1 to 30 carbon atoms, aromatic oxy groups having 6 to 30 carbon atoms, aliphatic thio groups having 1 to 30 carbon atoms, aromatic thio groups having 6 to 30 carbon atoms, heterocyclic thio groups having 1 to 30 carbon atoms, heterocyclic oxy groups having 1 to 30 carbon atoms, aromatic azo groups having 6 to 30 carbon atoms, heterocyclic groups having 1 to 30 carbon atoms, acyloxy groups having 1 to 30 carbon atoms (e.g. an acetoxy group or a benzoyloxy group), Sulfonyloxy groups having 1 to 30 carbon atoms (e.g. a methylsulfonyloxy group or a p-tolylsulfonyloxy group), carbamoyloxy groups having 1 to 30 carbon atoms (e.g. an N,N-dimethylcarbamoyloxy group, a pyrrolidinocarbonyloxy group or an N-ethylcarbamoyloxy group), thiocarbonyloxy groups having 2 to 30 carbon atoms (e.g. a methylthiocarbonyloxy group or a phenylthiocarbonyloxy group), and carbonyldioxy groups, which have 2 to 30 carbon atoms (e.g. a methoxycarbonyloxy group or a phenoxycarbonyloxy group).

In the general formula (A), R₂ and R₃, R₃ and T, or a plurality of R₂ may be linked to each other to form rings. Examples of R₂ linked to R₃ include -CH₂CO-, -OCO-, -NHCO-, -C(CH₃)₂CO-, -CH=CHCO-, etc. Examples of T linked to R₃ include -CH₂C- and -COO-. Examples in which a plurality of R₂ are linked to R₃ include -CH₂C- and -COO-. linked together include -(CH₂)₃-, -(CH₂)₄-, -OCO-, -OCONH-, -NHCONH-, -(CH=CH)₂-, -OCH₂O-, -OCH₂CH₂O- and -OC(CH₃)₂O-.

Examples of preferred substituent groups in the compounds represented by the general formula (A) are described below.

R₁ in the general formula (A) is preferably a halogen atom, -COR₄ or -SO₂R₄, and cases where R₄ is an amino group are more desirable. Examples of -COR₄ include a carbamoyl group, an N-ethylcarbamoyl group, an Nn-butylcarbamoyl group, an N-cyclohexylcarbamoyl group, an N-(2-ethylhexyl)carbamoyl group, an n-dodecylcarbamoyl group, an N-hexadecylcarbamoyl group, an N-(3-decyloxypropyl)carbamoyl group, an N-(3-dodecyloxypropyl)carbamoyl group, an N-[3-(2,4-di-t-pentylphenoxy)propyl]carbamoyl group, an N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl group, an N,N-dimethylcarbamoyl group, an N , N-dibutylcarbamoyl group, an N-methyl-N-dodecylcarbamoyl group, morpholinocarbamoyl group, an N-methyl-N-phenylcarbamoyl group, a N-(2-tetradecyloxyphenyl)carbamoyl group, an N-phenylcarbamoyl group, an N-(4-tetradecyloxyphenyl)carbamoyl group, an N-(2-propoxyphenyl)carbamoyl group, an N-(2-chloro-5-dodecyloxyphenyl)carbamoyl group and an N-(2-chlorophenyl)carbamoyl group, and examples of -SO₂R₄ include a sulfamoyl group, an N-methylsulfamoyl group, an N,N-diethylsulfamoyl group, an N,N-diisopropylsulfamoyl group, an N-(3-dodecyloxypropyl)carbamoyl group, an N-[3-(2,4-di-t-pentylphenoxy)propyl]carbamoyl group, an N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl group, a pyrrolidinosulfonyl group, an N-phenylsulfonyl group, an N-(2-butoxyphenyl)carbamoyl group and an N-(2-tetradecyloxyphenyl)carbamoyl group. The -COR₂ groups (wherein R₄ is an amino group) are most desirable for R₁.

l in (R₂)l in the general formula (A) is preferably 0 followed by l' = 1. When l' = 1, R₂ is preferably a halogen atom, an aliphatic group, an aliphatic oxy group, a carbonamido group, a sulfonamido group or a cyano group, and of these, a fluorine atom, a chlorine atom, a trifluoromethyl group, a methoxy group or a cyano group is most desirable. The R₂ group is preferably substituted in the 2-position or the 4-position with respect to the R₃NH group.

R₆ in R₃ of the general formula (A) is preferably an aliphatic group, an aromatic group, -OR₇ or -SR₇, and U is preferably -CO- or -SO₂-. Examples of aliphatic groups include a methyl group, a trifluoromethyl group, a trichloromethyl group, an ethyl group, a heptafluoropropyl group, a t-butyl group, a 1-ethylpentyl group, a cyclohexyl group, a benzyl group, an undecyl group, a tridecyl group, a 1-(2,4-di-t-pentylphenoxy)propyl group, etc., examples of aromatic groups include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-chlorophenyl group, a 4-methoxyphenyl group, a 4-nitrophenyl group and a pentafluorophenyl group. include a methoxy group, an ethoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a t-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a 2-ethylhexyloxy group, an n-decyloxy group, an n-dodecyloxy group, a 2-methoxyethoxy group, a benzyloxy group, a trichloroethoxy group, a trifluoroethoxy group, a phenoxy group and a p-methylphenoxy group, and examples of -SR₇ include a methylthio group, an ethylthio group, an allylthio group, an n-butylthio group, a benzylthio group, an n-dodecylthio group, a phenylthio group, a pt-octylphenylthio group, a p-dodecylphenylthio group and a p-octyloxyphenylthio group. R₃ is preferably an aliphatic oxycarbonyl group (wherein R₆ is an R₇O- group and U is a -CO- group), or an aliphatic or aromatic sulfonyl group (wherein R₆ is an aliphatic or aromatic group and U is a -SO₂- group), and most desirably is an aliphatic oxycarbonyl group.

T in the general formula (A) preferably represents a hydrogen atom, a halogen atom, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group or a heterocyclic thio group. Examples of aliphatic oxy groups include a methoxy group, an ethoxy group, a 2-hydroxyethoxy group, a 2-chloroethoxy group, a carboxymethoxy group, a 1-carboxyethoxy group, a methoxyethoxy group, a 2-(2-hydroxyethoxy)ethoxy group, a 2-methylsulfonylethoxy group, a 2-methylsulfonyloxyethoxy group, a 2-methanesulfonamidoethoxy group, a 2-carboxyethoxy group, a 3-carboxypropoxy group, a 2-(carboxymethylthio)ethoxy group, a 2-(1-carboxytridecylthio)ethoxy group, a 1-carboxytridecyl group, an N-(2-methoxyethyl)carbamoylmethoxy group, a 1-imidazolylmethoxy group and a 5-phenoxycarbonylbenzotriazol-1-ylmethoxy group. Examples of aromatic oxy groups include a 4-nitrophenoxy group, a 4-acetamidophenoxy group, a 2-acetamidophenoxy group, a 4-methylsulfonylphenoxy group and a 4-(3-carboxypropanamido)phenoxy group, examples of aliphatic thio groups include a methylthio group, a 2-hydroxyethylthio group, a carboxymethylthio group, a 2-carboxyethylthio group, a 1-carboxyethylthio group, a 3-carboxypropylthio group, a 2-dimethylaminoethylthio group, a benzylthio group, an n-dodecylthio group and a 1-carboxytridecylthio group, and examples of heterocyclic thio groups include a 1-phenyl-1,2,3,4-tetrazol-5-ylthio group, a 1-ethyl-1,2,3,4-tetrazol-5-ylthio group, a 1-(4-hydroxyphenyl)-1,2,3,4-tetrazol-5-ylthio group, a 4-phenyl-1,2,4-triazol-3-ylthio group, a 5-methyl-1,3,4-oxadiazol-2-ylthio group, a 1-(2-carboxyethyl)-1,2,3,4-tetra zol-5-ylthio group, a 5-methylthio-1,3,4-thiadiazol-2-ylthio group, a 5-methyl-1,3,4-thiadiazol-2-ylthio group, a 5-phenyl-1,3,4-oxadiazol-2-ylthio group, a 5-amino-1,3,4-thiadiazol-2-ylthio group, a benzoxazol-2-ylthio group, a 1-methyl-benzimidazol-2-ylthio group, a 1-(2-dimethylaminophenyl)-1,2,3,4-tetrazol-5-ylthio group, a benzothiazol-2-ylthio group, a 5-(ethoxycarbonylmethylthio)-1,3,4-thiadiazol-2-ylthio group, a 1,2,4-triazol-3-ylthio group, a 4-pyridylthio group and a 2-pyrimidylthio group. More desirably, T is a hydrogen atom, a chlorine atom, an aliphatic oxy group or an aliphatic thio group and most desirably is a hydrogen atom or an aliphatic oxy group.

The couplers represented by the general formula (A) may take the form of a dimer or a larger oligomer linked to each other via divalent groups or groups of higher valence for the substituent groups R₁, R₂, R₃ and T, respectively. In this case, the groups may be outside the specified number of carbon atoms indicated for each of the aforementioned substituent groups.

Cases where the couplers represented by the general formula (A) are in the form of an oligomer are typically homopolymers or copolymers of ethylenically unsaturated addition-polymerizable compounds having a cyan dye-forming coupler residual group (cyan dye-forming monomers). In such a case, the oligomer contains a repeating unit of the general formula (B) and one or more kinds of a cyan color-forming repeating unit represented by the general formula (B) may be contained in the oligomer, and it may be a copolymer containing one or more kinds of a non-color-forming ethylenic monomer as a copolymer component. General formula (B)

In this formula, R₁₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, H represents -CONH-, -COO- or a substituted or unsubstituted phenylene group, I represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, and J represents -CONH-, -NHCONH-, -NHCOO-, -NHCO- , -OCONH-, -NH-, -COO-, -OCO-, -CO-, -O-, -SO₂-, -NHSO₂- or -SO₂NH-. Further, a', b' and c' represent 0 or 1. K represents a cyano coupler residual group in which a hydrogen atom other than the hydrogen atom of the hydroxyl group at the 1-position has been removed from a compound which can be represented by the general formula (A).

Copolymers of cyan color-forming monomers providing a coupler unit of general formula (B) and the non-color-forming ethylenic monomers referred to below are the preferred oligomers.

Non-color-forming ethylenic monomers that do not couple with the oxidation product of primer aromatic amine developing agents include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acids (e.g., methacrylic acid), esters and amides derived from these acrylic acids (e.g., acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, N-methylolacrylamide, N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide, N-(3-sulfonatopropyl)acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, acetoacetoxyethyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, potassium styrene sulfinate, vinyl acetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2-vinylpyridine and 4-vinylpyridine.

The acrylic acid esters, methacrylic acid esters and the maleic acid esters are particularly desirable. Two or more kinds of a non-color-forming ethylenic monomer may be used together. For example, it is possible to use methyl acrylate with butyl acrylate, butyl acrylate with styrene, butyl methacrylate with methacrylic acid, methyl acrylate with diacetone acrylamide, N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide with acrylic acid or potassium styrene sulfinate with N-vinylpyrrolidone.

