EP0301477B1

EP0301477B1 - Silver halide color photosensitive material and method of processing thereof

Info

Publication number: EP0301477B1
Application number: EP19880112038
Authority: EP
Inventors: Kei C/O Fuji Photo Film Co. Ltd. Sakanoue; Hidetoshi C/O Fuji Photo Film Co. Ltd. Kobayashi
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1987-07-27
Filing date: 1988-07-26
Publication date: 1991-04-03
Also published as: JPS6431159A; JP2542858B2; EP0301477A3; DE3862257D1; EP0301477A2

Description

The present invention concerns a silver halide color photosensitive material. Comprising at least one silver halide emulsion layer on a support, which contains at least one bleaching accelerator releasing type coupler.
Silver halide color photosensitive materials are generally processed in a color developing step and a desilvering step. In the color developing step, exposed silver halide is reduced by a color developing agent to produce silver, while the oxidized color developing agent reacts with a coupler to provide a dyed image. The thus formed silver is oxidized with a bleaching agent in the succeeding desilvering step and further undergoes the effect of a fixing agent into a soluble silver complex which is then removed by dissolution.
In recent years, more rapid processing (i.e., shortening of the time required for the processing) is strongly demanded in the relevant field of the art and, particularly, shortening of the desilvering step which occupies nearly one-half of the processing time. However, shortening the desilvering step causes remarkable problems.
As a method of increasing the bleaching power, Research Disclosure Item Nos. 24241 and 11449 and JP-A-61-201247 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") describe couplers of a bleach accelerating compound releasing type, and it has been known that the desilvering performance can be improved by using a silver halide color photosensitive material containing such a coupler of the bleach accelerating compound releasing type.
However, if a photosensitive material containing a coupler of the bleach accelerating compound releasing type is used for rapid processing in the desilvering step it has been found that the color reproducibility of the cyan image is worsened remarkably.
On the other hand, various cyan image-forming couplers effective for the improvement of the reproducibility of the cyan image are known. For example, U.S. Patent 4,333,999, JP-A-57-207593, JP-A-57-2045448 and JP-A-58-11863, describe phenol type cyan couplers having a ureido group at the 2-position, JP-A-60-237448, JP-A-61-145557 and JP-A-61-153640 describe a naphthol type cyan coupler having an amido group at the 5- position and, further, 2,5-diacylamino substituted phenol type cyan coupler known in the field of color paper.
Also, in JP-A-61-201247 concerning a coupler of the bleach accelerating compound releasing type described above, a phenol type cyan coupler having a 4-cyanophenylureido group at the 2-position is used as a kind of cyan image-forming coupler effective for such a reproducibility.
In addition, it has been known that the situation is the same for the dark place storability of the cyan image. That is, dark heat fastness of a cyan color image can remarkably be improved, by using a phenol type cyan coupler having a ureido group at the 2-position, a 2,5-diacylamino substituted phenol type cyan coupler, or a naphthol type cyan coupler having an amido group at the 5-position.
However, all of the cyan couplers releasing a desilverization accelerator known at present have a serious drawback that they are poor in the color reproducibility and dark heat fastness. Furthermore, it has been found that if means for increasing the desilvering rate (for example, lowering the pH value of a bleach-fix bath) are used, worsening of the color reproducibility described above becomes remarkable for the existent desilvering accelerator releasing coupler.
Such disadvantages aggravate the problem of making the desilvering step easier and faster.
Although a coupler having a 2-ureido substituted phenol nuclei as described in JP-A-61-201247 can compensate the foregoing drawbacks, it results in additional drawbacks such as increased color residue of the sensitizing dye upon applying high speed processing or low replenishing processing, or poor coupling activity of the coupler.
EP-A-0 246 616 belonging to the state of the art according to Art. 54(3)EPC describes a silver halide colour photographic material comprising a support having provided thereon at least one silver halide emulsion layer containing specific cyan couplers.
It is the object of the present invention to provide a silver halide color photographic material excellent in speeding up the desilvering step and having satisfactory color reproducibility or image storability.
Said object is achieved by a silver halide colour photosensitive material comprising at least one silver halide emulsion layer on a support, which contains at least one bleaching accelerator releasing type coupler characterised in that said bleaching accelerator releasing type coupler is represented by the following formula (I) :
wherein R₁ is selected from the group consisting of a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amidino group, a guanidino group,

R₂ is selected from the group consisting of a halogen atom, a hydroxyd group, a carboxyl group, a sulfo group, an amino group, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl 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 thio group, an aromatic thio group, an aliphatic sulfonyl group, an aromatic sulfonyl group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic oxy carbonyl group, an aromatic oxy carbonyl group, an aliphatic oxy carbonylamino group, an aromatic oxy carbonylamino group, a sulfamoyl amino group, a heterocyclic group and an imido group ; f represents an integer of 0 to 3 ; R₃ is selected from the group consisting of a hydrogen atom and R₆Y or R₂ and R₃ may join with each other to form a ring; LINK represents a functional linkage group connecting by way of a hetero atom to the 4-position of a naphthol ring ; m represents 0 or 1 ; L is selected from the group consisting of a (n + 1) valent group, that is, an alkyl group with 1 to 8 carbon atoms, an aryl group with 6 to 10 carbon atoms and a heterocyclic group with 1 to 10 carbon atoms from which n hydrogen atoms have been removed X represents a water soluble substituent ; n represents an integer of 1 to 3 ; R₄ and Rε are both selected independently from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, an aliphatic oxy group or an aromatic oxy group, or R₄ and R₅ may join with each other to form a ring ; R₆ is selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group,

and an imido group ; Y is selected from the group consisting of
-CO-, -S0₂, -SO- and a single bond ; R₇ is selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group ; R₈ is selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group ; Rg and R₁₀ are both selected independently from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an aliphatic sulfonyl group and an aromatic sulfonyl group or R₉ and R_io may join with each other to form a ring and provided that when ℓ is 2 or more, each R₂ may be identical to or different from the other, or any R₂ may join with another R₂ to form a ring, and an R₂ may form a dimer or higher polymer which is obtained by way of a divalent or higher valent group in an of R₁, R₂ or R₃ and provided that the coupler of formula (I) is not

or
Furthermore a method of processing a silver halide colour photosensitive material is provided, wherein the above silver halide colour photosensitive material is processed by fixing or bleach-fixing after colour development
The alkyl group, alkenyl group and alkynyl group of the coupler of formula (I) may be linear, branched or cyclic and may be substituted or unsubstituted. The aryl group of the coupler of formula (1) may be substituted or unsubstituted and includes a condensed ring. Heterocyclic rings may be a substituted or unsubstituted, single or condensed heterocyclic ring. Specific examples of the alkyl, alkenyl and alkynyl groups suitable for the couplers to be used in the present invention include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 2-hexyldecyl, adamantly, trifluoromethyl, carboxymethyl, methoxyethyl, vinyl, allyl, hydroxyethyl, heptafluoropropyl, benzyl, phenetyl, phenoxyethyl, methylsulfonylethyl, methane sulfonamide ethyl, 3-(2-ethylhexyloxy)propyl, 3-n-decyloxypropyl, 3-n-dodecyloxypropyl, 3-n-tetradecyloxypropyl, oleyl, propargyl, ethynyl, 3-(2,4-di-t-pentylphenoxy)propyl, 4-(2,4-di-t-pentylphenoxy)butyl, 1-(2,4-di-t-pentylphenoxy)propyl, 1-(2,4-di-t-pentylphenoxy)pentyl, 1-(3-tetradecylphenoxy)propyl and 2-n-dodecylthioethyl.
Specific examples of aryl groups suitable for the couplers to be used in the present invention include phenyl, p-tolyl, m-tolyl, o-tolyl, 4-chlorophenyl, 4-nitrophenyl, 4-cyanophenyl, 4-hydroxyphenyl, 3-hydroxyphenyl, 1-naphthyl, 2-naphthyl, o-biphenyl, p-biphenyl, pentafluorophenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 4-methoxyphenyl, 4-t-butylphenyl, 4-t-octylphenyl, 4-carboxyphenyl, 4-methane sulfoneamidophenyl, 4-(4-hydroxyphenylsulfonyl)phenyl, 2-n-tetradecyloxyphenyl, 4-n-tetradecyloxyphenyl, 2-chloro-5-n-dodecy- loxyphenyl, 3-n-pentadecylphenyl, 2-chlorophenyl, 4-methoxycarbonylphenyl, 4-methylsulfonylphenyl, and 2,4-di-t-pentylphenyl.
Specific examples of the heterocyclic ring suitable for the couplers to be used in the present invention include 2-pyridyl, 3-piridyl, 4-piridyl, 2-furyl, 2-thienyl, 3-thienyl, 4-quinolyl, 2-imidazolyl, 2-benzimidazolyl, 4-pyrazolyl, 2-benzoxazolyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, 5-tetrazolyl, 1,3,4-thiadiazol-2-yl, 2-pro- lyl, 3-triazolyl, 4-oxazolyl, 4-thiazolyl, 2-pyrimidyl, 1,3,5-triazine-2-yl, 1,3,4-oxadiazol-2-yl, 5-pyrazolyl, 4-pyrimidyl, 2-pyrazyl, succinimido, phthalimido, morpholino, pyrroridino, piperidino, imidazolidine-2,4-di-ole-3-yl, imidazolidine-2,4-dion-1-yl, and oxazolyzine-2,4-dion-3-yl.
In the following representative substituents of the compounds of formula (I) are described.
In formula (I) R₁ represents a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amidino group, a guanidino group or a group represented by

