EP0436190A2

EP0436190A2 - Silver halide photographic material

Info

Publication number: EP0436190A2
Application number: EP90124957A
Authority: EP
Inventors: Shuichi C/O Konica Corporation Sugita; Shuji C/O Konica Corporation Kida
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1989-12-27
Filing date: 1990-12-20
Publication date: 1991-07-10
Also published as: JPH03198048A; EP0436190A3

Abstract

A silver halide photographic material containing a compound of the following formula (I) which is capable of releasing a development restrainer upon reaction with the oxidation product of a developing agent:

where Cp is a coupler residue that is capable of entering into a coupling reaction with the oxidation product of a color developing agent; TIME is a timing group bound to Cp at the coupling site; ℓ is 0 or 1; R₁ is -X-Y or a substituent; R₂ is a substituent when R₁ is -X-Y, and it is -X-Y when R₁ is a substituent; X is a linkage group; and Y is a hydrolyzable group.

Description

BACKGROUND OF THE INVENTION

This invention relates to a silver halide photographic material, more particularly to a silver halide color photographic material having improved photographic characteristics and keeping quality.
The development of color photographic materials having high sensitivity, good sharpness and high fidelity of color reproduction is one of the objectives in modern photographic industry. A known method of improving sharpness is to use DIR compounds which release development restrainers upon reaction with the oxidation product of color developing agents. As is well known, incorporating these DIR compounds in emulsions is effective for enhancing the sharpness of color image by the edge effect and further for improving the fidelity of color reproduction by the interimage effect. However, the conventional DIR compounds have the disadvantage that development restrainers released during color development diffuse from photographic materials into the developing solution which will eventually exhibit a development inhibiting action in the presence of accumulated restrainers.
With a view to solving this problem, improved methods have been proposed in JP-A-57-151944 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-58-205150, JP-A-60-218644, JP-A-60-221750, JP-A-61-11743 and U.S. Patent No. 4,782,012. The methods described in these patents are based on using couplers that exhibit a development inhibiting action when leaving groups are eliminated from the coupling site of a coupler and which, when released into the developing solution, will be decomposed into compounds that cause no adverse effects on the photographic performance of the light-sensitive material in which they are used. As a matter of fact, light-sensitive materials using those couplers could be subjected to continuous processing in large quantities with smaller reduction in sensitivity and with the contamination of the developing solution being markedly reduced. However, the light-sensitive material containing those couplers experience not only increased fog but also deterioration in sensitivity, sharpness and color reproduction during storage. Further, the couplers themselves are not considered to be satisfactory from the viewpoint of achieving the edge effect and the interimage effect at the same time.

SUMMARY OF THE INVENTION

An object, therefore, of the present invention is to provide a color light-sensitive material that achieves good sharpness and high fidelity of color reproduction and which also is improved in storage stability.
This object of the present invention can be attained by a silver halide photographic material containing a compound of the following formula (I) which is capable of releasing a development restrainer upon reaction with the oxidation product of a developing agent:

where Cp is a coupler residue that is capable of entering into a coupling reaction with the oxidation product of a color developing agent; TIME is a timing group bound to Cp at the coupling site; ℓ is 0 or 1; R₁ is -X-Y or a substituent; R₂ is a substituent when R₁ is -X-Y, and it is -X-Y when R₁ is a substituent; X is a linkage group; and Y is a hydrolyzable group.