The ethylenically unsaturated monomer used for copolymerization with the aforementioned vinyl-based monomer corresponding to the general formula (B) may be selected so as to have a favorable effect on the physical and/or chemical properties, e.g. solubility, compatibility with binders such as gelatin used in photographic colloidal compositions, Flexibility and heat resistance of the photographic colloidal compositions of the copolymer which is formed, as is well known in the art of polymer couplers.

Lipophilic non-color-forming ethylenic monomers (e.g. acrylic acid esters, methacrylic acid esters or maleic acid esters) are preferably selected as the main copolymer component in order to obtain lipophilic polymeric couplers that are soluble in organic solvents.

A solution of a lipophilic polymeric coupler obtained by polymerizing a vinyl-based monomer which provides a coupler unit represented by the aforementioned general formula (B) in an organic solvent can be prepared by emulsification and dispersion or by direct emulsification polymerization in the form of a latex in an aqueous gelatin solution.

The method disclosed in U.S. Patent 3,451,820 can be used for emulsification and dispersion of a lipophilic polymeric coupler in the form of a latex in an aqueous gelatin solution, and the method disclosed in U.S. Patents 4,080,211 and 3,370,952 can be used for emulsion polymerization.

Hydrophilic non-color forming ethylenic monomers such as N- (1,1-dimethyl-2-sulfonatoethyl)acrylamide, 3-sulfonatopropyl acrylate, sodium styrenesulfonate, potassium 2-styrenesulfinate, acrylamide, methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone or N-vinylpyridine are preferred copolymer components for obtaining hydrophilic polymeric couplers that are soluble in neutral or alkaline water.

Hydrophilic polymeric couplers can be added as an aqueous solution to a coating liquid, or they can be dissolved in a mixed solution consisting of water and an organic solvent which is miscible with water, such as a lower alcohol, tetrahydrofuran, acetone, ethyl acetone, cyclohexane, ethyl lactate, dimethylformamide or dimethylacetamide, and added in this form. They can also be dissolved in aqueous alkaline solutions or in alkali-containing organic solvents and added in this form. Small amounts of surfactants can also be added.

Actual examples of couplers represented by the general formula (A) which can be used in the present invention are shown below. (weight ratio) (weight ratio)

Examples of couplers other than those mentioned above represented by the general formula (A) that can be used in the present invention have been described in Japanese Patent Application (OPI) Nos. 237448/85, 153640/86 and 145557/86 and Japanese Patent Application No. 42090/87. Furthermore, these couplers can be prepared using the methods described in Japanese Patent Application Nos. 259752/85, 259753/85 and 205344/86 as well as those in the above-mentioned patent specifications.

The couplers represented by the general formula (A) may be added to an emulsion layer or a non-light-sensitive intermediate layer. Preferably they are added to an emulsion layer.

The amount added is 0.01 mol% to 100 mol%, preferably 0.1 mol% to 50 mol%, and most desirably 1 mol% to 20 mol% based on the total amount of silver deposited.

The compounds used in the present invention which release a bleaching accelerator are described in detail below.

The compounds represented by the following general formula (I) are preferred as the compounds releasing a bleaching accelerating agent in the present invention.

A-(L)p-Z (I)

wherein A represents a group whose bond to (L)pZ is cleaved by reaction with the oxidized product of the developing agent, L represents a timing group or a group whose bond to Z is cleaved by reaction with the oxidized product of the developing agent, p represents an integer from 0 to 3, and when p is 2 or 3, the p individual L groups may be the same or different, and Z means a group which, when the bond to A-(L)p has been cleaved, has a bleaching accelerating effect.

Further, compounds represented by the following general formula (I') are preferred.

A-(L₁)a-(L₂)b-Z (I')

wherein A represents a group whose bond to (L₁)a-(L₂)b-Z is cleaved by reaction with the oxidized product of the developing agent, L₁ represents a timing group or a group whose bond to (L₂)b-Z is cleaved by reaction with the oxidized product of the developing agent, L₂ represents a timing group or a group whose bond to Z is cleaved by reaction with the oxidized product of the developing agent, Z represents a group which, when the bond to A-(L₁)a-(L₂)b has been cleaved, has a bleaching-accelerating effect, and a and b each represent a value of 0 or 1.

More precisely, A in the general formulas (I) and (I') represents a coupling residue group or a redox group.

Known coupler residue groups can be used for the coupler residue group represented by A. For example, it may be a yellow coupler residue group (e.g., an open-chain ketomethylene coupler residue group), a magenta coupler residue group (e.g., a 5-pyrazolone type, pyrazolimidazole type or pyrazolotriazole type coupler residue group), a cyan coupler residue group (e.g., a phenol type or naphthol type coupler residue group), or a colorless coupler residue group (e.g., an indanone type or acetophenone type coupler residue group). Further, it may be a heterocyclic type coupler residue group described in U.S. Patents 4,315,070, 4,183,752, 3,961,959 or 4,171,223. When A in the general formula (I') represents a coupler residue group, the preferred examples of A are the coupler residue groups represented by the following general formula (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9) or (Cp-10). These couplers preferably have a high coupling rate.

general formula (Cp-1)

R₅₁₁ H NH-R₅₂

general formula (Cp-2)

R₅NH H NHR₅₃ general formula (Cp-3) general formula (Cp-4) general formula (Cp-5) general formula (Cp-6) general formula (Cp-7) general formula (Cp-8) general formula (Cp-9) general formula (Cp-10)

In the formulas shown previously, the free bond extending from the coupling position indicates the bond position of the coupling elimination group.

In cases where a diffusion resistant group of R₅₁, R₅₂, R₅₃, R₅₄, R₅₅, R₅₆, R₅₃, R₅₆, R₅₇, R₅₄, R₅₆, R₅₇, R₅₆, R₅₆, R₅₆, R₅₆, R₅₆, R₅₆, in the formulas indicated above, it is selected so that the total number of carbon atoms is from 8 to 40 and preferably from 10 to 30, and in other cases the total number of carbon atoms is preferably not more than 15. In the case of a bis-type, telomeric or polymeric coupler, any of the substituent groups mentioned above may represent the divalent group connecting the repeating units. In this case, the number of carbon atoms may be outside the range indicated above.

R₅₁₁ - R₆₃, d and e are described in detail below.

Here, R₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R₄₂ represents an aromatic group or a heterocyclic group, and R₄₃, R₄₄ and R₄₅ represent hydrogen atoms, aliphatic groups, aromatic groups or heterocyclic groups.

R₅₁₁ has the same meaning as R₄₁. R₅₂ and R₅₃ each have the same meaning as R₄₂. R₅₄ represents a group with the same meaning as R₄₁, a

an R₄₁S group, an R₄₃O group, an

or an N C group. R₅₅ represents a group having the same meaning as R₄₁.

R₅₆ and R₅₇ each represent groups having the same meaning as R₄₃ or an R₄₁S group, an R₄₃-O group, a

R₅₈ represents a group having the same meaning as R₄₁.

R₅�9 represents a group having the same meaning as R₄₁, a

an R₄₁O group, an R₄₁S group, a halogen atom or a

Furthermore, d means a value from 0 to 3.

When d is greater than 1, the majority of R₅₉ groups represent the same substituent group or different substituent groups. Further, the R₅₉ groups may be divalent groups which are bonded together to form a ring structure. The groups shown below are typical examples of divalent groups for forming ring structures.

Here, f means an integer from 0 to 4 and g means an integer from 0 to 2.

R₆₀₀ represents a group having the same meaning as R₄₁. R₆₁ represents a group having the same meaning as R₄₁. R₆₂ represents a group having the same meaning as R₄₁, an R₄₁CONH-, an R₄₁OCONH-, an R₄₁SO₂NH-, an

an R₄₃O group, an R₄₁S group, a halogen atom or a

R₆₃ represents a group having the same meaning as R₄₁, a

one

an R₄₁SO₂ group, an R₄₁OCO group, an R₄₁SO₂ group, a halogen atom, a nitro group, a cyano group or an R₄₃CO group. Furthermore, e represents an integer of 0 to 4. When two or more R₆₂ or R₆₃ groups are present, they may represent the same group or different groups.

In the foregoing description, the aliphatic group is a saturated or unsaturated, a chain or cyclic, a linear or branched, a substituted or unsubstituted aliphatic group having 1 to 32, preferably 1 to 22, carbon atoms. Typical examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, an isobutyl group, a t-amyl group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, an octyl group, a 1,1,3,3-tetrabutylmethyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group.

The aromatic group is preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group having 6 to 20 carbon atoms.

The heterocyclic group is a substituted or unsubstituted, preferably 3- to 8-membered, heterocyclic group in which the heteroatoms are selected from a nitrogen atom, an oxygen atom or a sulfur atom, and which has 1 to 20, and preferably 1 to 7, carbon atoms. Typical examples of heterocyclic groups include a 2-pyridyl group, a 2-thienyl group, a 2-furyl group, a 1-imidazolyl group, a 1-indolyl group, a phthalimido group, a 1,3,4-thiadiazol-2-yl group, a 2-quinolyl group, a 2,4-dioxo-1,3-imidazolidin-5-yl group, a 2,4-dioxo-1,3-imidazolidin-3-yl group, a succinimido group, a 1,2,4-triazol-2-yl group or a 1-pyrazolyl group.

When the aforementioned aliphatic groups, aromatic groups and heterocyclic groups have substituent groups, the substituent groups may be, for example, halogen atoms, R₄₇O groups, R₄₆S groups,

R₄�6SO₂ groups, R₄�7OCO groups,

Groups having the same meaning as R₄₆,

R₄�6COO groups, R₄�7OSO₂ groups, cyano groups or nitro groups. Here, R₄�6 represents an aliphatic group, an aromatic group or a heterocyclic group and R₄�7, R₄�8 and R₄�9 each represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. The meaning of the terms an aliphatic group, an aromatic group and a heterocyclic group is the same as defined above. The preferred ranges for R₅₁ to R₆₁, d and e are described below.

R₅₁ is preferably an aliphatic group or an aromatic group. R₅₂, R₅₃ and R₅₅ are preferably aromatic groups. R₅₄ is preferably a R₅₁CONH group or a

R₅₆ and R₅₇ are preferably aliphatic groups, R₄₁-O-groups or R₄₁S-groups.

R₅�8 is preferably an aliphatic group or an aromatic group. In the general formula (Cp-6), R₅�9 is preferably a chlorine atom, an aliphatic group or an R₄₁CONH group, and d is preferably 1 or 2. R₆₀ is preferably an aromatic group. In the general formula (Cp-7), R₅�9 is preferably an R₄₁CONH group. In the general formula (Cp-7), d is preferably 1. R₆₁ is preferably an aliphatic group or an aromatic group. In the general formula (Cp-8), e is preferably 0 or 1. For R₆₂ an R₄₁OCONH group, an R₄₁CONH group or an R₄₁SO₂NH group is preferred, and these are preferably substituted in the 5-position of the naphthol ring. In the general formula (Cp-9), R₆₃ is preferably an R₄₁CONH group, an R₄₁SO₂NH group, an

an R₄₁SO₂ group, a

a nitro group or a cyano group.

In the general formula (Cp-10), R₆₃ is preferably a

an R₄₃OCO group or an R₄₃CO group.