wherein R₄ and R₅ each represents an alkyl, alkenyl or alkynyl group with 1 to 30 carbon atoms. An aryl group with 6 to 30 carbon atoms, a heterocyclic group with 1 to 30 carbon atoms, an amino group with 0 to 30 carbon atoms (for example, amino, methylamino, dimethylamino, n-butylamino, anilino, N-(2-n-tetradecyloxyphenyl)amino, pyrolidino, morpholino, piperidino, 2-ethylhexylamino, n-dodecylamino, N-methyl-N-dodecylamino, 3-dodecyloxypropylamino, 3-(2,4-di-t-pentylphenoxy)propylamino, 4-(2,4-di-t-pentylphenoxy)butylamino) ; an aliphatic oxy group with 1 to 30 carbon atoms (forexample, methoxy, ethoxy, buthoxy, methoxyethoxy, n-dodecyloxy, 3-(2,4-di-t-pentylphenoxy)propoxy) ; or an aromatic oxy group with 6 to 30 carbon atoms (for example, phenoxy, 4-n-dodecyloxyphenoxy, 4-methoxycarbonylphenoxy). R₄ and R₅ may join with each other to form a ring. If R₁ represents a halogen atom, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom oran iodine atom. If R, represents an amidino group orguanidino group, the number of carbon atoms thereof is from 1 to 30 which may be substituted with an aliphatic group, an aromatic group, a hydroxyl group, an aliphatic oxy group, an acyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, an acyloxy group, an aliphatic sulfonyloxy group or an aromatic sulfonyloxy group, or two nitrogen atoms may join with each other to form a heterocyclic ring such as imidazole or benzimidazole.
In formula (I) R_z represents a halogen atom, (for example, fluorine, chlorine, bromine or iodine), a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, an amino group with 0 to 30 carbon atoms (for example, amino, methylamino, dimethylamino, pyrrolidino, anilino), an alkyl, alkenyl or alkynyl group with 1 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms, a carbonamido group with 1 to 30 carbon atoms (for example, formamido, acetoamido, trifluoroacetoamido, benzoamido), a sulfonamido group with 1 to 30 carbon atoms (for example, methane sulfonamido, trifluoromethane sulfonamido, n-butane sulfonamido, p-toluene sulfonamido), a carbamoyl group with 1 to 30 carbon atoms (for example, carbamoyl, N,N-dimethylcarbamoyl, N-methylcarbamoyl, pyrrolidinocarbonyl, N-n-hexadecylcarbamoyl), a sulfamoyl group with 0 to 30 carbon atoms (for example, sulfamoyl, N-methylsulfamoyl, N,N-dimethylsulfamoyl, morpholino sulfonyl, N-n-dodecyl- sulfamoyl), a ureido group with 1 to 30 carbon atoms (for example, ureido, 3-methylureido, 3-phenylureido, 3,3-dimethylureido), an acyl group with 1 to 30 carbon atoms (for example, acetyl, pivaloyl, benzoyl, dodecanoyl), an acyloxy group with 1 to 30 carbon atoms (for example, acetoxy, benzoyl), an aliphatic oxy group with 1 to 30 carbon atoms, an aromatic oxy group with 6 to 30 carbon atoms, an aliphatic thio group with 1 to 30 carbon atoms, an aromatic thio group with 6 to 30 carbon atoms, an aliphatic sulfonyl group with 1 to 30 carbon atoms, an aromatic sulfonyl group with 6 to 30 carbon atoms, an aliphatic sulfinyl group with 1 to 30 carbon atoms, an aromatic sulfinyl group with 6 to 30 carbon atoms, an aliphatic oxy carbonyl group with 2 to 30 carbon atoms, an aliphatic oxy carbonyl group with 7 to 30 carbon atoms, an aliphatic oxy carbonylamino group with 2 to 30 carbon atoms, an aromatic oxy carbonylamino group with 7 to 30 carbon atoms, a sulfamoylamino group with 0 to 30 carbon atoms (for example, sulfamoylamino, 3,3-dimethylsulfamoylamino, piperidino sulfonylamino), a heterocyclic group with 1 to 30 carbon atoms, or an imido group with 4 to 30 carbon atoms (for example, succinimido, maleinimido, phthalimido, diglycolimido, 4-nitrophthalimido).
In formula (1), R₃ represents a hydrogen atom or RaY, in which R_e represents a hydrogen atom, an alkyl, alkenyl or alkynyl group with 1 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms, a heterocyclic group with 1 to 30 carbon atoms,

-SO₂R₇, -SO₂OR₇, or an imido group with 4 to 30 carbon atoms (for example, succinimido, maleinimido, phthalimido, diacetylimido) ; Y represents
-CO-, -SO₂-, -SO- or single bond, R₇ represents an alkyl, alkenyl or alkynyl group with 1 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms or a heterocyclic group with 1 to 30 carbon atoms ; R₈ represents a hydrogen atom, an alkyl, alkenyl or alkynyl group with 1 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms or a heterocyclic group with 1 to 30 carbon atoms ; Rg and R₁₀ represent independently a hydrogen atom, an alkyl, alkenyl or alkynyl group with 1 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms, a heterocyclic group with 1 to 30 carbon atoms, an acyl group with 1 to 30 carbon atoms (forexample, acetyl, trifluoroacetyl, benzoyl, p-chlorobenzoyl) or a sulfonyl group with 1 to 30 carbon atoms (for example, methane sulfonyl, n-butane sulfonyl, benzene sulfonyl, p-nitrobenzene sulfonyl). R₉ and R₁₀ may join with each other to form a ring.
In formula (I) the group represented by LINK may be present or absent. It is preferred that the group LINK is absent but it may also be properly selected depending on the purpose. In the case of using the group represented by LINK, the following known functional linkage groups may be induded :

(1) groups utilizing the cleavage reaction of a hemiacetal :

They are described, for example, in U.S. Patent 4,146,396 and JP-A-60-249148 and JP-A-60-249149 and represented by the following formula (in this case the symbol ^* represents the coupling active position of a coupler represented by formula (I), that is, the position coupled to the 4-position of 1-naphthol, while the symbol ^** represents the position bonding to S, that is, the sulfur atom in formula (I)) :
wherein W represents an oxygen atom, a sulfur atom or
R₁₁ and R₁₂ each represents a hydrogen atom or a substituent; R₁₃ represents a substituent ; t represents 1 or 2. If t is 2, each
may be indentical to or different from the other. Typical examples of the substituent suitable for use as R₁₁, R₁₂, or R₁₃ are a R₁₅ group, a R₁₆CO- group, a R₁₅SO₂- group, a
group or a
group. In this case R₁₅ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group ; R₁₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R_11' R₁₂, R₁₃ can represent a divalent group, and any two of R₁₁, R₁₂ and R₁₃ can be joined to form a cyclic structure. Specific examples of the group represented by formula (T-1) are set forth below.