DETAILED DESCRIPTION OF THE INVENTION

The coupler residue represented by Cp in the general formula (I) may either be a residue that generates a yellow, magenta or cyan dye or a residue that generates a substantially colorless product. Typical examples of the yellow coupler residue represented by Cp are described in U.S. Patent Nos. 2,298,443, 2,407,210, 2,875,057, 3,048,194, 3,265,506, 3,447,928, and Farbkuppler eine Literaturuversiecht Agfa Mitteilung (Band II), pp. 112-126, 1961, etc. Among the compounds described in these references, acyl acetanilides such as benzoyl acetanilide and pivaloyl acetanilide are preferred.
Typical examples of the magenta coupler residue represented by Cp are described in U.S. Patent Nos. 2,369,489, 2,343,703, 2,311,182, 2,600,788, 2,908,573, 3,062,653, 3,152,896, 3,519,429, 3,725,067, 4,540,654, JP-A-59-162548, Agfa Mitteilung (Band II), ibid, pp. 126-156, 1961, etc. Among the compounds described in these references, pyrazolones and pyrazoloazoles (e.g. pyrazoloimidazole and pyrazolotriazole) are preferred.
Typical examples of the cyan coupler residue represented by Cp are described in U.S. Patent Nos. 2,367,531, 2,423,730, 2,474,293, 2,772,162, 2,395,826, 3,002,836, 3,034,892, 3,041,236, 4,666,999 and Agfa Mitteilung (Band II), ibid, pp. 156-175, 1961. Among the compounds described in these references, phenols and naphthols are preferred.
Typical examples of the coupler residue represented by Cp which forms a substantially colorless product are described in U.K. Patent No. 861,138, U.S. Patent Nos. 3,632,345, 3,928,041, 3,958,993, 3,961,959, etc. Among the compounds described in these patents, cyclic carbonyl compounds are preferred.
Typical examples of the timing group represented by TIME include those which release photographically useful groups by an intramolecular nucleophilic substitution reaction as described in U.S. Patent No. 4,248,962 and JP-A-57-56837, as well as those which release photographically useful groups by an electron transfer reaction along conjugated chains as described in JP-A-56-114946 and JP-A-57-154243. Other examples of the timing group are described in JP-A-57-188035, JP-A-58-98728, JP-A-59-206834, JP-A-60-7429, JP-A-60-214358, JP-A-50-225844, JP-A-60-229030, JP-A-60-233649, JP-A-60-237446 and JP-A-60-237447.
Preferred examples of the yellow coupler residue represented by Cp in the general formula (I) are represented by the following general formulas (II) and (III):

where R₃ and R₄ each represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or a halogen atom, with the alkyl, cycloalkyl, aryl and heterocyclic group being optionally bound via at least one member of the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom; the alkyl, cycloalkyl, aryl and hetero ring may also be bound via one or more of the following bonding groups, namely, acylamino, carbamoyl, sulfonamido, sulfamoyl, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamide, sulfone, sulfonyloxy, etc.
The alkyl, cycloalkyl, aryl and hetero ring may further contain one or more of the following substituents, namely, a halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxy, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamido, hetero ring, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxyl, imido, acyl, etc.
When more than one each of R₃ and R₄ is present, two or more R₃'s or R₄'s may be the same or different.
Preferred examples of the magenta coupler residue represented by Cp in the general formula (I) are those represented by the following general formulas (IV), (V), (VI) and (VII):

where R₃ and R₄ are the same as defined for R₃ and R₄ in the general formulas (II) and (III).
Preferred examples of the cyan coupler residue represented by Cp in the general formula (I) are those represented by the following general formulas (VIII), (IX) and (X):

where R₃ and R₄ are the same as defined for R₃ and R₄ in the general formulas (II) and (III).
Preferred examples of the coupler residue which forms a substantially colorless product as represented by Cp in the general formula (I) are those represented by the following general formulas (XI) - (XIV):

where R₅ may be a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyloxy group or a heterocyclic group; X is an oxygen atom or =NR₆ (where R₆ is an alkyl group, an aryl group, a hydroxyl group, an alkoxyl group or a sulfonyl group); and Z is the nonmetallic atomic group necessary to form a 5- to 7-membered carbon ring (e.g. indanone, cyclopentanone or cyclohexanone) or a 5- to 7-membered hetero ring (e.g. piperidone, pyrrolidone or hydrocarbostyryl);

where R₅ and X are the same as defined for R₅ and X in the general formula (XI); R₇ is an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, a heterocycloxy group, an alkylamino group, a dialkylamino group or an anilino group;

where R₈ and R₉ which may be the same or different each represents an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, a formyl group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, an ammoniumyl group or
(where A is the nonmetallic atomic group necessary to form, taken together with the nitrogen atom, a 5- to 7-membered hetero ring such as phthalimido, triazole or tetrazole);

where R₁₀ may be an alkyl group, an aryl group, an anilino group, an alkylamino group or an alkoxy group; and B is an oxygen atom, a sulfur atom or a nitrogen atom.
Examples of TIME useful in the present invention include, but are not limited to, those which are represented by the following general formulas (XV), (XVI) and (XVII):

where X is the atomic group necessary to form an optionally substituted benzene or naphthalene ring; Y is -O-, -S- or
and is bound at the coupling site to the coupler residue represented by Cp in the general formula (I); R₁₁, R₁₂ and R₁₃ are each a hydrogen atom, an alkyl group or an aryl group; and
which is substituted in the position ortho or para to Y is bound to the sulfur atom in the development restraining group;