Typical examples of R₅₁₁ to R₆₃ are described below.

R₅₁ may be a t-butyl group, a 4-methoxyphenyl group, a phenyl group, a 3-{2-(2,4-di-t-amylphenoxy)butanamido}phenyl group or a methyl group. R₅₂ and R₅₃ can be 2-chloro-5-dodecyloxycarbonylphenyl groups, 2-chloro-5-hexadecylsulfonamidophenyl groups, 2-chloro-5-tetradecanamidophenyl groups, 2-chloro-5-{4-(2,4-di-t-amylphenoxy)butanamido}phenyl groups, 2-chloro-5-{2-(2,4-di-t-amylphenoxy)butanamido}phenyl groups, 2-methoxyphenyl groups, 2-methoxy- 5-tetradecyloxycarbonylphenyl groups, 2-chloro-5-(1-ethoxycarbonyl-ethoxycarbonyl)phenyl groups, 2-pyridyl groups, 2-chloro-5-octyloxycarbonylphenyl groups, 2,4-dichlorophenyl groups, 2-chloro-5-(1-dodecyloxycarbonylethoxy-carbonyl)phenyl groups, 2-chlorophenyl groups or 2-ethoxyphenyl groups.

R₅₄ may be a 3-{2-(2,4-di-t-amylphenoxy)butanamido}benzamido group, a 3-{4-(2,4-di-t-amylphenoxy)butanamido}benzamido group, a 2-chloro-5-tetradecanamidoanilino group, a 5-(2,4-di-t-amylphenoxyacetamido)benzamido group, a 2-chloro-5-dodecenylsuccinimidoanilino group, a 2-chloro-5-{2-(3-t-butyl-4-hydroxyphenoxy)tetradecanamido}anilino group, a 2,2-dimethylpropanamido group, a 2-(3-pentadecylphenoxy)butanamido group, a pyrrolidino group or an N,N-dibutylamino group. R₅₄ is preferably a 2,4,6-trichlorophenyl group, a 2-chlorophenyl group, a 2,5-dichlorophenyl group, a 2,3-dichlorophenyl group, a 2,6-dichloro-4-methoxyphenyl group, a 4-{2-(2,4-di-t-amylphenoxy)butanamido}phenyl group or a 2,6-dichloro-4-methanesulfonylphenyl group. R₅₆ may be a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a 3-phenylureido group or a 3-(2,4-di-t-amylphenoxy)propyl group. R₅₇ may be a 3-(2,4-di-t-amylphenoxy)propyl group, a 3-[4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]tetradecanamido}phenyl]propyl group, a methoxy group, a methylthio group, an ethylthio group, a methyl group, a 1-methyl-2-(2-octyloxy-5-[2-octyloxy-5-(1,1,3,3-tetramethylbutyl)phenylsulfonamido]phenylsulfonamido)ethyl group, a 3-{4-(4-dodecyloxyphenylsulfonamido)phenyl}propyl group, a 1,1-dimethyl-2-(2-octyloxy-5-(1,1,3,3-tetramethylbutyl)phenylsulfonamido]ethyl group or a dodecylthio group. R₅�8 may be a 2-chlorophenyl group, a pentafluorophenyl group, a pentafluoropropyl group, a 1-(2,4-di-t-amylphenoxy)propyl group, a 3-(2,4-di-t-amylphenoxy)propyl group, a 2,4-di-t-amylphenoxymethyl group or a furyl group. R₅�9 may be a chlorine atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a 2-(2,4-di-t-amylphenoxy)butanamido group, a 2-(2,4-di-t-amylphenoxy)hexanamido group, a 2-(2,4-di-t-octylphenoxy)octanamido group, a 2-(2-chlorophenoxy)tetradecanamido group, a 2-{4-(4-hydroxyphenylsulfonyl)phenoxy}tetradecanamido group or a 2-{2-(2,4-di-t-amylphenoxyacetamino)phenoxy}butanamido group. R₆₀ may be a 4-cyanophenyl group, a 2-cyanophenyl group, a 4-butylsulfonylphenyl group, a 4-propylsulfonylphenyl group, a 4-chloro-3-cyanophenyl group, a 4-ethoxycarbonylphenyl group or a 3,4-dichlorophenyl group. R₆₁ may be a 4-cyanophenyl group, a 2-cyanophenyl group, a 4-butylsulfonylphenyl group, a 4-propylsulfonylphenyl group, a 4-chloro-3-cyanophenyl group, a 4-ethoxycarbonylphenyl group or a 3,4-dichlorophenyl group. may be a dodecyl group, a hexadecyl group, a cyclohexyl group, a 3-(2,4-di-t-amylphenoxy)propyl group, a 4-(2,4-di-t-amylphenoxy)butyl group, a 3-dodecyloxypropyl group, a t-butyl group, a 2-methoxy-5-dodecyloxycarbonylphenyl group or a 1-naphthyl group. R₆₂ may be an iso-butyloxycarbonylamino group, an ethoxycarbonylamino group, a phenylsulfonylamino group, a methanesulfonamido group, a benzamido group, a trifluoroacetamido group, a 3-phenylureido group, a butoxycarbonylamino group or an acetamido group. R₆₃ may be a 2,4-di- t-amylphenoxyacetamido group, a 2-(2,4-di- t-amylphenoxy)butanamido group, a hexadecanesulfonamido group, an N-methyl-N-octadecylsulfamoyl group, an N,N-dioctylsulfamoyl group, a 4-t-octylbenzoyl group, a dodecyloxycarbonyl group, a chlorine atom, a nitro group, a cyano group, an N-{4-(2,4-di-t-amylphenoxy)butyl}carbamoyl group, a N-3-(2,4-di-t-amylphenoxy)propylsulfamoyl group, a methanesulfonyl group or a hexadecylsulfonyl group.

When A in the general formula (I) represents a redox group, it is more specifically a group that can be represented by the general formula (II) below.

A₁-P-(X=Y)n-Q-A₂ (II)

In this formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, at least one of the n individual X and Y groups represents a methine group having a group -(L₁)a-(L₂)b-Z as a substituent, and the other X and Y groups represent substituted or unsubstituted methine groups or nitrogen atoms, n represents an integer of 1 to 3 (representing n individual X and n individual Y groups which are the same or different), and A₁ and A₂ each represent hydrogen atoms or groups which can be split off with alkali. Here, cases where any two substituent groups P, X, Y, Q, A₁ and A₂ are used as the formula. are divalent and are linked together to form a ring structure. For example, (X=Y)n can form a benzene ring or a pyridine ring.

When P and Q represent substituted or unsubstituted imino groups, the imino groups are preferably substituted with sulfonyl groups or acyl groups.

Then P and Q can be represented by the following general formulas:

Here, * indicates the position where the group is bonded to A₁ or A₂, and ** indicates the position of one of the dangling bonds of the (X=Y)n group.

In these formulas, the group represented by G is preferably a straight-chain, branched or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 32, and preferably 1 to 22 carbon atoms (e.g. a methyl group, an ethyl group, a benzyl group, a phenoxybutyl group or an isopropyl group), a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms (e.g. a phenyl group, a 4-methylphenyl group, a 1-naphthyl group or a 4-dodecyloxyphenyl group), or a 4- or 7-membered heterocyclic group whose heteroatom is selected from a nitrogen atom, a sulfur atom or an oxygen atom (e.g. a 2-pyridyl group, a 1-phenyl-4-imidazolyl group, a 2-furyl group or a benzothienyl group).

P and Q in the general formula (II) are preferably each independently oxygen atoms or groups which can be represented by the general formula (N-1).

When A₁ and A₂ represent groups which can be cleaved with alkali (hereinafter referred to as "precursor groups"), they are preferably groups which can be hydrolyzed such as acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups or sulfonyl groups, precursor groups of the type for which a reverse Michael reaction is used as described in US Patent 4,009,029, precursor groups of the type for which an anion formed after ring-opening cleavage is used as an intramolecular nucleophilic group as described in US Patent 4,310,612, precursor groups in which an anion transfers an electron via a conjugated system, thereby causing a cleavage reaction as described in US Patents 3,674,478, 3,932,480 or 3,993,661, precursor groups in which a cleavage reaction is effected by the electron transfer of an anion reacted after ring-opening cleavage as described in U.S. Patent 4,335,200, or a precursor group utilizing an imidomethyl group as described in U.S. Patents 4,363,865 or 4,410,618.

In the general formula (II), P preferably represents an oxygen atom and A₂ preferably represents a hydrogen atom.

Further, in the general formula (II), X and Y are preferably substituted or unsubstituted methine groups, except for X and Y groups which are methine groups having -(L₁)a-(L₂)b-Z as a substituent group.

Of the groups which can be represented by the general formula (II), those which can be represented by the following general formulas (III) and (IV) are particularly desirable.

In these formulas, * indicates the position to which the -(L₁)a(L₂)bZ group is bonded, and P, Q, A₁ and A₂ have the same meaning as described in connection with the general formula (II). Further, R₆₄ represents a substituent group, and q represents 0 or an integer of 1 to 3. When q is 2 or 3, the 2 or 3 R₆₄ groups may be the same or different, and when the R₆₄ groups are substituent groups on adjacent carbon atoms, cases where they are divalent groups and are bonded to each other to form a ring structure are also included. In such a case, a condensed benzene ring can be formed to give, for example, ring structures such as naphthalenes, benzonorbornanes, chromanes, indoles, benzothiophenes, quinolines, benzofurans, 2,3-dihydrobenzofurans, indanes and indenes, and these may have one or more substituent groups. Examples of preferable substituent groups when substituent groups are present on these condensed rings and preferable examples of R₆₄ when R₆₄ does not form a condensed ring are given below. That is, these groups include an R₄₁ group, halogen atoms, an R₄₃O group, an R₄₃S group, a

an R₄₃OOC group, an R₄₁SO₂ group, an

an R₄₃CO group, an R₄₁COO group, an

a cyano group or a

Here, R41, R43, R44 and R45 have the same meaning as described above. Typical examples of R64 are given below. That is, a methyl group, an ethyl group, a t-butyl group, a methoxy group, a methylthio group, a dodecylthio group, a 3-(2,4-di-t-amylphenoxy)propylthio group, an N-3-(2,4-di-t-amylphenoxy)propylcarbamoyl group, an N-methyl-N-octadecyloxycarbamoyl group, a methoxycarbonyl group, a dodecyloxycarbonyl group, a propylcarbamoyl group, a hydroxyl group or an N,N-dioctylcarbamoyl group. An example of a case where two R₆₄ groups form a ring is provided by the group shown below:

P and Q preferably represent oxygen atoms in the general formulas (III) and (IV).

A₁ and A₂ preferably represent hydrogen atoms in the general formulas (III) and (IV).

The groups represented by L₁ and L₂ in the general formula (I') may or may not be used in the invention. They are not preferably used, but they may be suitably selected for a particular purpose. When L₁ and L₂ represent timing groups, they may consist of the well-known linking groups given below.

(1) Groups where a hemiacetal cleavage reaction is applied.

These have been described, for example, in US Patent 4,146,396 and Japanese Patent Application (OPI) Nos. 249148/85 and 249149/85, and they are groups that can be represented by the general formula given below. Here, * indicates the position bonded to the left side in the general formula (II), and ** indicates the Position bound to the right-hand side in formula (II).