(2) groups causing a cleavage reaction utilizing the intramolecular nucleophilic substitution reaction : There can be mentioned a timing group, for example, described in U.S. Patent 4,248,962, which can be represented by the following formula :

In the formula, Nu represents a nucleophilic group in which an oxygen atom or a sulfur atom is an example of the nucleophilic species ; E represents an electrophilic group capable of cleaving the bonding with the symbol ^** upon nucleophilic attack from Nu. LINK represents a linkage group for sterically relating Nu and E such that they can conduct an intramolecular nucleophilic substitution reaction. Specific examples of the groups represented by Formula (T-2) are described below.

(3) groups causing a cleavage reaction utilizing the electron transfer reaction along the conjugated system;

They are described, for example, in U.S. Patents 4,409,323 and 4,421,845, JP-A-57-188035, JP-A-58-98728, JP-A-58-209736, JP-A-58-209738 and JP-A-58-209738 and represented by formula (T-3).
wherein the symbol ^*, the symbol ^**, W, R₁₁, R₁₂ and t have the same meanings as explained for formula (T-1), provided that R₁₁ and R₁₂ may join with each other to form a constituent for a benzene ring or a heterocyclic ring. Specific examples can include the following groups.

(4) groups utilizing the cleavage reaction due to ester hydrolysis :

They are linkage groups described, for example, in West German Patent Application (OLS) No. 2,626,315 and can include the following groups. In the formula the symbol ^* and the symbol ^** have the same meanings as those explained for formula (T-1).

(5) groups utilizing the cleavage reaction of the imino ketal group.

They are linkage groups, for example, described in U.S. Patent 4,546,073 and represented by the following formula.
wherein the symbol ^*, the symbol ^** and W have the same meanings as those for formula (T-1), R₁₄ has the same meanings as for R₁₃ of formula (T-1). Specific examples of the groups represented by the general formula (T-6) can include the following groups :

(6) groups that function as a coupler or reducing agent after the coupling reaction (e.g., hydroquinone, catechol, pyrogallol or an aminophenol derivative) and carry out releasing by the coupling reaction or redox reaction :

They are described, for example, in U.S. Patent 4,438,193 and 4,618,571, and JP-A-60-203943, JP-A-60-213944 and JP-A-61-236551 and specific examples can include the following groups:

(7) groups posessing in combination one or more of the mechanisms of (1) to (6) :

They are described, for example, in JP-A-57-56837, JP-A-60-214358, JP-A-60-218645, JP-A-60-229030 and JP-A-61-156217 and specific examples can include the following groups:

In formula (I), L represents a (n + 1) valent group, that is, those groups formed by removing n number of hydrogen atoms from a linear, branched or cyclic alkyl group with 1 to 8 carbon atoms, an aryl group with 6 to 10 carbon atoms which may be substituted with a halogen atom or an alkyl group, or a heterocyclic group with 1 to 10 carbon atoms (for example, tetrazol-1-yl, 1,3,4-triazol-1-yl, 2-methyl-1,3,4-triazol-1-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-triazol-2-yl, 1-methyl-1,3,4-triazol-2-yl, thiazol-2-yl, oxazol-2-yl, imidazol-2-yl, 1-methylimidazol-2-yl, pyrimidin-2-yl respectively) : X represents a water soluble substituent, and n represents an integer of 1 to 3.
In formula (I), the groups represented by X are those groups with not more than 8 carbon atoms, for example, a carboxyl group, a sulfo group, a hydroxyl group, an amino group, an alkoxy group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, a sulfamyl group, an acryl group, an amidino group, an alkylsulfonyl group, a phosphono group, a phosphonooxy group, or those groups containing at least one of these aforementioned groups.
In formula (I), R₂ and R₃ or a plurality of R₂ may join with each other to form a ring. Examples of R₂ and R₃ joined with each other can include: -CH₂CO-, -OCO-, -NHCO-, C(CH₃)₂CO and -CH=CHCO-. Examples of a plurality of R₂joined with each other can include -(CH₂)₄-, -OCO-, -OCONH-, -NHCONH-, -(CH=CH)₂-, -OCH₂0-, -OCH₂CH₂0- and -OC(CH₃)₂0-.
Examples of preferred substituents in the compound represented by formula (I) are described below.
In formula (I) R₁ is preferably a halogen atom, -COR₄ or -S0₂R₄, and the case in which R₄ represents an amino group is further preferred.
Examples of -COR₄ include carbamoyl, N-ethylcarbamoyl, N-n-butylcarbamoyl, N-cyclohexylcarbamoyl, N-(2-ethylhexyl)carbamoyl, N-dodecylcarbamoyl, N-hexadecylcarbamoyl, N-(3-decyloxypropyl)carbamoyl, N-(3-dodecyloxypropyl)carbamoyl, N-(3-(2,4-di-t-pentylphenoxy)propyl)carbamoyl, N-(4-(2,4-di-t-pentyl- phenoxy)butyl)carbamoyl, N,N-dimethylcarbamoyl, N,N-dibutylcarbamoyl, N-methyl-N-dodecylcarbamoyl, morpholinocarbonyl, N-methyl-N-phenylcarbamoyl, N-(2-tetradecyloxyphenyl)carbamoyl, N-phenylcarbamoyl, N-(4-tetradecyloxyphenyl)carbamoyl, N-(2-propoxyphenyl)carbamoyl, N-(2-chloro-5-dodecyloxyphenyl)carbamoyl and N-(2-chlorophenyl)carbamoyl. Examples of -S0₂R₄ include sulfamoyl, N-methylsulfamoyl, N,N-diethylsulfamoyl, N,N-diisopropylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N-(3-(2,4-di-t-pentylphenoxy)propyl)sulfamoyl, N-(4-(2,4-di-t-pentylphenoxy)butyl)sulfamoyl, pyrrolidinosul- fonyl, N-phenylsulfonyl, N-(2-butoxyphenyl)sulfamoyl and N-(2-tetradecyloxyphenyl)sulfamoyl. As R₁, -COR₄ in which R₄ is an amino group is particularly preferred.
For (R₂)_f in formula (I) ℓ= 1 is desirable and ℓ= 0 is even more desirable. 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 : a fluorine atom, a chlorine atom, a trifluoromethyl group, a methoxy group or a cyano group being particularly preferred. The substitution position of R₂ is preferably at the 2-position or the 4-position relative to R₃NH-.
In the case where R₃ in formula (I) is represented by R₆Y, R_s is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group -OR₇ or -SR7 ; Y is preferably -CO- or -S02-. Examples of the alkyl group include methyl, trifluoromethyl, trichloromethyl, ethyl, heptafluoropropyl, t-butyl, 1-ethylpentyl, cyclohexyl, benzyl, undecyl, tridecyl and 1-(2,4-di-t-pentylphenoxy)propyl. Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, 2-chlorophenyl, 4-methoxyphenyl, 4-nitrophenyl and pentafluorophenyl. Examples of-OR₇ include methoxy, ethoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentyloxy, n-hexyloxy, n-octyloxy, 2-ethylhexyloxy, n-decyloxy, n-dodecyloxy, 2-methoxyethoxy, benzyloxy, trichloroethoxy, trifluoroethoxy, phenoxy and p-methylphenoxy. Examples of -SR₇ include methylthio, ethylthio, allylthio, n-butylthio, benzyl- thio, n-dodecylthio, phenylthio, p-t-octylphenylthio, p-dodecylphenylthio, and p-octyloxyphenylthio. R₃ is, more preferably, an aliphatic oxy carbonyl group in which R_e is R₇0 and Y is -CO-, or an aliphatic or aromatic sulfonyl group in which R_e is an alkyl, alkenyl, alkynyl or aryl group and y is -SO_z-. R₃ is most preferably an aliphatic oxy carbonyl group.
In formula (I), LINK is preferably represented by formula (T-1), (T-2) or (T-3) described above, but it is generally preferred when m = 0, that is, not using the functional connection group.
In formula (I), L is preferably an alkylene group or a heterocyclic group, more preferably, an alkylene group.
In formula (1), X is, preferably, a substituent in which the π-substituent constant is 0.5 or less, preferably, the substituent constant has a negative value. The value is determined by the method as described in "Substituent Constants for Correlation Analysis in Chemistry and Biology" written by C. Hansch and A. Leo, published by John Wiley, 1979. Examples of X and π-substituent constants (within ( )) are shown below.
In formula (I) n is preferably 1 or 2 and, more preferably 1.
Further, in formula (I) most preferred -S-L-(X)_n is represented by the following formula (II) :
wherein R₁₇ and R₁₈ represent a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, p represents an integer of 1 to 8, and Z represents a hydroxyl group, a carboxyl group, a sulfo group or an amino group with 0 to 8 carbon atoms (for example, amino, methylamino, ethylamino, methoxyethylamino, butylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, piperidino, pyrrolidino, morpholino). In case where p represents an integer of 2 to 8, each
may be identical to or different from the others, and the number of carbon atoms in
is from 1 to 8. Among the groups represented by Z, the carboxyl group is particularly preferred.
In formula (I), examples of -S-L-(X)_n are shown below.
The coupler represented by formula (I) may form a dimer or higher polymer joined with another by way of divalent or higher valent groups at the substituents R₁, R₂ and R₃ respectively. In this case, the range for the number of carbon atoms shown for each of the substituents as described above may be beyond the scope of the above definition.
In the case where the coupler represented by formula (I) forms a polymer, typical examples thereof include a homopolymer or copolymer of addition polymerizable ethylenically unsaturated compounds having a cyan dye forming coupler residue (cyan color forming monomer). In this case, the polymer contains repeating units of formula (III) and one or more of cyan color-forming repeating units represented by formula (III) may be contained in the polymer and it may be a copolymer containing one or more of the non-color-forming ethylenic monomer as the copolymerization ingredient.