where Y, R₁₁ and R₁₂ are each the same as defined in the general formula (XV); R₁₄ may be a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group or a heterocyclic group; and R₁₅ may be a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an acid amido group, a sulfonamido group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group.
As in the general formula (XV), the timing group TIME is bound via Y to the coupling site of the coupler residue represented by Cp in the general formula (I), or via

to the sulfur atom in the development restraining group.
An example of the timing group that releases a development restraining group by an intramolecular nucleophilic substitution reaction is represented by the following general formula (XVII):

where Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom and it is bound at the coupling site to the coupler residue represented by Cp in the general formula (I); E is an electrophilic group having an electron-lean carbonyl, thiocarbonyl, phosphinyl or thiophosphinyl group and it is bound to the sulfur atom in the development restraining group; X is a bonding group that sterically relates Nu and E and which, after Nu is released from the coupler residue represented by Cp in the general formula (I), undergoes an intramolecular nucleophilic reaction involving the formation of a 3- to 7-membered ring to thereby release a development restrainer.
Examples of the substituents represented by R₁ and R₂ in the general formula (I) include a hydrogen atom and a halogen atom, as well as groups such as nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxyl, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamido, hetero ring, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxyl, imido and acyl. Among these, a hydrogen atom, an alkyl group and an aryl group are preferred.
In the general formula (I), X represents a simple bond, alkylene, cycloalkylene, phenylene, alkenylene,
-O-, -S- (where R₁₃ may be a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group) or combinations of these groups. Among these, alkylene,
and combinations of these groups are preferred.
Examples of the hydrolyzable group represented by Y in the general formula (I) include -COOR₁₆, -OCOR₁₆, -OSO₂R₁₆ and
with -COOR₁₆ being preferred. Examples of the group represented by R₁₆ include an alkyl group (e.g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or hexyl), a cycloalkyl group (e.g. cyclopentyl or cyclohexyl), an aryl group (e.g. phenyl or naphthyl), and a heterocyclic group (e.g. pyridinyl, imidazolyl or pyrrolyl). These groups may have substituents such as a halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxyl, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamido, hetero ring, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxyl, imido and acyl. An alkyl group and an aryl group are preferred as R₁₆.
A preferred example of the compound of the general formula (I) is the one represented by the following general formula (I'):