In this formula, W represents an oxygen atom, a sulfur atom or a

R₆₅ and R₆₆ represent hydrogen atoms or substituted groups, R₆₇ represents a substituent group, and t represents 1 or 2. When t is 2, the two

be the same or different.

Typical examples of R₆₅ and R₆₆ as substituent groups and of R₆₇ are an R₆�9 group, an R₆�9CO group, an R₆�9SO₂ group, a

Here, R₆₉ is a group having the same meaning as R₄₁ described above, and R₇₀ is a group having the same meaning as R₄₃.

Cases in which R 65 , R 66 and R 67 each represent divalent groups and they are bonded together to form a ring structure are also included. The groups shown below are actual examples of groups which can be represented by the general formula (T-1).

(2) Groups in which a cleavage reaction is effected using an intramolecular nucleophilic substitution reaction.

For example, the timing groups described in U.S. Patent 4,248,962. These can be represented by the general formula (T-2) given below.

*-Nu-Link-E-** (T-2)

In this formula, * indicates the position where it is bonded to the left side in the general formula (II), and ** indicates the position where it is bonded to the right side in the general formula (II), Nu means a nucleophilic group, an oxygen atom or a sulfur atom being examples of nucleophilic species, E means an electrophilic group which is a group which is nucleophilically attacked by Nu and which can cleave the bond marked by **. Further, Link means a linking group which provides such a steric arrangement that Nu and E can undergo an intramolecular nucleophilic substitution reaction. Actual examples of groups which can be represented by the general formula (T-2) are shown below.

(3) Groups in which a cleavage reaction is effected using an electron transfer reaction via a conjugated system.

For example, those described in US Patent 4,409,323 or 4,421,845 are groups that can be represented by the general formula (T-3) given below.

In this formula, *, **, W, R65, R66 and t have the same meaning as in the general formula (T-1).

Groups such as those listed below are current examples of such groups.

(4) Groups where a cleavage reaction due to the hydrolysis of an ester is used.

For example, linking groups described in West German Patent Application (OLS) No. 2,626,315 are groups as indicated below. In these formulas, * and ** have the same meaning as described in connection with the general formula (T-1).

*-O- ** (T-4) *-S- -** (T-5)

(5) Groups where an iminoketal cleavage reaction is applied.

For example, the linking groups described in US Patent 4,546,073 are groups represented by the formula (T-6) below.

In this formula, *, ** and W have the same meaning as described in connection with the general formula (T-1), and R₆�8 represents a group having the same meaning as R₆₇. The following groups are actual examples of groups that can be represented by the general formula (T-6).

When the group represented by L₁ in the general formula (I') is a group which reacts with the oxidized product of the developing agent after the splitting off of A and from which the group (L₂)b-Z will split off, it is more specifically a group which forms a coupler or a group which forms a redox group after splitting off A. Similarly, when the group represented by L₂ is a group which reacts with the oxidized product of the developing agent after the splitting off of the A'(L₁)b group with the splitting off of the Z group, it is more specifically a group which forms a coupler or a group which forms a redox group after splitting off A'(L₁)b.

The groups that form couplers, for example, in the case of a phenol coupler, are those in which A-, or A- (L₁)b- are bonded to an oxygen atom obtained by removal of the hydrogen atom of a hydroxyl group. Furthermore, in the case of 5-pyrazolone couplers, they are those in which A- or A-(L₁)b- are bonded to an oxygen atom obtained by removal of a hydrogen atom from the hydroxyl group of the tautomeric 5-hydroxypyrazole form. In these examples, a phenol coupler or 5-pyrazolone coupler is formed starting from the elimination of A- or A-(L₁)b-, respectively. These have (L₂)b-Z or Z at the coupling position.

When L₁ and L₂ represent groups which become couplers, they are preferably groups which can be represented by the following general formulas (V), (VI), (VII) or (VIII). In these formulas, * indicates the position of the bond on the left side in the general formula (I'), and ** indicates the position of the bond on the right side.

In these formulas, V₁ and V₂ represent substituent groups, V₃, V₄, V₅ and V₆ represent nitrogen atoms or substituted or unsubstituted methine groups, V₇ represents a substituent group, and x represents an integer of 0 to 4. When x is 2 or more, the V7 groups may be the same or different, and two V7 groups may be bonded together to form a ring structure. V8 represents a -CO- group, a -SO2- group, an oxygen atom, a substituted imino group, V9 represents a group of non-metal atoms to form a 5- to 8-membered ring in combination with

and V₁₀ represents a hydrogen atom or a substituent group. However, V₁ and V₂ may each be a divalent group and may combine with each other to form a 5- to 8-membered ring in combination with

be.

V₁ preferably represents an R₇₁₁ group and an R₇₂ group, an R₇₂CO group, a

an R₇₂SO₂ group, an R₇₂S group, an R₇₂O group or a

are preferred examples of the V₂ group. Examples of rings formed by joining V₁ and V₂ include indenes, indoles, pyrazoles and benzothiophenes.

When V3, V4, V5 or V6 is a substituted methine group, preferred substituent groups are an R71 group, an R73O group, an R71S group or an R71CONH group.

halogen atoms, an R₇₁₁ group, an R₇₁₁CONH group, an R₇₁₁SO₂NH group, an R₇₃O group, an R₇₁₁S group, an

an R₇₁₁CO group and an R₇₃OOC group are preferred examples of V₇. Examples of ring structures formed by connecting multiple V₇ groups include naphthalenes, quinolines, oxyindoles, Benzodiazipine-2,4-diones, benzimidazole-2-ones and benzothiophenes.

When V₈ represents a substituted imino group, it is preferably an R₇₃N group.

Preferred ring structures represented by V�9 with

are indoles, imidazolinones, 1,2,5-thiadiazolin-1,1-dioxides, 3-pyrazolin-5-ones, 3-iso-oxazolin-5-ones or rings of the type shown below.

An R₇₃ group, an R₇₃O group, an and an R₇₁₁S group are preferred examples of V₁₀.

R₇₁₁ and R₇₂₂ in the above description represent aliphatic groups, aromatic groups or heterocyclic groups, and R₇₃, R₇₄ and R₇₅ represent hydrogen atoms, aliphatic groups, aromatic groups or heterocyclic groups. Here, aliphatic groups, aromatic groups and heterocyclic groups have the same meaning as previously described in connection with R₄₁. However, the total number of carbon atoms contained in these groups is preferably not more than 10.

The groups listed below are typical examples of groups that can be represented by the general formula (V).

The following groups are typical examples of groups that can be represented by the general formula (VI).

The following groups are typical examples of groups that can be represented by the general formula (VII).

The following groups are typical examples of groups that can be represented by the general formula (VIII).

Groups that can be represented by the following general formula (IX) are preferred when the groups represented by L₁ and L₂ in the general formula (I') are groups that become redox groups.

*P'-(X'=Y')n'-Q'-A'2 (IX)

In this formula, * indicates the position where the group is bonded to the left side in the general formula (I), A'₂, P', Q' and n' have the same meaning as A₂, P, Q and n respectively as previously described in connection with the general formula (II), at least one of the n' individual X' groups and n' individual Y' groups represents a methine group having -(L₂)-Z or Z as a substituent group, and the other X' and Y' groups are substituted or unsubstituted methine groups or nitrogen atoms. Cases where any two substituent groups A'₂, P', Q', X' and Y' are divalent groups and a ring structure is formed are also included here. Ring structures of this type are, for example, benzene rings or pyridine rings.

P' in the general formula (IX) preferably represents an oxygen atom, and Q' preferably represents an oxygen atom or one of the groups shown below. Here, * indicates the free bond bonded to (X'=Y')n', and ** indicates the free bond bonded to A'₂.

In these formulas, G' has the same meaning as G previously described in connection with the general formulas (N-1) and (N-2).

Q' is most desirably an oxygen atom or a group which is

can be displayed.

The groups which can be represented by the following general formulas (X) and (XI) are particularly preferred among the groups which can be represented by the general formula (IX).

In these formulas, * indicates the position of the bond on the left side to L₁ or L₂ in the general formula (I), and ** indicates the position of the bond on the right side. R₇₆ has the same meaning as R₆₄ described in connection with the general formula (III) or the general formula (IV). Furthermore, y represents an integer of 0 to 3, and when y is 2 or more, the R₇₆ groups may be the same or different. Further, cases where two R₇₆ groups are bonded together to form a ring structure are also included.

The groups indicated below are particularly desirable examples of R₇₆. That is, alkoxy groups (e.g. a methoxy group or an ethoxy group), acylamino groups (e.g. an acetamido group or a benzamido group), sulfonamido groups (e.g. a methanesulfonamido group or a benzenesulfonamido group), alkylthio groups (e.g. a methylthio group or an ethylthio group), carbamoyl groups (e.g. an N-propylcarbamoyl group, an Nt-butylcarbamoyl group or an N-iso-propylcarbamoyl group), alkoxycarbonyl groups (e.g. a methoxycarbonyl group or a propoxycarbonyl group), aliphatic groups (e.g. a methyl group or a t-butyl group), halogen atoms (e.g. a fluorine group or a chlorine group), sulfamoyl groups (e.g. an N-propylsulfamoyl group or a sulfamoyl group), acyl groups (e.g. an acetyl group or a benzoyl group), a hydroxyl group and a carboxyl group. In addition, a typical example of a case where two R₇₆ groups are bonded together to form a ring structure is shown below: (here, * and ** have the same meaning as described in connection with the general formula (IX).

The group represented by Z in the general formula (I') is a known bleach accelerator residual group. For example, it may be one of the many mercapto compounds described in the U.S. Patent 3,893,858, British Patent No. 1,138,842 or Japanese Patent Application (OPI) No. 141623/78, a compound having a disulfide bond described in Japanese Patent Application (OPI) No. 95630/78, a thiazolidine derivative described in Japanese Patent Application (OPI) No. 9854/78, an iso-thiourea derivative described in Japanese Patent Application (OPI) No. 94927/78, a thiourea derivative described in Japanese Patent Application (OPI) No. 8506/70 or 26586/74, a thioamido compound described in Japanese Patent Application (OPI) No. 42349/74, a dithiocarbamic acid salt described in Japanese Patent Application (OPI) No. 26506/80, or an arylenediamine compound described in U.S. Patent 4,552,834. Those of these compounds in which the A-(L₁)a-(L₂)b group in the general formula (I') is bonded to a substitutable heteroatom contained in the molecule are preferred.

The group represented by Z is most desirably a group which can be represented by the general formulas (XII), (XIII) or (XIV) below.