wherein R represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or a chlorine atom; A represents -CONH-, -COO- or a substituted or unsubstituted phenylene group ; B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group; L' represents -CONH-, -NHCONH-, - NHCOO-, -NHCO-, -OCONH-, -NH-, -COO-, -OCO-, -CO-, -O-, -SO_z-, -NHS0₂- or -S0₂NH-, a, b, c represents 0 or 1. Q represents a cyan coupler residue formed by removing other hydrogen atoms than the hydrogen atom at the hydroxy group on the 1-position of the compound represented by formula (I).
As the polymer, a copolymer of the cyan color forming monomer giving the coupler unit of formula (III) with the following non-color-forming ethylenic monomer is preferred.
The non-color-forming ethylenic monomer, which is not coupled with oxidation products of an aromatic primary amine developing agent, can include acrylic acid ; a-chloroalkylacrylic acid ; a-alkylacrylic acid (for example, methacryl acid), esters or amides derived from these acrylic acids (for example, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, N-methylolacrylamide, N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide, N-(3-sulfonatopropyl)acrylamide, methylacrylate, ethylacrylate, n-propylacrylate, n-butylacrylate, t-butylacrylate, isobutylacrylate, acetoacetoxyethylacrylate, n-hexylacrylate, 2-ethylhexylacrylate, n-octylacrylate, laurylacrylate, methylmethacrylate, ethylmethacrylate, n-butylmethacrylate, p-hydroxymethacrylate) ; vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl laurate) ; acrylonitrile ; methacrylonitrile ; aromatic vinyl compound (for example, styrene and derivatives thereof such as vinyltoluene, divinyl benzene, potassium styrene sulfinate, vinyl acetophenone, sulfostyrene) ; itaconic acid ; citraconic acid; crotonic acid ; vinylidene chloride ; vinylalkyl ether (for example, vinylethyl ether, maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine, 2- and 4-vinyl pyridine).
Acrylic acid ester, methacrylic acid ester and maleic acid esters are particularly preferred. Two or more of the non-color-forming ethylenic monomers can be used together. For instance, the following combinations can be used : methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methylacrylate and diacetone acrylamide, N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide and acrylic acid, potassium styrene sulfinate and N-vinylpyrrolidone.
As is well-known in the field of polymer couplers, the ethylenically unsaturated monomer for copolymerization with a vinylic monomer corresponding to formula (III) described above can be selected such that a preferred effect can be given to the copolymer formed with respect to physical properties and/or chemical properties of the copolymer, such as solubility, compatibility with a binder for the photographic colloid composition (for example, gelatin), flexibility and heat stability.
For obtaining an oleophilic polymer coupler soluble in organic solvent, it is preferred to select, as the copolymerization ingredient, mainly oleophilic non-color-forming ethylenic monomer, for example, acrylic acid ester, methacrylic acid ester, maleic acid ester, vinyl benzene.
The emulsion of the cyan polymer couplerfor use in the material of this invention may be prepared by emulsion-dispersing a solution of the oleophilic coupler obtained by polymerization of the vinylic monomer giving the coupler unit dissolved in an organic solvent in an aqueous gelatin solution in the form of a latex or may be prepared by a direct emulsion polymerization method.
For emulsion-dispersing the oleophilic polymer coupler in an aqueous gelatin solution in the form of a latex, the method described in U.S. Patent 3,451,820 can be used and for the emulsion polymerization, the method described in U.S. Patents 4,080,211 and 3,370,952 can be used.
For obtaining a hydrophilic polymer coupler soluble in neutral or alkaline water, it is preferred to use, as a copolymerization ingredient, hydrophilic non-color-forming ethylenic monomers such as N-(1,1-dimethyl-2-sul- fonatoethyl)acrylamide, 3-sulfonate propylacrylate, sodium styrenesulfonate, potassium 2-styrene sulfinate, propylacrylate, methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone and N-vinylpyridine.
The hydrophilic polymer coupler can be added as an aqueous solution to a coating liquid, and it is also possible to add same after being dissolved in a mixed solvent of a water miscible organic solvent such as a lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexane, ethyl lactate, dimethyl formamide or dimethylacetoamide and water. Further, the coupler may be added after being dissolved in an aqueous alkali solution or an alkali-containing organic solvent Furthermore, a small amount of a surface active agent may be added.
Specific examples of the coupler represented by formula (1) used in the present invention are shown below.
The compounds represented by formula (I) can, for example, be synthesized according to the methods described in EP-A-161626, and JP-A-61-201247. Further, a compound having a functional linkage group can be synthesized according to the methods described in those patent literatures set forth above for the explanation of the functional linkage groups, for example, U.S. Patents 4,146,396, 4,246,962, 4,409,323 and 4,421,845.
General synthesizing methods for the compounds not containing timing groups are described below. The compounds represented by formula (I) used in the present invention can be synthesized by the methods shown below as (1), (2), (3).

(1) Thioetherifying reaction of 4-mercapto-1-naphthols in the presence of a base :
R' represents-L-(X)_n or a precursor thereof and G represents a group capable of splitting by a nucleophilic substitution reaction, for example, a halogen atom, a nitro group, a sulfonyl group and a sulfonyloxy group.
(2) Nucleophilic substitution reaction between 4-halogeno-1-naphthols and mercaptans in the presence of a base:
In the formula G and R' have the same meanings as G and R' in (1) above.
(3) Reaction between 1-naphthols and sulfenyl halide, sulfene amide, sulfene imide, disulfide, thiuram disulfide or thiol sulfonic acid ester :
wherein R' has the same meaning as R' in (I) above and V represents a halogen atom, an amino group, an imido group, an alkyl, an aryl or a heterocyclic thio group, an amidinothio group or a sulfonyl group.

Synthesis examples are shown below.