where Cp, TIME, X, ℓ, R₂ and R₁₆ have the same meanings as defined in the general formula (I). A particularly preferred example is such that R₁₆ is an unsubstituted alkyl group.
Typical examples of the compound of the general formula (I) are listed below but it should be understood that the present invention is by no means limited to these examples.
Two examples of the synthesis of compounds represented by the general formula (I) are described below.
Compound $\binom{1}{~}$
(7.7 g) and compound $\binom{2}{~}$
(1.5 g) were dissolved in 50 ml of acetonitrile and the solution was heated under reflux for 2 h. After distilling off acetonitrile under vacuum, 50 ml of ethyl acetate was added and following washing with water, ethyl acetate was distilled off under vacuum. By subsequent column chromatography, compound $\binom{3}{~}$
was obtained in an amount of 5.1 g.
Then, compound $\binom{3}{~}$
(4.3 g) was dissolved in acetonitrile (25 ml) and compound $\binom{4}{~}$
(0.7 g) was added at 5°C or below. Following addition of triethylamine (0.5 g) over a period of 1 h, the mixture was stirred for 20 h. After the reaction, acetonitrile was removed and the end compound (2 g) was obtained by column chromatography.
Compound $\binom{1}{~}$
(14.5 g) and compound $\binom{2}{~}$
(20.2 g) were heated under reflux at 100 - 115°C for 20 h. After the reaction, ethyl acetate (100 ml) was added and following washing with water, ethyl acetate was distilled off under vacuum to obtain compound $\binom{3}{~}$
in an amount of 10 g.
Compound $\binom{4}{~}$
(33 g) and compound $\binom{3}{~}$
(10 g) were dissolved in chloroform (100 ml) and 40 ml of a 10% aqueous solution of sodium bicarbonate was added over a period of 30 minutes, followed by stirring for an additional 24 h. After the reaction, the chloroform layer was separated and the solvent was distilled off under vacuum. The solid residue was recrystallized from an ethyl acetate-hexane solvent system to obtain illustrative compound 9 in an amount of 24 g.
In both syntheses, the compounds obtained were identified as the desired products by taking NMR, MS and IR spectra.
The compound represented by the general formula (I) (which is hereinafter sometimes referred to as the "DIR coupler" of the present invention) may be incorporated in any layers, such as silver halide emulsion layers and/or non-light-sensitive hydrophilic colloidal layers, in a photographic material. Preferably, the DIR coupler is incorporated in silver halide emulsion layers. More preferably, the DIR coupler of the present invention is incorporated in a red-sensitive silver halide emulsion layer and/or a blue-sensitive silver halide emulsion layer.
The DIR couplers of the present invention may be incorporated in hydrophilic colloidal layers in a color photographic material by the following procedure: the DIR couplers, taken either individually or in combination, are dissolved in a mixture of a known high-boiling point solvent such as dibutyl phthalate, tricresyl phosphate or dinonyl phenol and a known low-boiling point solvent such as butyl acetate or propionic acid; the solution is then mixed with an aqueous gelatin solution containing a surfactant, followed by dispersion using a high-speed rotary mixer, a colloid mill or an ultrasonic disperser, with the resulting dispersion being directly added to a silver halide emulsion; alternatively, the dispersion is allowed to set, shredded into noodles, which are then washed with water and added to a silver halide emulsion.
The DIR couplers of the present invention are used in amounts that preferably range from 0.005 to 20 mol % of silver halide, more preferably from 0.01 to 10 mol % of silver halide. The DIR couplers of the present invention may be used either individually or as admixtures.
Any customary silver halide emulsions may be used in the photographic material of the present invention. Such emulsions may be chemically sensitized in the usual manner, or they may be optically sensitized with spectral sensitizers to have sensitivity in a desired wavelength region.
Antifoggants, stabilizers, etc. may be added to silver halide emulsions. Gelatin is advantageously used as a binder for silver halide emulsions.
Emulsion layers and other hydrophilic colloidal layers may be hardened. Plasticizers or dispersions (latices) of synthetic polymers that are either insoluble or slightly soluble in water may also be contained in emulsion layers and other hydrophilic colloidal layers.
Couplers are used in emulsion layers in a color photographic material. Also usable are colored couplers which are capable of color correction, competing couplers, as well as those compounds which, upon coupling with the oxidation product of developing agents, release photographically useful fragments such as a development accelerator, a bleach accelerator, a developing agent, a silver halide solvent, a toning agent, a hardener, a foggant, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer.
The photographic material of the present invention may have a filter layer, an anti-halation layer, an anti-irradiation layer, etc. These layers and/or emulsion layers may contain dyes that will dissolve out of the photographic material during development or which are bleachable.
The photographic material of the present invention may also contain a matting agent, a lubricant, an image stabilizer, a surfactant, an anti -color fog agent, a development accelerator, a development retarder or a bleach accelerator.
Supports that can be used in the present invention include paper laminated with a resin such as polyethylene, a polyethylene terephthalate film, baryta paper, a triacetyl cellulose film etc.
In order to produce dye image using the photographic material of the present invention, it may be subjected to known procedures of color photographic processing.
The following examples are provided for the purpose of further illustrating the present invention but are in no way to be taken as limiting. In the following examples, the amounts of components or additives in silver halide photographic materials are based on one square meter unless otherwise noted. The amounts of silver halides and colloidal silver are calculated for silver.

Example 1

Multi-layered color photographic material (sample 1) was prepared by forming the following layers in the order written on a triacetyl cellulose film base.

Sample 1 (comparison):

First layer:

Anti-halation layer (HC-1)
Gelatin layer containing black colloidal silver

Second layer:

Intermediate layer (IL)
Gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone

Third layer:

Less red-sensitive silver halide emulsion layer (RL-1)

Fourth layer:

Highly red-sensitive silver halide emulsion layer (RH-1)

Fifth layer:

Intermediate layer (IL)
same gelatin layer as the second layer

Sixth layer:

Less green-sensitive silver halide emulsion layer (GL-1)

Seventh layer:

Highly green-sensitive silver halide emulsion layer (GH-1)

Eighth layer:

Yellow filter layer (YC-1)
Gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-ocytlhydroquinone

Ninth layer:

Less blue-sensitive silver halide emulsion layer (BL-1)

Tenth layer:

Highly blue-sensitive silver halide emulsion layer (BH-1)

Eleventh layer:

First protective layer (Pro-1)
Gelatin layer containing 0.5 g of silver iodobromide grains (1 mol% AgI, r = 0.07 µm), as well as uv absorbers UV-1 and UV-2

Twelfth layer:

Second protective layer (Pro-2)
Gelatin layer containing polymethyl methacrylate particles (diameter, 1.5 µm) and formaldehyde scavenger (HS-1)
Besides the compounds mentioned above, a gelatin hardener (H-1) and a surfactant were also added to each layer.
The following compounds were incorporated in the respective layers of sample 1.