In these formulas, * indicates the position of the bond with A'(L₁)a-(L₂)b-, R₃₁ represents a divalent aliphatic group having 1 to 8 and preferably 1 to 5 carbon atoms, R₃₂ represents a group having the same meaning as R₃₁, a divalent aromatic group having 6 to 10 carbon atoms, or a 3- to 8-membered and preferably a 5- or 6-membered divalent heterocyclic group. X₁ represents an -O- group, an -S- group, a -COO- group, an -SO₂- group, a a -S- -group, - - group, a

X₂ represents an aromatic group having 6 to 10 carbon atoms, X₃ represents a 3- to 8-membered, and preferably a 5- or 6-membered heterocyclic group having at least one carbon atom bonded to sulfur within the ring, Y₁ represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, a phosphonic acid group or a salt thereof, an amino group (which may be substituted with an aliphatic group(s) having 1 to 4 carbon atoms), a -NHSO₂-R₃₅ group or a -SO₂NH-R₃₅ group (here, the term salt represents a salt such as a sodium salt, a potassium salt or an ammonium salt), Y₂ represents a group having the same meaning as for Y₁ or a hydrogen atom, r means 0 or 1, l means an integer from 0 to 4, m means an integer from 1 to 4 and u means an integer from 0 to 4. In addition, the m individual Y₁ groups are bonded to each of the substitutable positions of R₃₁{(X₁)rR₃₂}l, X₂{(X₁)rR₃₂}l and X₃{(X₁)rR₃₂}l, and when m is 2 or more, the m individual Y₁ groups may be the same or different, and when l is 2 or more, the l individual {(X₁)rR₃₂} groups may be the same or different. Here, R₃₃, R₃₄ and R₃₅ each represent a hydrogen atom or an aliphatic group having 1 to 8, and preferably 1 to 5, carbon atoms. When R₃₁ When R₃ to R₃₅ are aliphatic groups, they may be chain or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic groups. Unsubstituted groups are preferred, but they may have, for example, halogen atoms, alkoxy groups (eg methoxy groups, ethoxy groups) or alkylthio groups (eg methylthio groups, ethylthio groups) as substituent groups.

The aromatic groups represented by X2 and the aromatic groups when R32 represents an aromatic group may have substituent groups. For example, they may have the previously mentioned substituents enumerated as the substituent groups for the aliphatic group.

The heterocyclic groups represented by X3 and the heterocyclic groups when R2 represents a heterocyclic group are saturated or unsaturated, substituted or unsubstituted heterocyclic groups having oxygen atoms, sulfur atoms or nitrogen atoms as heteroatoms. For example, they may be pyridine rings, imidazole rings, piperidine rings, oxylane rings, suphorane rings, imidazolidine rings, thiazipine rings or pyrazole rings. The previously mentioned groups which have been enumerated as substituent groups for aliphatic groups may also be substituent groups in this case.

Actual examples of groups that can be represented by the general formula (XII) are shown below.

Actual examples of groups that can be represented by the general formula (XIII) are given below.

Actual examples of groups that can be represented by the general formula (XIV) are given below.

The compounds of the present invention which can be represented by the general formula (I') also include dimers, telomers and polymers. For example, in the case of polymers, they are polymers derived from monomers which can be represented by the general formula (XV) and having a repeating unit which can be represented by the general formula (XVI), and copolymers having at least one kind of non-color-forming monomer containing at least one ethylenic group which cannot couple with the oxidized product of a primary aromatic amine developing agent. Here, two or more monomers which can be represented by the general formula (XV) can be simultaneously polymerized.

In these formulas, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom. A₁₁ represents -CONH-, -NHCONH-, -NHCOO-, -COO-, -SO₂-, -CO-, -NHCO-, -SO₂NH-, -NHSO₂-, -OCO-, -OCONH-, -NH- or -O-, A₁₂ represents -CONH- or -COO-, and A₁₃ represents an unsubstituted or a substituted alkylene group, an aralkylene group, or an unsubstituted or substituted arylene group having 1 to 10 carbon atoms, and the alkylene groups may be either linear chain or branched. (Examples of alkylene groups include methylene groups, methylmethylene groups, dimethylmethylene groups, dimethylene groups, trimethylene groups, tetramethylene groups, pentamethylene groups, hexamethylene groups, decylmethylene groups, the aralkylene groups include e.g. benzylidene groups, and arylene groups include e.g. phenylene groups and naphthyline groups.

QQ represent the residues of compounds which can be represented by the general formula (I'), and these can be bonded to any position of the substituent groups described above, with the exception of the group represented by Z.

Furthermore, i, j and k mean 0 or 1, but i, j and k cannot be 0 at the same time.

The substituents for the alkylene groups, aralkylene groups and arylene groups which can be represented by A₁₃ include aryl groups (e.g. phenyl groups), nitro groups, hydroxyl groups, cyano groups, sulfo groups, alkoxy groups (e.g. methoxy groups), aryloxy groups (e.g. phenoxy groups), acyloxy groups (e.g. acetoxy groups), acylamino groups (e.g. acetylamino groups), sulfonamido groups (e.g. methanesulfonamido groups), sulfamoyl groups (e.g. methylsulfamoyl groups), halogen atoms (e.g. fluorine atoms, chlorine atoms or bromine atoms), carboxyl group, carbamoyl groups (e.g. methylcarbamoyl groups), Alkoxycarbonyl groups (e.g. methoxycarbonyl groups) and sulfonyl groups (e.g. methylsulfonyl groups). When two or more of these substituent groups are present, they may be the same or different. The non-color-forming ethylenic monomer which does not undergo a coupling reaction with the oxidation products of a primary aromatic amine developing agent may be an acrylic acid, an α-chloroacrylic acid, an α-alkylacrylic acid or an ester or an amide derived from these acrylic acids, methylenebisacrylamide, a vinyl ester, acrylonitrile, an aromatic vinyl compound, a maleic acid derivative or a vinylpyridine. Two or more kinds of non-color-forming ethylenic unsaturated monomers used here may be used simultaneously.

Cases where any two of the groups represented by A, L₁, L₂ and Z in the general formula (I') have free bonds other than the free bonds shown in the general formula (I') are included in the invention. The effect of the invention can be achieved even if the second free bond is not cleaved during development. Examples of these free bonds are given below.

The most desirable examples of the above-mentioned forms are those which can be represented by the general formula (XVII) below.

In this formula, L2, b, Z, R58 and R59 have the same meaning as previously described, h and v each represent 0 or 1, and A14 represents a divalent organic radical forming a 5- to 8-membered ring.

Examples of A₁₄ include a

Actual examples of compounds capable of releasing a bleach accelerator that can be used in accordance with the invention are given below.

The compounds described in Research Disclosure Item Nos. 24241 and 11449, Japanese Patent Application (OPI) No. 201247/86, and Japanese Patent Application Nos. 252847/86, 268870/86, and 268871/86 can be used in the same manner.

In addition, the bleach accelerator-releasing compounds used in the present invention can be easily prepared following the descriptions in the aforementioned patent specifications.

The amount of the bleach accelerator-releasing compound of the present invention added to the photosensitive material is preferably 1 x 10-7 mol to 1 x 10-1 mol, and most desirably 1 x 10-6 mol to 5 x 10-2 mol, per square meter of photosensitive material. The bleach accelerator-releasing compounds of the present invention can be added to all layers of a photosensitive material, but they are preferably added to the photosensitive emulsion layers, and the effect becomes more pronounced when they are added to more of the photosensitive emulsion layers. When they are added to a non-photosensitive layer, a side effect such as decrease in sensitivity can be reduced.

The silver halide color photographic materials used in the present invention are described below. Any silver halide such as silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride or silver chloroiodide can be used for the emulsion layers of the light-sensitive material. However, the use of silver iodobromide is particularly desirable. When silver iodobromide is used, the silver iodine content is usually not more than 40 mol%, preferably not more than 20 mol%.

The aforementioned silver halide grains may be so-called regular grains having a regular crystalline shape such as a cubic, octahedral or tetradecahedral shape, or they may have an irregular shape such as a spherical shape, or they may have crystal defects such as twin crystal planes, or alternatively they may have a complex shape consisting of these shapes. In addition, mixtures of grains having different crystal shapes may also be used.

The silver halides mentioned above can be monodisperse emulsions, which have a narrow distribution, or polydisperse emulsions, which have a broad distribution.

In addition, tabular grains having an aspect ratio of at least 5 can also be used in the aforementioned emulsion layers.

The crystal structure of the aforementioned emulsion grains may be uniform, or the inner parts and outer parts of the grains may be made of materials having different halogen compositions, and the grains may have a layered structure. These emulsion grains have been described in British Patent 1,027,146, U.S. Patents 3,505,068 and 4,444,877, and Japanese Patent Application (OPI) No. 143331/85, etc. In addition, the silver halides having different compositions may be bonded via epitaxial linkage, and further they may be bonded with compounds other than silver halides, such as silver thiocyanate or lead oxide.

The aforementioned emulsions may be of the surface latent image type in which the latent image is basically formed on the surface, or of the internal latent image type in which the latent image is formed inside the grains, or of the type in which the latent image is formed both on the surface and inside the grains. In addition, the Grains may be of the type in which the interior of the grain has been chemically sensitized. The photographic silver halide emulsions which can be used for the invention can be prepared in a conventional manner using the known methods, and they can be prepared, for example, according to the methods described in "I. Emulsion Manufacture (Emulsion Preparation and Types)" on pages 22 to 23 of Research Disclosure, Vol. 176, No. 17643 (December 1978), and on page 648 of Research Disclosure, Vol. 187, No. 18716 (November 1979).

If necessary, various silver halide solvents (e.g., ammonia, potassium thiocyanate, or the thione compounds and thioethers described in U.S. Patent 3,271,157, Japanese Patent Application (OPI) Nos. 12360/76, 82408/78, 144319/78, 100717/79, or 155828/79) can be used in preparing the photographic emulsions of the present invention.

Emulsions of the type containing silver halide grains having an average grain diameter greater than 0.1 µm and in which at least 95% by weight of the grains are within ± 40% of the average grain diameter are typical of monodisperse emulsions. Emulsions in which the average grain diameter is 0.25 to 2 µm and in which at least 95% by weight or 95% of the silver halide grains (expressed as the number of grains) are within ± 20% of the average grain diameter can be used in accordance with the invention.

Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts and iron salts or their complex salts may be present during the formation or physical ripening of the silver halide grains.

The emulsions used in the invention are usually used after chemical ripening and spectral Sensitization has been carried out after physical ripening. The additives used in these processes are described in Research Disclosure Nos. 17643 (December 1978) and 18716 (November 1979), and the references in these descriptions are given in the table below.

Known additives for photographic purposes which can be used in the present invention are also described in the two Research Disclosures mentioned above, and the references in these descriptions are given in the following table. Additive type 1. Chemical sensitizers 2. Accelerators 3. Spectral sensitizers, strong color sensitizers 4. Brighteners 5. Antifogging agents and stabilizers 6. Light absorbers, filter dyes, UV absorbers 7. Antistain agents 8. Color image stabilizers 9. Film hardeners 10. Binders 11. Plasticizers, lubricants 12. Coating aids, surfactants 13. Antistatic agents

The Known spectral sensitizers described recently can be used for the color photographic materials of the present invention, but the use of compounds represented by the general formula (IV) or (V) in the description on pages 90 to 100 of the specification of Japanese Patent Application No. 313598/86 and the actual examples of these compounds are preferred for the processing method of the present invention.