Synthesis Example

Synthesis of Exemplified Compound (5) :

26,4 g of 5-isobutoxycabonylamino-1-hydroxy-N-(3-dodecyloxy propyl)-2-naphthoamide was dissolved in 300 ml of methylene chloride and cooled to 0°C, to which 6.8 g of sulfuryl chloride was dropped under stirring for about 10 min. After stirring for 1 h, the solution of methylene chloride was washed with 300 ml of water and then concentrated under reduced pressure. 8.5 g of N,N-dimethylaminoethanethiol hydrochloride, 30 g of potassium carbonate and 400 ml of N,N-dimethylformamide were added to the residue and then heated under reflux for 3 h under a nitrogen gas stream. The reaction solution was cooled, 300 ml of ethyl acetate was added and extracted after neutralization. After sufficiently washing the ethylacetate solution with water, it was concentrated and fractionated by using a chromatographic column packed with silica gel using a mixed solvent of ethyl ace- tate/n-hexane (1/2) as a developing solvent The fractionated developing solution was concentrated to obtain 18.6 g of the oily compound (5), that is, 5-isobutoxycarbonylamino-4-(2-N,N-dimethylamino ethylthio)-1-hydroxy-N-(3-dodecyloxypropyl)-2-naphthoamide. Yield : 5.9%.

The addition amount of the bleach accelerator releasing type coupler represented by formula (I) to the photosensitive material is preferably from 1 x 10-⁷ mol to 1 x 10-¹ mol, particularly, from 1 x 10^-6 mol to 5x 10-² mol per m² of the photosensitive material. While the bleach accelerator releasing compound used according to the present invention can be added to any of the layers in the photosensitive material, it is preferred to add same to the photosensitive emulsion layer, particularly, a red-sensitive emulsion layer.
In the following the silver halide used in the emulsion layer of the photosensitive material is explained in more detail. Any silver halide, that is, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride and silver chloroiodide may be used, but the use of silver iodobromide is particularly preferred. In the case of using silver iodobromide, the silver iodide content is usually less than 40 mol%, preferably, less than 20 mol% and more preferably, less than 10 mol%.
The silver halide grains may be so-called regular grains having a regular crystal body such as a hexahed- ron, an octahedron or tetradecahedron or those of irregular crystal forms such as spheres, those having crystal defects such as twine planes or mixed forms thereof. Furthermore, a mixture of grains of various crystal forms may be used.
The silver halide may either be a monodispersed emulsion having a narrow distribution or a polydispersed emulsion having a broad distribution.
For the emulsion layer described above, tabular grains with an aspect ratio of 5 or more may be used.
The cristal structure of the emulsion grains mav hA uniform or one having a different halogen composition compositions may be joined by epitaxial junction, or may be joined with other compounds than silver halide such as silver rhodanate or lead oxide.
The emulsion described above may of a (A) a surface latent image type whereby latent images are formed mainly on the surface of the grains, or of (B) an internal latent image type whereby latent images are formed to the inside of the grains, or of (C) a type whereby the latent images are formed both on the surface as well as on the inner side of the grains. Grains in which the inside thereof is chemically sensitized may be used.
Silver halide photographic emulsions usable in the present invention can be produced by properly using known methods. For example, the emulsion can be prepared according to the method described in Research Disclosure vol. 176, No. 17643 (December 1978), pages 22 to 23, "Emulsion Preparation and Types", vol 187, No. 18716 (November 1979), page 648.
For the preparation of the photographic emulsion it is possible if required to use various types of silver halide solvents, for example, ammonia or potassium rhodanate or thioethers and thion compounds as described in U.S. Patent 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 or JP-A-54-155828.
As the monodispersed emulsion, typical silver halide grains have an average grain size of not less than 0.1 pm in which at least 95% by weight thereof is within ± 40% of the average grain size. Those emulsions with average grain size from 0.25 to 2 µm in which at least 95% by weight of the number of silver halide grains are within the range of an average grain size ± 20% can be used.
In the course of forming or physically ripening silver halide grains, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex thereof, a rhodium salt or a complex thereof, an iron salt or a complex salt may be present alone or with other of the above mentioned salts.
The emulsion used in the present invention is usually subjected to chemical ripening and spectral sensitization after the physical ripening.
The additives used in such steps are described in Research Disclosure No. 17643 (December, 1978), and No. 18716 (November, 1979) described above and the relevant portions of the literatures are summarized in the table below.
Known photographic additives usable in the present invention are also described in the two Research Disclosures described in the paragraph above, and the relevant portions are also shown hereinafter in the following table.
Although known spectral sensitizers as described above are used for the color photosensitive material of the present invention, it is preferred in the processing method of the present invention to use those compounds and specific compounds represented by formula (IV) or (V) as described in pages 90 to 110 of JP-A-63-163853.
In the present invention, various color couplers can be used in addition to the cyan image forming coupler of formula (I) and specific examples thereof are described in patent literatures set forth in Research Disclosure (RD) No. 17643, VII-C to G. As the color forming coupler, those couplers giving three primary colors by a subtractive color process (that is, yellow, magenta and cyan) by color development are important, and the following couplers can be used preferably in the material of the present invention in addition to the diffusion resistant 4-equivalent or 2-equivalent couplers specifically described in the patent literatures set forth in Research Disclosure No. 17643, VII-C and D.
Typical examples of the yellow couplers usable herein include known oxygen atom releasing type yellow couplers or nitrogen atom releasing type yellow couplers. a-Pivaloyl acetoanilide type couplers are excellent in the fastness of the color forming dye, particularly, light fastness, whereas a-benzoyl acetoanilide type couplers can provide a high color forming density.
The magenta couplers usable in the present invention include hydrophobic 5-pyrazolone type and pyrazoloazole type couplers having ballast groups. Among the 5-pyrazolone type couplers, those substituted at the 3-position with an aryl amino group or an acyl amino group are preferred in view of the hue and the color forming density of the color forming dye.
The cyan coupler usable in the present invention further includes hydrophobic and diffusion resistant naphthol and phenol type couplers, and 2-equivalent naphthol type couplers of the oxygen atom releasing type can be mentioned as preferred typical examples. Furthermore, those couplers capable of forming a cyan dye fast to humidity and temperature are preferably used and typical examples thereof include phenol type cyan couplers having an ethyl or a higher alkyl group at the metaposition of the phenol nuclei and 2,5-diacrylamino substituted phenol type couplers, phenol type couplers having a phenyl ureido group at the 2-position and a diacylamino group at the 5-position as described in U.S. Patent 3,772,002, and 5-amidonaphthol type cyan couplers as described in EP-A-161626.
A coupler in which the color forming dye has an adequate diffusing property may be used to improve the granular property. For such couplers, specific examples of a magenta coupler are found in U.S. Patent 4,366,237, and specific examples of a yellow, magenta or cyan coupler are found in European Patent 96,570.
The dye-forming couplers and the particular couplers described above may form a dimer or a higher polymer. Typical examples of polymerized dye-forming couplers are described in U.S. Patent 3,451,820. Specific examples of polymerized magenta couplers are described in U.S. Patent 4,367,282.
Couplers releasing a photographically useful residual group upon coupling can also be used preferably in the present invention. As DIR coupler releasing development inhibitors, those patented couplers described in RD 17643, VII-F (described above) are useful.
Those couplers releasing a nucleating agent, a development accelerator or a precursor thereof upon development imagewise can be used for the photosensitive material according to the present invention. Specific examples of such compounds are described in British Patents 2,097,140 and 2,131,188. In addition, it is possible to use DIR redox compound releasing couplers as described in JP-A-60-185950, and couplers releasing dyes restoring color after splitting as described in EP-A-173302.
The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods. Examples of high boiling point organic solvents used for the oil-in-water droplet dispersion method are described in U.S. Patent 2,322,027. The steps and the effect of the latex dispersion method and specific examples of latices for impregnation are described in U.S. Patent 4,199,363, German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
The photosensitive material of the present invention may also contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, non- coloring couplers, an sulfonamido phenol derivatives as an anti-color fogging agent or an anti-color mixing agent
Known anti-discoloration agents may be used for the photosensitive material of the present invention. Typical examples of known anti-discoloration agents include hydroquinones, 6-hydroxychromans, 5-hydroxycuma- rans, spirochromans, p-alkoxyphenols, hindered phenols such as bisphenols, gallic acid derivatives, methylene dioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating or alkylating phenolic hydroxy groups in each of the compounds. Furthermore, metal complexes typically represented by a (bissalicylaldoxymato)nickel complex and a (bis-N,N-dialkyldithiocarbamato)nickel complex may also be used.
In the photosensitive material according to the present invention the photographic emulsion layer and other layers are coated on a typical flexible support such as plastic films.
The photographic emulsion layer and other hydrophilic colloid layers can be coated by utilizing various known coating methods, for example, dip coating, roller coating, curtain coating and extrusion coating.
The present invention can be applied to various color photosensitive materials. Typical examples thereof include general-purpose or cinema use color negative films, color reversal films for slide or television use, color papers, color positive films, and color reversal papers.
The colordeveloper used forthe development of the photosensitive material according to the present invention is an aqueous alkaline solution using an aromatic primary amine color developing agent as the main ingredient. While an aminophenol type compound is also useful as the color developing agent, a p-phenylene diamine compound is preferably used and typical examples thereof include 3-methyl-4-amino-N,N-diethylaniline, 3-methy)-4-amino-N-ethyt-N-p-hydroxyethy)aniiine, 3-methyl-4-amino-N-ethyl-N-fi-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-J3-methoxyethyl aniline, as well as a sulfate, a hydrochloride, a phosphate, a p-toluene sulfonate, a tetraphenyl borate, a p-(t-octyl) benzene sulfonate thereof. Usually a salt form of these drammes is more stable and used more preferably man the Tree state.
The aminophenol derivative includes, for example, o-aminophenol, p-aminophenol, 4-amino-2-methylphenol, 2-amino-3-methylphenol and 2-oxy-3-amino-1,4-dimethylbenzene.
In addition, those as described in "Photographic Processing Chemistry" written by L.F.A Mason, published from by Focal Press, pages 226 to 229 (1966), in U.S. Patents 2,193,Ot5, 2,592,364, JP-A-48-64933, may be used. If required, two or more color developing agents may be used in combination.
The color developer may also contain a pH buffer such as an alkali metal carbonate, a borate or a phosphate ; a development inhibitor or an anti-foggant such as a bromide, a iodide, benzoimidazoles, benzothiazoles, and mercapto compounds; a preservative such as hydroxylamine, triethanol amine, compounds described in German Patent Application (OLS) No. 2,622,950, sulfite or hypersulfite ; an organic solvent such as diethylene glycol ; a development promoter such as a benzyl alcohol, polyethylene glycol, a quaternary ammonium salt, amines, a thiocyanate and, 3,6-thiaoctane-1,8-diol ; a dye-forming coupler ; a competing coupler; a nucleating agent such as sodium boronhydride; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone ; a tackifier ; and a chelating agent such as ethylenediamine tetraacetic acid, nitrilotriacetic acid, cyclohexane diamine tetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediamine triacetic acid, diethylenetriamine pentaacetic acid, triethylenetetramine hexaneacetic acid and aminopolycarboxylic acid represented by the compounds as described in JP-A-58-195845, 1-hydroxyethylinden-1,1'-diphosphonic acid, organic phosphonic acid as described in Research Disclosure No. 18170 (May, 1979), aminophosphonic acid such as aminotris(methylene phosphonic acid), ethylenediamine-N,N,N',N'-tetramethylene phosphonic acid, phosphono carboxylic acid as described in Research Disclosure No. 18170 (May, 1979).
The color developing agent is used in a concentration of 0.1 g to 30 g per 1 I of the usual color developer solution, more preferably, in a concentration of from 1 g to 15 g per 1 I of the color developer solution. Further, the pH value of the color developer is usually 7 or higher and, most generally, 9 to 13.
In the present invention, the silver halide color photographic material is color developed as described above after imagewise exposure, and then processed with a processing solution having a bleaching performance.
A processing solution having a bleaching performance designates processing solutions having a performance of oxidizing metal silver resulting from the developing reaction and colloidal silver contained in the photosensitive material thereby converting them into a soluble silver salt such as a silver thiosulfate complex or an insoluble silver salt such as silver bromide, and they include, a bleaching solution, or a bleach-f_lxing solution. In the present invention, it is preferred to carry out processing with a processing solution having a bleach-fixing performance directly after processing with the color development.
The bleaching agent used in the processing solution having the bleaching performance includes a ferric complex salt such as ferricyanate ferric complex salts or citrate ferric salts, and a peroxide such as a persulfate or hydrogen peroxide. Preferred is a aminopolycarboxylic acid ferric complex salt, which is a complex of ferric ions with an aminopolycarboxylic acid or a sait thereof.
Typical examples of the aminocarboxylic acids and salts thereof include:

(1) diethylenetriamine pentaacetic acid,
(2) pentasodium salt of diethylenetriamine pentaacetic acid,
(3) ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid,
(4) trisodium ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetate.
(5) triammonium ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetate.
(6) 1,2-diaminopropane tetraacetic acid,
(7) disodium 1,2-diaminopropane tetraacetate,
(8) nitrilotriacetic acid,
(9) sodium nitrilotriacetic acid salt,
(10) cyclohexanediamine tetraacetate,
(11) cyclohexanediamine tetraacetic acid disodium salt,
(12) N-methyliminodiacetic acid,
(13) iminodiacetic acid,
(14) dihydroxyethyl glycine,
(15) ethylether diamine tetraacetic acid,
(16) glycol ether diamine tetraacetic acid,
(17) ethylenediamine tetrapropionic acid,
(18) 1,3-diaminopropane tetraacetic acid and
(19) ethylenediamine tetra-acetic acid.

Among the compounds described above, (1), (2), (6), (7), (10), (11), (16), (18) are particularly preferred.
The aminocarboxylic acid ferric complex salt may be used in the form of a complex salt, or a ferric ion complex salt may be formed in a solution using a ferric salt, for example, ferric sulfate, ferric chloride, ferric sulfate, ammonium ferric sulfate and ferric phosphate with aminocarboxylic acid. In the case of using an aminocarboxylic acid ferric complex salt as a complex salt, the complex salt may be used alone or as a mixture of two or more of them. On the other hand, in the case of forming a complex salt in a solution using a ferric salt and an aminocarboxylic acid, one or more ferric salts may be used. Furthermore, one or more aminocarboxylic acids may be used. Further, in any case, aminopolycarboxylic acid may be used in excess amounts for forming the ferric ion complex salts.
Further, at least one of an aminopolycarboxylic acid Fe (III) complex salt described above, except for (19), and an ethylenediamine tetraacetic acid Fe (111) complex salt may be used in combination.
The processing solution having the bleaching function containing the ferric complex salt described above may contain metal ion complex salts such as of cobalt, nickel and copper other than iron ions.
The amount of the bleaching agent per one liter of the processing solution having the bleaching performance is from 0.1 mol to 1 mol, preferably, from 0.2 mol to 0.5 mol. Further, the pH value of the bleaching solution is preferably from 4.0 to 8.0, particularly, from 5.0 to 7.5 and more preferred 5,7 or less.
The processing bath having the bleaching performance can contain, in addition to the bleaching agent and the compound as described above, a re-halogenating agent such as a bromide, (for example, potassium bromide, sodium bromide, ammonium bromide) ora chloride, (forexample, potassium chloride, sodium chloride and ammonium chloride). In addition, those additives known to be used for a tin bleach-fixing solution such as one or more inorganic acids, organic acids and salts thereof having pH buffering performance can be added, for example, a nitrate (such as sodium nitrate and ammonium nitrate), boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid.
In the present invention, the fixing bath subsequent to the bleaching bath or a processing bath having bleach-fixing performance can be incorporated with those compounds known as fixing agents such as a thiosulfate, (for example, sodium thiosulfate, ammonium thiosulfate, ammonium sodium thiosulfate and potassium thiosulfate), a thiocyanate (such as ammonium thiocyanate and potassium thiocyanate), thiourea and a thioether. The addition amount of these fixing agents is preferably less than 3 mol and, particularly preferably less than 2 mol per 1 of the processing solution having the fixing performance or the processing solution having the bleach-fixing performance.
The processing solution having the bleach-fixing performance can contain so-called sulfite ion releasing compounds such as a sulfite, (for example, sodium sulfite and ammonium sulfite), a hydrogensulfite or an aldehyde and a hypersulfite addition product (for example, carbonyl-bisulfite). Furthermore, it is possible to incorporate aminopolycarboxylic acid salts as shown from (1) to (19), or organic phosphonic acid compounds such as ethylenediamine tetrakismethylenephosphonic acid, diethylenetriamine pentakismethylenephos- phonic acid, 1,3-diaminopropane tetrakis methylenephosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid and 1-hydroxyethyiidene-1,1'-diphosphonic acid.
In the present invention at least one bleaching accelerator selected from compounds having a mercapto group or a disulfide bond, isothiourea derivatives and thiazolidine derivatives may be incorporated in the processing solution having the bleaching function for conducting the processing. The amount of such compounds per 1 I of the processing solution having the bleach-fixing performance is preferably from 1 x 10^-5 to 1 x 10-¹ mol and, more preferably, from 1 x 1 Q-4 to 5 x 10-².
The bleaching accelerator incorporated in the processing solution having the bleaching performance is selected from the compounds having a mercapto group or a disulfide bond, a thiazolidine derivative, a thiourea derivative and isothio derivatives, as long as they are effective in bleaching acceleration. These compounds and specific examples are preferably described in JP-A-63-163853.
For adding the compound into the processing solution, it is generally preferred to previously dissolve same in water or an alkaline organic acid organic solvent. If the compound is added in the form of powder directly to the processing bath having the bleaching function, this causes no undesired effect at all for the bleaching acceleration.
Furthermore, the bleaching accelerator can be incorporated into the photosensitive material of the present invention. In this case, the bleaching accelerator can be incorporated into any one of the blue-sensitive, green-sensitive and red-sensitive emulsion layers, or a gelatin layer at the uppermost, intermediate or the lowermost layer.
The processing bath having the bleach-fixing performance according to the method of the present invention may be a step including one vessel. Alternatively, it may be constituted as a step including two or more vessels in which replenishing solution is supplied to the group of vessels in a multi-stage countercurrent system. Furthermore, the processing solutions in the group of the vessels may be circulated to form a uniform processing solution as the whole and the replenishing solution may be supplied to one of the vessels of the group.
The silver halide color photosensitive material according to the present invention is usually applied to desilvering processing such as fixing or bleach-fixing and, thereafter, subjected to a water washing and/or stabilizing step.
The amount of washing water in the water washing step can be set within a wide range depending on the characteristics of the photosensitive material, for example, the material used such as coupler, the application use and, further, the temperature of the washing water, the number ofwaterwashing vessels (number of steps), the replenishing system such as countercurrent or normal current type as well as other various conditions. The relationship between the number of water washing vessels and the amount of water in the multi-stage countercurrent system can be determined by the method described in "Journal of the Society of Motion Picture and Television Engineers", Vol. 64, pages 248 to 253 (May, 1955).
According to the multi-stage countercurrent system described in the literature above, although the amount of washing water can be remarkably decreased, this results in problems such as bacteria propagation due to the increase in the water staying time within the vessel causing deposition of suspending matters to the photosensitive material. In the processing of the color photosensitive material according to the present invention, a method of reducing calcium and magnesium as described in JP-A-62-288838 can be used extremely effectively as a countermeasure for such problem. Furthermore, an isothiazolone compound or cyabendazoles, chlorine type fungicides such as chlorinated sodium isocyanurate or other benzotriazole, as described in JP-A-57-8542, as well as bacteriocides described in "Chemistry of Bacteriocide and Fungicide" written by Hiroshi Horiuchi, "Microorganism Fungicide, Bacteriocide and Fungicide Technology" edited by Eisei Gijutsukai, "Bacteria and Fungi Control Encyclopedia" edited by Nippon Bacteria and Fungi Controlling Society can be used.
The pH value forthe washing water in the processing of the photosensitive material according to the present invention is from 4 to 9, preferably, 5 to 8. The temperature and the time for water washing can also be set variously depending on the characteristics and the application uses of the photosensitive material and it is generally selected within a range from 20 to 10 min at 15 to 45°C, preferably, from 30 to 5 min at 25 to 40°C.
Furthermore, the photosensitive material according to the invention can be processed directly with a stabilizing solution instead of water washing. In such a stabilizing processing, any known method can be used as described in JP-A-57-8543, JP-A-58-14834, JP-A-59-184343, JP-A-60-220345, JP-A-60-238832. JP-A-60-239784, JP-A-60-239749, JP-A-61-4054 and JP-A-61-118749.
Particularly, stabilizing baths containing 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound or an ammonium compound can preferably be used.
In addition, there is a case of applying a further stabilizing processing subsequent to the water washing processing. A stabilizing bath containing formalin and a surface active agent used as the final bath for the camera film type color photosensitive material can be mentioned as an example.
The following examples illustrate the present invention.

EXAMPLE 1

On a cellulose triacetate film support applied with primer coating, Specimen 101 which is a multi-layered color photosensitive material comprising each of the layers of the composition shown below was prepared. (Composition of the photosensitive layer)
The coating amount was shown, for the silver-halide and colloidal silver by the amount of silver represented by g/m² unit, for the coupler, additive and gelatin, by the amount represented by g/m² unit and, for the sensitizing dye, by the mol number per one mol of silver halide in one identical layer.

First Layer (Anti-halation layer)

Second Layer (Intermediate layer)

Third Layer (First red-sensitive emulsion layer)

Fourth Layer (Second red-sensitive emulsion layer)

Fifth layer (Third red-sensitive emulsion layer)

Sixth Layer (Intermediate layer)

Seventh Layer (First green-sensitive emulsion layer)

Eighth Layer (Second green-sensitive emulsion layer)

Ninth Layer (Third green-sensitive emulsion layer)

Tenth Layer (Yellow filter layer).

Eleventh Layer (First blue-sensitive emulsion layer)

Twelfth Layer (Second blue sensitive emulsion layer)

Thirteenth Layer (First protective layer)

Fourteenth Layer (Second protective layer)

In addition to the ingredients described above, a surface active agent was added as a coating aid to each of the layers. The specimen prepared as described above is referred to as Specimen 101.
The chemical structural formula or chemical names of the compounds used in the present invention are shown below.

x/y=7/3 (weight ratio)
Solv-1 Tricresyl phosphate
Solv-2 Dibutyl phthalate
Solv-3 Bis(2-ethylhexyl)phthalate

Specimens 102 to 110

Specimens 102 to 110 were prepared in the same manner as Specimen 101 by using comparative compounds A, B and C and compounds of the formula (1) each in an equal molar amount instead of the coupler EXC-6 added to the fifth layer in Specimen 101.
After cutting the obtained Specimens 101 to 110 into 35 mm width, a standard object was photographed and a running test was carried out respectively through the following processing steps (I) to (III). After the end of the running, each of Specimens 101 to 110 was exposed with 20 CMS by white light, each of the running solutions was passed and the practical allowable range of residual silver amount measured by fluorescent X-ray was less than 30 mg/m².
Measurement for Dmin and measurement for sensitivity were also conducted.
Furthermore, the specimens passed through the processing (lll) were stored under 80°C, 70% relative humidity atmosphere for 30 days in a dark place to examine the color image fastness.
The result is shown in Table 1.

Processing Operation (I) (temperature 38°C)

In the above processing step, the stabilization steps (1), (2) and (3) were conducted as a countercurrent system of (3) → (2) → (1). The amount of the fixing solution carried to the water washing vessel was 2 ml per 1 m.

(Color development solution)

(Bleaching solution)

(Fixing solution)

(Stabilizing solution)

Processing Operation (II) (Temperature 38°C)

In the above processing step, the water washing (1) and (2) were conducted as a countercurrent system of (2) → (1). The composition for each of the processing solutions is described below.

(Color developing solution)

Bleaching solution: In common with the mother liquid and

replenishing solution

Bleach-Fixing solution:

In common with the mother liquid and replenishing solution

Tap water passed through a column packed with Na type strongly acidic cationic exchange resin (Diaion SK-1 B) manufactured by Mitsubishi Chemical Industries Ltd., to adjust to the water quality : 2 mg/l of calcium and 1.2 mill of magnesium was used as the water for washing.

Stabilizing solution

Same as in the processing step (I).