In addition to the aforementioned cyan image-forming couplers of formula (A), various color couplers can be used in the present invention, and actual examples are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-C to G. The couplers which form the three primary colors of the subtractive process (i.e., yellow, magenta and cyan) during color development are important as color-forming couplers, and so are the couplers described in the patents described in sections VII-C and D of the aforementioned RD 17643, which are effective diffusion-resistant four-equivalent or two-equivalent couplers. Those indicated below are preferred in the present invention.

The well-known oxygen atom eliminating yellow couplers or nitrogen eliminating yellow couplers are typical of the yellow couplers that can be used. The couplers based on α-pivaloylacetanilide provide colored dyes that have excellent fastness, especially light fastness, while couplers based on α-benzoylacetanilide provide high color densities.

Hydrophobic 5-pyrazolone-based and pyrazoloazole-based magenta couplers having ballast groups can be used in the present invention. 5-pyrazolone-based couplers having an arylamino group or an acylamino group substituted at the 3-position are preferred from the viewpoint of the color depth of the colored dye that is formed and the color density.

Diffusion-resistant, hydrophobic naphthol- and phenol-based cyan couplers can also be used in the present invention, and typically the two-equivalent naphthol-based oxygen elimination type couplers are preferred. In addition, the use of couplers capable of forming cyan dyes that are resistant to humidity and temperature is preferred, and typical examples include phenol-based cyan couplers having an alkyl group consisting of an ethyl group or a larger group in the meta-position of the phenol ring as described in U.S. Patent 3,772,002, the 2,5-diacylamino-substituted phenol-based couplers, and the phenol-based couplers having a phenylureido group in the 2-position and a diacylamino group in the 5-position.

The graininess can be improved by the combined use of couplers whose colored dyes have an appropriate degree of diffusibility. Current examples of magenta couplers of this type are described in U.S. Patent 4,366,237, and current examples of yellow, magenta and cyan couplers of this type are described in European Patent 96,570.

The dye-forming couplers and the previously mentioned special couplers may be in the form of polymers consisting of at least dimers. Typical examples of polymerized dye-forming couplers have been described in U.S. Patent 3,451,820. Actual examples of polymerized magenta couplers have been described in U.S. Patent 4,367,282.

According to the invention, the use of couplers which release photographically useful residues as a result of coupling is preferred. The DIR couplers which release development inhibitors, described in the patents described in the aforementioned RD 17643, Section VII-F are effective.

Couplers which release a nucleating agent or development inhibitor or their precursors in the form of the image during development can be used for the light-sensitive materials of the present invention. Actual examples of these compounds have been described in British Patents 2,097,140 and 2,131,188. Also, the redox compound-releasing DIR couplers described in Japanese Patent Application (OPI) No. 185950/85 and the couplers which release dyes which are recolored after elimination as described in European Patent 173,302A can be used.

The couplers used in the present invention can be added to the light-sensitive material using a variety of known dispersion methods. Examples of high boiling organic solvents that can be used for the oil-in-water dispersion method have been described in U.S. Patent 2,322,027. In addition, actual examples of the process and effect of the latex dispersion method and latexes for impregnation have been described in U.S. Patent 4,199,363 and West German Patent Applications (OLS) 2,541,274 and 2,541,230.

The light-sensitive materials of the present invention may also contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers or sulfonamidophenol derivatives as anti-color fogging agents and anti-color mixing agents.

The known anti-fading agents can be used for the light-sensitive materials of the present invention. Typical examples of known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols, hindered phenols centered in bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ethers and ester derivatives obtained by silylation and alkylation of the phenolic hydroxyl groups of these compounds. Furthermore, metal complexes can also be used, typical examples of which are (bis-salicylaldoxymato)nickel complex and (bis-N,N-dialkyldithiocarbamato)nickel complex.

The photographic emulsion layers and other layers are coated on a flexible support such as a plastic film normally used for photographic materials.

A variety of known coating methods such as the dip coating method, the roller coating method, curtain coating method or extrusion coating method can be used to apply the photographic emulsion layers and other hydrophilic coating layers.

The invention can be used for numerous color photographic materials. Typical examples of such materials include color negative films for general purposes and projections, color reversal films for slides and television purposes, color papers, color positive films and color reversal papers.

The color developing baths used for color development of the light-sensitive materials of the present invention are alkaline aqueous solutions containing primary aromatic amine-based color developing agents as the main component. Aminophenol-based compounds are effective as color developing agents, but the use of p-phenylenediamine-based compounds is preferred, and typical examples thereof include 3-methyl-4-amino-N,N-diethylaniline, 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 their sulfates, hydrochlorides, phosphates or p-toluenesulfonates, tetraphenylborates and p-(t-octyl)benzenesulfonates. These amines are generally more stable as salts than in the free state and the use of the salts is preferred.

Aminophenol-based derivatives include, for example, o-aminophenol, p- aminophenol, 4-amino-2-methylphenol, 2-amino-3-methylphenol and 2-oxy-3-amino-1,4-dimethylbenzene.

Those described on pages 226 to 229 of "Photographic Processing Chemistry" by L.F.A. Mason, published by Focal Press (1966), and those described in U.S. Patents 2,193,015 and 2,592,364 and Japanese Patent Application (OPI) No. 64933/73 can also be used. If necessary, combinations of two or more of the aforementioned color developing agents can be used.

The color developing bath may contain pH buffers such as the carbonates, borates or phosphates of alkali metals, development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles and mercapto compounds, preservatives such as hydroxylamine, triethanolamine, the compounds described in West German Patent Application (OLS) 2,622,950, sulfites and bisulfites, organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, poly(ethylene glycol), quaternary ammonium salts, amines, thiocyanates, 3,6-thiaoctane-1,8-diol, dye-forming couplers, competitive couplers, germinants such as sodium borohydride, developing aids such as 1-phenyl-3-pyrazolidone, viscosity-increasing agents, and chelating agents such as the aminopolycarboxylic acids, typical examples of which are Ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, Triethylenetetraaminehexaacetic acid and the compounds described in Japanese Patent Application (OPI) No. 195845/83, 1-hydroxyethylidene-1,1'-diphosphonic acid, the organic phosphonic acids described in Research Disclosure No. 18170 (May 1979), aminophosphonic acids such as aminotris(methylenephosphonic acid), ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid and the phosphonocarboxylic acids described in Research Disclosure No. 18170 (May 1979).

The color developing agents are generally used in a concentration of about 0.1 g to about 30 g, and preferably in a concentration of about 1 g to about 15 g per liter of color developing bath. Furthermore, the pH of the color developing bath is normally about 7 or more, and generally a pH of about 9 to 13 is used.

According to the invention, the silver halide color photographic material is subjected to a color development process of the type described after imagewise exposure and is then processed in a processing bath having a bleaching effect.

The processing bath having a bleaching effect is a processing bath capable of converting the metallic silver generated by the development reaction and the colloidal silver contained in the sensitive material into soluble silver salts such as a silver thiosulfate complex salt or into an insoluble silver salt such as silver bromide by oxidation, e.g., a bleaching bath or a bleach-fixable. Immediate processing in a processing bath having a bleach-fixing effect after the color development process is preferred in the present invention.

Oxidizing agents such as iron(III) complex salts such as iron(III) cyanide complex salts or iron(III) citrate complex salts and oxidizing substances such as persulfates or hydrogen peroxide can be used according to the invention as bleaching agents which are used in the processing baths, which have a bleaching effect, can be used, however the aminopolycarboxylic acid iron(III) complex salts consisting of iron(III) ions and aminopolycarboxylic acid, or their salts are preferred.

Typical examples of these aminopolycarboxylic acids and their salts are given below.

1. Diethylenetriaminepentaacetic acid

2. Pentasodium salt of diethylenetriaminepentaacetic acid

3. Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid

4. Trisodium salt of ethylenediamine-N-(β-oxyethyl)-N,N',N'- triacetic acid

5. Triammonium salt of ethylenediamine-N-(β-oxyethyl)-N,N',N'- triacetic acid

6. 1,2-Diaminopropanetetraacetic acid

7. Disodium salt of 1,2-diaminopropanetetraacetic acid

8. Nitrilotriacetic acid

9. Sodium salt of nitrilotriacetic acid

10. Cyclohexanediaminetetraacetic acid

11. Disodium salt of cyclohexanediaminetetraacetic acid

12. N-methyl-iminodiacetic acid

13. Iminodiacetic acid

14. Dihydroxyethylglycin

15. Ethyl ether of diaminetetraacetic acid

16. Glycol ether of diaminetetraacetic acid

17. Ethylenediaminetetrapropionic acid

18. 1,3-Diaminopropanetetraacetic acid

19. Ethylenediaminetetraacetic acid.

Of course, these acids and salts are not limited to the illustrative examples given above.

Of these compounds, those with numbers 1, 2, 6, 7, 10, 11, 12, 16 and 18 are particularly desirable.

The aminocarboxylic acid-iron(III) complex salts may be used in the form of the complex salt, or the ferric ion complex salts may be formed in solution by using, for example, ferric sulfate, ferric chloride, ferric ammonium sulfate or ferric phosphate and the aminopolycarboxylic acid. When used in the form of a complex salt, either one kind of complex salt or two or more kinds of complex salts may be used. On the other hand, when a complex salt is formed in solution by using a ferric salt and an aminopolycarboxylic acid, one kind or more kinds of ferric salts may be used. Further, one kind or more than one kind of aminopolycarboxylic acids may be used. In addition, in either case, the aminopolycarboxylic acid may be used in excess of the amount required to form the ferric ion complex salt.

Combinations of ethyleneaminediaminetetraacetic acid iron(III) complex salts with at least one other kind of iron(III) complex salts of aminopolycarboxylic acids than that indicated above with No. 19 can be used.

Metal ion complex salts of e.g. cobalt, nickel or copper can be used as well as iron ions in the processing baths that have bleaching effect, which contain the previously mentioned iron(III) complex salts.

In the present invention, the amount of bleaching agents used is 0.1 mol to 1 mol, and preferably 0.2 mol to 0.5 mol/L processing bath having bleaching effect. In addition, the pH of the bleaching bath is preferably 4.0 to 8.0, and most desirably 5.0 to 7.5.

Rehalogenating agents such as bromides, e.g. potassium bromide, sodium bromide and ammonium bromide, or chlorides, e.g. potassium chloride, sodium chloride and ammonium chloride, can be used as well as the bleaching agent and the aforementioned compounds having bleaching action may be contained in the processing baths of the invention. In addition, the known additives which are usually used in bleach-fixing baths, e.g. nitrates such as sodium nitrate or ammonium nitrate, and one or more kinds of inorganic acids, organic acids or salts thereof which have pH buffering action such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphoric acid, phosphorous acid, sodium phosphate, citric acid, sodium citrate or tartaric acid may be added to the processing bath.

According to the invention, compounds known as fixing agents, for example, the thiosulfates such as sodium thiosulfate, ammonium thiosulfate, ammonium sodium thiosulfate and potassium thiosulfate, thiocyanates such as ammonium thiocyanate and potassium thiocyanate, thiourea or thioethers may be contained in a fixing bath used after the bleaching bath or in a processing bath having a bleach-fixing action.

The amount of these fixing agents added is preferably not more than 3 mol and most desirably not more than 2 mol per liter of processing bath having fixing or bleach-fixing action.

According to the invention, for example, sulfites or disulfites such as sodium sulfate or ammonium sulfite and so-called sulfite ion-releasing compounds, e.g. disulfite adducts of aldehydes such as carbonyl disulfite, can be contained in the processing baths which have bleach-fixing action.

In addition, aminopolycarboxylic acid salts as listed under numbers 1 to 19 or organic phosphonic acid compounds such as ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentakismethylenephosphonic acid, 1,3-diaminopropanetetrakismethylenephosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid and 1-hydroxyethylidene-1,1'-diphosphonic acid can be used.

According to the present invention, the processing can be carried out by containing at least one kind of bleach accelerating agents in the processing bath having bleaching action, which is selected from the compounds having a mercapto group or a disulfite bond, the isothiourea derivatives and the thiazolidine derivatives. These compounds are preferably added in an amount of 1 x 10-5 mol to 1 x 10-1 mol, and most desirably in an amount of 1 x 10-4 mol to 5 x 10-2 mol/L of the bath having bleach-fixing action.

The bleaching accelerating agent contained in the processing bath having a bleaching effect according to the invention is selected from the compounds having mercapto groups or disulfite bonds, the thioazolidine derivatives, the thiourea derivatives and the isothiourea derivatives, with the proviso that they have a bleaching accelerating effect.

The compounds represented by the general formulas (a) to (g) and the actual examples described on pages 63 to 77 of the specification of Japanese Patent Application No. 313598/86 are preferred.

These compounds are usually pre-dissolved in water or an alkaline solution, an organic acid or organic solvent for addition to the processing bath, but they can be added directly in the form of a powder to the processing bath having bleaching action, which has no effect on the bleaching accelerating effect.

In addition, according to the present invention, a bleaching accelerating agent may be contained in the light-sensitive material. In this case, the bleaching accelerating agent may be contained in any of blue-sensitive, green-sensitive or red-sensitive emulsion layers or in the gelatin layers such as the top layer, the interlayers and the bottom layer.

The processing bath of the present invention having bleach-fixing action may be used in one tank processing, or it may be used for processing in two or more tanks, and the replenisher solution may be supplied to this tank group in a multi-stage countercurrent system, and further, the processing baths of this tank group may be alternately circulated to form a processing bath which is uniform throughout, and the replenisher solution may be supplied to one of the baths of this tank group.

The silver halide color photographic materials of the present invention are generally subjected to a washing and/or a stabilizing process after a desilvering process such as fixing or bleach-fixing.

The amount of water used in the washing process can be adjusted over a wide range depending on the properties of the photosensitive material (e.g., in accordance with the materials such as couplers used) and the application of the photosensitive material, and also on the temperature of the washing water, the number of washing tanks (number of stages), and whether a countercurrent replenishment system or a series-connected replenishment system is used, and many other conditions. The relationship between the amount of water used and the number of washing tanks in a multi-stage countercurrent system can be derived using the method described on pages 248 to 253 of volume 64 of the Journal of the Society of Motion Picture and Television Engineers (May 1955).

The amount of washing water can be largely reduced by using the multi-stage countercurrent system, which is used in the aforementioned reference, but may involve problems of bacterial growth and adhesion of the suspended matter produced thereby to the photosensitive material due to the increased residence time of the water in the tanks. The method of reducing the calcium and magnesium contents described in Japanese Patent Application (OPI) No. 288838/87 can be effectively used as a means of solving problems of this kind in the processing of color photographic materials according to the invention. Furthermore, the isothiazole compounds and thiabendazoles described in Japanese Patent Application (OPI) No. 8542/82, chlorine-based disinfectants such as chlorinated sodium isocyanurate, benzotriazoles, and the disinfectants published by Horiguchi in "The Chemistry of Disinfectants and Fungicides" in the Hygiene Technology Association publication entitled "Microbiological Disinfection, Disinfection and Fungicidal Techniques" and in the Japanese Antibacterial and Antifungal Society publication entitled "A Dictionary of Biocides and Fungicides" can also be used.

The pH of the washing water in processing photosensitive materials of the present invention is 4 to 9, and preferably 5 to 8. The water temperature and the washing time can be varied according to the properties and application of the photosensitive material, but generally a washing time of between 20 seconds and 10 minutes at a temperature of between 15°C and 45°C, and preferably between 30 seconds and 5 minutes at a temperature of between 25°C and 40°C is selected.

Furthermore, the light-sensitive materials of the present invention can be processed in a direct stabilization bath instead of the aforementioned washing treatment. For this stabilization process, the known methods described in Japanese Patent Application (OPI) Nos. 8543/82, 14834/83, 184343/84, 220345/85, 238832/85, 239784/85, 239749/85, 4054/86 and 118749/86 may be used. The use of stabilizing baths containing 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, bismuth compounds or ammonium compounds is particularly desirable.

In addition, there are also cases where a stabilizing process is carried out after the aforementioned washing process, and in these cases, the stabilizing baths containing formaldehyde and a surfactant used as finishing baths for color photographic materials for film purposes can be used.

The invention is explained below using examples.

example 1

Sample 101, a multilayer color light-sensitive material consisting of layers whose compositions are given below, was prepared on an undercoat support of cellulose triacetate film.

The coating amounts are given for the silver halides and colloidal silver in g silver/m² units, for the couplers, additives and gelatin in g/m² units and for the sensitizing dyes in units mol/mol silver halide in the same layer.

First layer (anti-halation layer)

Black colloidal silver 0.2

Gelatin 1.3

ExM-8 0.06

UV-1 0.1

UV-2 0.2

Lsgm-1 0.01

Lsgm-2 0.01

Second layer (intermediate layer)

Fine-grained silver bromide (average grain size 0.07 um) 0.10

Gelatin 1.5

UV-1 0.06

UV-2 0.03

ExC-2 0.02

ExF-1 0.004

Lsgm-1 0.1

Lsgm-2 0.09

Third layer (first red-sensitive emulsion layer)

Silver iodobromide emulsion (AgI 2 mol%, high internal AgI content type, diameter of the corresponding sphere 0.3 µm, coefficient of variation of the corresponding sphere diameter 29%, regular crystals, grains mixed with twin crystals, diameter/thickness ratio 2.5) 0.4 (coating silver weight)

Gelatin 0.6

ExS-1 1.0 X 10⊃min;⊃4;

ExS-2 3.0 x 10�min;₄

ExS-3 1.0 x 10⊃min;⊃5;

ExC-3 0.06

ExC-4 0.06

ExC-7 0.04

ExC-2 0.03

Lsgm-1 0.03

Lsgm-2 0.012

Fourth layer (second red-sensitive emulsion layer)

Silver iodobromide emulsion (AgI 5 mol%, high internal AgI content type, diameter of the corresponding sphere 0.7 um, coefficient of variation of the corresponding sphere diameter 25%, regular crystals, grains mixed with twin crystals, diameter/thickness ratio 4) 0.7 (coating silver weight)

Gelatin 0.5

ExS-1 1.0 x 10⊃min;⊃4;

ExS-2 3.0 x 10-4

ExS-3 1.0 x 10⊃min;⊃5;

ExC-3 0.24

ExC-4 0.24

ExC-7 0.04

ExC-2 0.04

Lsgm-1 0.15

Lsgm-2 0.02

Fifth layer (third red-sensitive emulsion layer)

Silver iodobromide emulsion (AgI 10 mol%, high internal AgI content type, diameter of corresponding sphere 0.8 µm, coefficient of variation of corresponding sphere diameter 16%, regular crystals, grains mixed with twin crystals, diameter/thickness ratio 1.3) 1.0 (coating silver weight)

Gelatin 1.0

ExS-1 1.0 x 10⊃min;⊃4;

ExS-2 3.0 x10⊃min;⊃4;

ExS-3 1.0 x 10⊃min;⊃5;

ExC-6 0.13

Lsgm-1 0.01

Lsgm-2 0.05

Sixth layer (intermediate layer)

Gelatin 1.0

Cpd-1 0.03

Lsgm-1 0.05

Seventh layer (first green-sensitive emulsion layer)

Silver iodobromide emulsion (AgI 2 mol%, high internal AgI content type, diameter of corresponding sphere 0.3 µm, coefficient of variation of corresponding sphere diameter 28%, regular crystals, grains mixed with twin crystals, diameter/thickness ratio 2.5) 0.30 (coating silver weight)

ExS-4 5.0 x 10-4

ExS-6 0.3 x 10⊃min;⊃4;

ExS-5 2.0 x 10⊃min;⊃4;

Gelatin 1.0

ExM-9 0.2

ExY-14 0.03

ExM-8 0.03

Lsgm-1 0.5

Eighth layer (second green-sensitive emulsion layer)

Silver iodobromide emulsion (AgI 4 mol%, high internal AgI content type, diameter of corresponding sphere 0.6 µm, coefficient of variation of corresponding sphere diameter 38%, regular crystals, grains mixed with twin crystals, diameter/thickness ratio 4) 0.40 (coating silver weight)

Gelatin 0.5

ExS-4 5.0 x 10-4

ExS-5 2.0 x 10⊃min;⊃4;

ExS-6 0.3 x 10⊃min;⊃4;

ExM-9 0.25

ExM-8 0.03

ExM-10 0.015

ExY-14 0.01

Lsgm-1 0.2

Ninth layer (third green-sensitive emulsion layer)

Silver iodobromide emulsion (AgI 6 mol%, high internal AgI content type, diameter of corresponding sphere 1.0 µm, coefficient of variation of corresponding sphere diameter 80%, regular crystals, grains mixed with twin crystals, diameter/thickness ratio 1.2) 0.85 (coating silver weight)

Gelatin 1.0

ExS-7 3.5 x 10⊃min;⊃4;

ExS-8 1.4 x 10⊃min;⊃4;

ExM-11 0.1

ExM-12 0.03

ExM-13 0.20

ExM-8 0.02

ExY-14 0.02

Lsgm-1 0.20

Lsgm-2 0.05

Tenth layer (yellow filter layer)

Gelatin 1.2

Yellow colloidal silver 0.08

Cpd-2 0.1

Lsgm-1 0.3

Eleventh layer (first blue-sensitive emulsion layer)

Silver iodobromide emulsion (AgI 4 mol%, high internal AgI content type, diameter of the corresponding sphere 0.5 µm, coefficient of variation of the corresponding sphere diameter 15%, octahedral grains) 0.4 (coating silver weight)

Gelatin 1.0

ExS-9 2 x 10⊃min;⊃4;

ExY-16 0.9

ExY-14 0.07

Lsgm-1 0.20

Twelfth layer (second blue-sensitive emulsion layer)

Silver iodobromide emulsion (AgI 10 mol%, high internal AgI content type, diameter of corresponding sphere 1.3 µm, coefficient of variation of corresponding sphere diameter 25%, regular crystals, grains mixed with twin crystals, diameter/thickness ratio 4.5) 0.5 (coating silver weight)

Gelatin 0.6

ExS-9 1 x 10⊃min;⊃4;

ExY-16 0.25

Lsgm-1 0.07

Thirteenth layer (first protective layer)

Gelatin 0.8

UV-1 0.1

UV-2 0.2

Lsgm-1 0.01

Lsgm-1 0.01

Fourteenth layer (second protective layer)

Fine-grained silver bromide (average grain size 0.07 um) 0.5

Gelatin 0.45

Poly(methyl methacrylate) grains (diameter 1.5 µm) 0.2

H-1 0.4

Cpd-3 0.5

Cpd-4 0.5

In addition to the compounds listed above, a surfactant was added to each layer as a coating aid. The sample prepared in this way was Sample 101.