Processing Operation (III) (Temperature 38°C)

(Color development solution)

(Bleach-fixing solution)

Washing water

The following three types of water was used.

(1) Tap Water

(2) Ion exchange processed water

The tap water was processed by using a strongly acidic cationic exchange resin (Na type) manufactured by Mitsubishi Chemical Industries Ltd. to adjust the water quality as described below.

(3) Tap water added to a chelating agent

Disodium ethylenediamine tetraacetate was added to 500 mgll of the tap water described above. pH 6.8
Processing was carried out by using the steps and processing solutions as described above.

Comparative Coupler A

Compound described in Research Disclosure No. 11449 (1973)

Comparative Coupler B

Compound described in JP-A-61-201247

Comparative Coupler C

Compound described in JP-A-61-201247

Specimens 101 to 110 were processed in the same manner as in the processing step (III) exceptfor changing the replenishing amount in the water washing step from 10 ml to 125 ml (referred to as Processing step (IV)).
Dmin of the specimen (magenta) after processing was measured and compared with that in the processing step (III).
As a result, Dmin was reduced by 0.05 for Specimen 104, but it was substantially the same for other specimens.
From the result, it can be seen that although the comparative coupler C is excellent in the dark discoloration property, the increase in Dmin is large when the amount of replenishing washing water is low.
As is apparent from the results of Table 1, the coupler of formula (l) shows remarkable effects in the reduction of the residual silver amount and the fastness of cyan color image, with no side effect such as increase in Dmin and has sufficient sensitivity as well.

Example 2

The same running processing was carried out as in Example 1 while changing the pH value of the bleach-fixing bath used in the processing step (III) to 6.0, 5.7, 5.5. Then the residual silver amount and the density of the cyan dye image were measured for Specimens 101 to 110 subjected to wedge exposure.
Then, after processing the processing agent strips with the bleaching solution in the processing step (I) for 4 min thereby sufficiently recovering the concentration, the concentration was measured.
The result is shown in Table 2.
It can be seen that the use of the coupler of formula (I) provides a sufficient cyan concentration even when passed through a bleach-fixing bath at a low pH effective for the improvement of the desilvering rate, and it can satisfy both the improvement of the desilvering property when using a bleach-fixing bath at a low pH and the stability of the cyan dye image (resistivity to the reduction in color restorability).

EXAMPLE 3

On a cellulose triacetate film support applied with primer coating, Specimen 201, that is, a multi-layered color photosensitive material comprising each of the layers of the composition shown below was prepared. (Composition of the photosensitive layer)
The coating amount was shown, for the silver-halide and colloidal silver, by the amount of silver represented by g/m² unit, for the coupler, additive and gelatin by the amount represented by glm² unit and, for the sensitizing dye, by the mol number per one mol of silver halide in one identical layer.

First Laver (Anti-halation layer)

Second Layer (Intermediate layer)

Third Layer (Low-sensitive red-sensitive emulsion layer)

Fourth Layer (High-sensitive red-sensitive emulsion layer)

Fifth layer (Intermediate layer)

Sixth Layer (Low-sensitive green-sensitive emulsion layer)

Seventh Layer (High-sensitive green-sensitive emulsion layer)

Eighth Layer (Intermediate layer)

Ninth Layer (Donor layer having interlayer effect to red sensitive layer)

Tenth Layer (Yellow filter layer)

Eleventh Layer (Low-sensitive blue-sensitive emulsion layer)

Twelfth Layer (High-sensitive blue-sensitive emulsion layer)

Thirteenth Layer (First protective layer)

Fourteenth Layer (Second protective layer)

In addition to the ingredients described above, stabilizer Cpd-3 for the emulsion (0.04 g/m²) and surface active agent Cpd-4 (0.01 g/m²) were added as coating aid to each of the layers.

Solv-1 tricresyl phosphate
Solv-2 dibutyl phthalate

Specimens 202 to 210

Specimens 202 to 210 were prepared by replacing coupler EXC-6 added to the fourth layer in Specimen 201 by the comparative coupler and the coupler of formula (I) used in Example 1.
When the same test as in Example 2 was applied to the obtained Specimens 201 to 210, substantially the same effects could be obtained.

Claims

1. A silver halide colour photosensitive material comprising at least one silver halide emulsion layer on a support, which contains at least one bleaching accelerator releasing type coupler characterised in that said bleaching accelerator releasing type coupler is represented by the following formula (I) :

wherein R₁ is selected from the group consisting of a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amidino group, a guanidino group,

R₂ is selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an amino group, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl 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 thio group, an aromatic thio group, an aliphatic sulfonyl group, an aromatic sulfonyl group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic oxy carbonyl group, an aromatic oxy carbonyl group, an aliphatic oxy carbonylamino group, an aromatic oxy carbonylamino group, a sulfamoyl amino group, a heterocyclic group and an imido group ; frepresents an integer of 0 to 3 ; R₃ is selected from the group consisting of a hydrogen atom and R₆Y, or R₂and R₃ may join with each other to form a ring ; LINK represents a functional linkage group connecting by way of a hetero atom to the 4-position of a naphthol ring ; m represents 0 or 1 ; L is selected from the group consisting of a (n + 1) valent group, that is, an alkyl group with 1 to 8 carbon atoms, an aryl group with 6 to 10 carbon atoms and a heterocyclic group with 1 to 10 carbon atoms from which n hydrogen atoms have been removed ; X represents a water soluble substituent; n represents an integer of 1 to 3 ; R₄ and R₅ are both selected independently from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, an aliphatic oxy group or an aromatic oxy group, or R₄ and R₆ may join with each other to form a ring ; R_e is selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group,

and an imido group ; Y is selected from the group consisting of

-SO₂, -SO- and a single bond ; R₇ is selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group ; R₈ is selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group ; Rg and R₁₀ are both selected independently from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an aliphatic sulfonyl group and an aromatic sulfonyl group or Rg and R₁₀ may join with each other to form a ring and provided that when ℓ is 2 or more, each R₂ may be identical to or different from the other, or any R₂ may join with another R₂ to form a ring, and an R₂ may form a dimer or higher polymer which is obtained by way of a divalent or higher valent group in an of R₁, R₂ or R₃ and provided that the coupler of formula (1) is not

or

2. The material of claim 1, wherein R_e represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, -OR₇ or SR₇ and Y represents -CO- or -S0₂-.

3. The material of claim 1, wherein X is a substituent in which the n-substituent constant is 0.5 or less.

4. A method of processing a silver halide colour photosensitive material wherein a silver halide colour photosensitive material according to any of claims 1 to 3 is processed by fixing or bleach-fixing after colour development.

5. The method of claim 4, wherein the pH value of the fix or bleach-fix bath is 5.7 or less.

6. The method of claim 4, wherein the bleaching agent used in said fix or bleach-fix bath is selected from the group consisting of :

(1) diethylenetriamine pentaacetic acid,

(2) pentasodium salt of diethylenetriamine pentaacetic acid,

(3) ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid,

(4) trisodium ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetate,

(5) triammonium ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetate,

(6) 1,2-diaminopropane tetraacetic acid,

(7) disodium 1,2-diaminopropane tetraacetate,

(8) nitrilotriacetic acid,

(9) sodium nitrilotriacetic acid salt,

(10) cyclohexanediamine tetraacetate,

(11) cyclohexanediamine tetraacetic acid disodium salt,

(12) N-methyliminodiacetic acid,

(13) iminodiacetic acid,

(14) dihydroxyethyl glycine,

(15) ethylether diamine tetraacetic acid,

(16) glycol ether diamine tetraacetic acid,

(17) ethylenediamine tetrapropionic acid,

(18) 1,3.diaminopropane tetraacetic acid and

(19) ethylenediamine tetraacetic acid.

7. The method of any of claims 4 to 6 which comprises a step of water washing or stabilisation directly after fixing or bleach-fixing, the water washing or the stabilisation step including a plurality of vessels and, upon replenishing a processing solution in a multi-stage counter current system, the replenishing amount being from 0.1 to 50 times of the amount of the processing solution carried from the preceeding bath per unit area of the silver halide colour photosensitive material to be processed.