The chemical structural formulas or chemical names of the compounds used in the examples are given below. (weight ratio)

Lsgm-1 tricresyl phosphate

Lsgm-2 dibutyl phthalate

Lsgm-3 Bis(2-ethylhexyl)phthalate Molecular weight: about 20,000

The sample prepared in this way was sample 101.

Preparation of sample 102

Sample 102 was prepared in the same manner as Sample 101 except that an amount of comparative compound A, the structural formula of which is shown below, which was equimolar with the total amount of ExC-3 and ExC-4 in Sample 101 was used in place of ExC-3, ExC-4 which had been added to the third and fourth layers in Sample 101. Comparison compound A

Preparation of samples 103 to 110

Samples 103 to 110 were prepared in the same manner as Sample 102 except that equimolar amounts of inventive compounds as shown in Table 3 below were used in place of Comparative Compound A and Coupler ExC-6 in the fifth layer of Sample 102.

The obtained samples 101 to 110 were cut into strips of 35 mm width, and then a standard photographic object was photographed and 500 m running tests were carried out using processing operations (I) and (III) in Tables 1 and 2 described below. At the conclusion of the running tests, samples 101 to 110 were subjected to 20 CMS wedge exposure using white light and processed using processing operations (I) and (III). Then, the residual silver contents were measured using the X-ray fluorescence method and density measurements were also carried out. Table 1 Processing procedure (1) (Temperature 38ºC) Processing (I) Procedure Time Replenishment rate * Colour development Bleaching Fixation Stabilisation Drying (50ºC) *: Per 1 mx 35 mm width.

In the processing described above, stabilizations (1), (2) and (3) consisted of a countercurrent system running from (3) (2) (1). In addition, the carryover of fixer into the washing tank was 2 ml per m. Colour developing bath Tank (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1-Hydroxyethylidene-1,1-diphosphonic acid Sodium sulphite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulphate Water to Bleaching bath tank (g) Refill solution (g) Ethylenediaminetetraacetic acid iron(III) ammonium salt 1,3-Diaminopropanetetraacetic acid iron(III) ammonium salt Ammonia Ammonium nitrate Ammonium bromide Water on Fixing bath tank (g) Refill solution (g) Disodium salt of ethylenediaminetetraacetic acid Sodium sulphite Sodium bisulfite Ammonia thiosulphate solution (70 %) Water to Stabilization bath Tank refill solution (g) Formaldehyde (37 % w/v) Polyoxyethylene p-monononylphenyl ether (average degree of polymerization 10) 5-chloro-2-methyl-4-isothiazolin-3-one Water to TABLE 2 Processing procedure (II) (temperature 38ºC) Processing Processing time Tank capacity Refill rate * Colour development Bleaching-fixing Washing Stabilisation *: Per m of light-sensitive material 35 mm width

In the processing described above, washing (1), (2) and (3) was carried out in a countercurrent system of (3) (2) (1). Colour developing bath tank (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1-Hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate Water to pH (adjusted with potassium hydroxide Bleach-fixing bath tank (g) Replenisher (g) Ethylenediaminetetraacetic acid iron(III) ammonium salt Diethylenetriaminepentaacetic acid iron(III) ammonium salt Disodium salt of ethylenediaminetetraacetic acid Sodium sulphite Ammonia thiosulphate solution (70% w/v) Ammonia (26%) Water to

Irrigation water

The three species listed below were used.

(1) Town Water

Calcium 26 mg/l

Magnesium 9 mg/l

pH7.2

(2) Ion exchange water

The tap water described above was treated with a strong acidic cation exchange resin (Na form) manufactured by Mitsubishi Kasei Chemical Industries, Ltd. to obtain the water quality described below.

Calcium 1.1 mg/l

Magnesium 0.5 mg/l

pH6.6

(3) Tap water with added gelling agent The disodium salt of ethylenediaminetetraacetic acid was added to the previously mentioned tap water in an amount of 500 mg/l.

pH6.7

The samples were processed in these processing baths according to the processing procedures described previously.

The results obtained are shown in Table 3 below. Table 3 Sample number Coupler in layers 3 and 4 Coupler in layer 5 Processing procedure Residual silver content (mg/m²) Dmin* (Magenta) (Comparison) (Invention) Table 3 (cont.) Sample number Coupler in layers 3 and 4 Coupler in layer 5 Processing procedure Residual silver content (mg/m²) Dmin* (magenta) (comparison) *: Dmin is the value including the film base density of 0.36 after desilvering

The results shown in Table 3 above clearly show that the preferred lower minimum density (Dmin) was obtained both in processing (I) using separate bleach and fix baths and in processing (II) using a bleach-fix bath when the couplers of the present invention were used rather than in cases where a ureidophenol type cyan coupler was used. In the case of processing (II), which is high speed processing, a good, almost constant minimum density was obtained using the couplers of the present invention, but in cases where a ureidophenol type cyan coupler was used, a considerable increase in minimum density was obtained.

In addition, when observing the change in the gradation of the cyan layer when 50 ppm ferric chloride was added to the processing step (II), no major change was observed in any of the samples 101 to 110.

It was clearly shown that the amount of residual silver was not more than 30 mg/m², and images were obtained without any particular practical problems.

The samples of the invention have a satisfactorily low residual silver content for practical purposes and it is known that the increase and fluctuation of Dmin for magenta was small.

By means of the invention it is possible to obtain silver halide color photographic materials which are superior in terms of desilvering speed and which are improved in terms of recoloring properties and minimum image density.

Claims (13)

1. A silver halide color photographic material comprising a support having at least one silver halide emulsion layer thereon, wherein the material (1) contains at least one kind of cyan dye-forming coupler represented by the general formula (A) wherein R₁ represents a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amidine group, a guanidine group or a group represented by R₂ represents a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an amino group, a cyano group, a nitro group, an aliphatic group, an aromatic group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, an acyl group, an acyloxy group, an aliphatic oxy group, an aromatic oxy group, an aliphatic sulfonyl group, an aromatic sulfonyl group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, a sulfamoylamino group, a heterocyclic group or an imido group, l' represents an integer of 0 to 3, R₃ represents a hydrogen atom or R₆U, and T represents a hydrogen atom or a group which can be eliminated by a coupling reaction with the oxidized product of an aromatic primary amine developing agent, wherein R₄ and R₅ each independently represent an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an aliphatic oxy group or an aromatic oxy group, and R₆ represents a heterocyclic group. a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group -SO₂OR₇ or an imido group and U represents NR₉, -CO-, -SO₂-, -SO- or a single bond, wherein R₇ represents an aliphatic group, an aromatic group or a heterocyclic group, R₈ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R₇ and R₁₀ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an aliphatic sulfonyl group or an aromatic sulfonyl group when l' is 2 or 3, the R₂ groups may be the same or different and may be linked together to form a ring, and R₃, or R₃ and T, may be linked together to form rings, further dimers or oligomers or polymers which may also be formed with each other via divalent groups or groups having a valence greater than 2 for each of R₁, R₂, R₃ or T, characterized in that the material further contains (2) at least one kind of compound which reacts with the oxidized product of a primary aromatic amine developing agent to release a bleach accelerator. 2. A silver halide photographic material as claimed in claim 1, wherein R₁ in the general formula (A) represents a halogen atom, -SO₂R₄ or -COR₄. 3. A silver halide photographic material according to claim 1, wherein l' in (R₂)1' is 0. 4. The silver halide photographic material of claim 1, wherein R₆ in the general formula (A) represents an aliphatic group, an aromatic group, -OR₇ or -SR₇. 5. The silver halide photographic material according to claim 1, wherein T in the general formula (A) represents a hydrogen atom, a halogen atom, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group or a heterocyclic thio group. 6. A silver halide photographic material according to claim 1, wherein the coupler represented by the general formula (A) is present in an amount of 0.1 mol% to 100 mol% based on the total amount of silver applied. 7. The silver halide photographic material according to claim 6, wherein the coupler represented by the general formula (A) is used in an amount of 0.01 mol% to 50 mol% based on the total amount of silver coated. 8. The silver halide photographic material according to claim 7, wherein the coupler represented by the general formula (A) is used in an amount of 1 mol% to 20 mol% based on the total amount of silver coated. 9. A silver halide photographic material according to claim 1, wherein the compound which releases a bleaching accelerating agent is represented by the general formula (I) A(L)p-Z (I) wherein A represents a group whose bond with (L)p-Z is severed by the reaction with the oxidized product of the developing agent, L represents a timing group or a group whose bond with Z is severed by the reaction with the oxidized product of the developing agent, p represents an integer from 0 to 3, and when p is 2 or 3, the p individual L groups may be the same or different, and Z represents a group which, when the bond with A-(L)p has been severed, has a bleaching accelerating effect. 10. A silver halide photographic material according to claim 9, wherein the compound represented by the general formula (I) is represented by the general formula (I') A-(L)p-(Z₂)b-Z (I') wherein A represents a group whose bond with (L)p-(Z2)b-Z is severed by the reaction with the oxidized product of the developing agent, L1 represents a timer group or a group whose bond with (L)p-Z is severed by the reaction with the oxidized product of the developing agent, L2 represents a timer group or a group whose bond with Z is severed by the reaction with the oxidized product of the developing agent, Z represents a group which, when the bond with A-(L)p-(Z2)b is severed, has a bleaching accelerating effect, and a and b each have a value of 0 or 1. 11. The silver halide color photographic material according to claim 10, wherein the group represented by Z is a group represented by the general formula (XII), (XIII) or (XIV) wherein * indicates the position of the bond with A-(L)a-(Z₂)b-, R₃₁ represents a divalent aliphatic group which to 8 carbon atoms, R₃₂ is a group having the same meaning as R₃₁, a divalent aromatic group having 6 to 10 carbon atoms, or a 3- to 8-membered divalent heterocyclic group, X₁ is an -O- group, an -S- group, an -COO- group, an -SO₂- group, a an -S- - group, a - - group, a Group means X₂ represents an aromatic group having 6 to 10 carbon atoms, X₃ represents a 3- to 8-membered heterocyclic group having at least one carbon atom bonded to sulfur within the ring, Y₁ represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, a phosphonic acid group or a salt thereof, an amino group, a -NHSO₂-R₃₅ group, or a -SO₂NH-R₃₅ group, Y₂ represents a group having the same meaning as those defined for Y₁ or represents a hydrogen atom, r represents 0 or 1, l represents an integer from 0 to 4, m represents an integer from 1 to 4 and u represents an integer from 0 to 4. 12. The silver halide color photographic material according to claim 1, wherein the compound releasing a bleaching accelerator is used in an amount of 1x10-7 to 5x10-1 mol per m² of the light-sensitive material. 13. The silver halide color photographic material according to claim 1, wherein the compound releasing a bleaching accelerator is used in an amount of 1x10-6 to 5x10-2 mol per m2 of the light-sensitive material.