Spectral sensitizer I:: Anhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide
Spectral sensitizer II:: Anhydro-9-ethyl-3,3'-di(sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide
Spectral sensitizer III:: Anhydro-5,5'-diphenyl-9-ethyl-3,3'-di(3-sulfopropyl) oxacarbocyanine hydroxide
Spectral sensitizer IV:: Anhydro-9-ethyl-3,3'-di (3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroxide
Spectral sensitizer V:: Anhydro-3,3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine hydroxide

D-1: Compound described in JP-B-63-27701 ("JP-B" refers to an "examined Japanese patent publication)

D-4: Compound described in U.S. Patent No. 4,782,012

Samples 2 - 5 were prepared by replacing the DIR compound (D - 1) in the third and fourth layers of sample 1 with equimolar amounts of the compounds shown in Table 1 below.
Each of the thus prepared samples 1 - 5 was divided into two lots, one of which was left to stand at 55°C for 7 days at 20% r.h. before exposure. The samples including the untreated lots were exposed to white light through an optical wedge and processed by the scheme shown below. The sensitivity of the red-sensitive layers and the fog that occurred were measured. At the same time, the sharpness of image was also measured and the results were shown in terms of the relative values of MTF at a resolution of 30 lines/mm, with the value for sample 1 taken as 100. The results of the measurements are shown in Table 1 below.
The processing solutions used in the color developing, bleaching, fixing and stabilizing steps had the following compositions.
As is clear from Table 1, the samples prepared in accordance with the present invention were markedly improved in image sharpness and further they experienced less thermal fogging and reduction in sensitivity during storage. Reduction in sensitivity was also negligible even when the samples of the present invention were subjected to continuous processing.

Example 2

A basic sample was prepared by coating multiple layers in superposition on a triacetate base in the order indicated below.

(1) Red-sensitive silver iodobromide emulsion layer containing 0.5 g of cyan coupler (C-2), 2.4 g of gelatin and 1.6 g of silver halide;
(2) Intermediate gelatin layer containing 0.5 g of gelatin and 0.1 g of 2,5-di-t-octylhydroquinone;
(3) Blue-sensitive silver iodobromide emulsion layer containing 1.70 g of yellow coupler (Y-1), 2.4 g of gelatin and 1.6 g of silver halide; and
(4) Protective layer containing 0.8 g of gelatin.

Five additional samples 6 - 10 were prepared by adding specific DIR couplers (see Table 2) to the yellow coupler containing third layer in the amounts also shown in Table 2. Each of these samples was divided into two lots, one being exposed to white light through an optical wedge and the other exposed to red light through an optical wedge. Each lot of the samples were then processed as in Example 1. Gamma values were determined from the characteristic curves of cyan dye as obtained for each sample by color development and the gamma by exposure to red light (γ_R) was divided by the gamma by exposure to white light (γ_W). The results are shown in Table 2 below.

D-5: Compound described in JP-B-63-27701

D-6: Compound described in U.S. Patent No. 4,782,012

As is clear from Table 2, the samples using the DIR compounds of the present invention provided large γ_R/ γ_W values and obviously produced a greater interimage effect than when the conventional DIR couplers were used.

Claims

A silver halide photographic material containing a compound of the following formula (I) which is capable of releasing a development restrainer upon reaction with the oxidation product of a developing agent:
where Cp is a coupler residue that is capable of entering into a coupling reaction with the oxidation product of a color developing agent; TIME is a timing group bound to Cp at the coupling site; ℓ is 0 or 1; R₁ is -X-Y or a substituent; R₂ is a substituent when R₁ is -X-Y, and it is -X-Y when R₁ is a substituent; X is a linkage group; and Y is a hydrolyzable group.
A silver halide photographic material according to claim 1 wherein the coupler residue represented by Cp in the general formula (I) is a yellow coupler residue represented by the following general formula (II) or (III):
where R₃ and R₄ are each at least one member of the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group and a halogen atom, with the alkyl, cycloalkyl, aryl and heterocyclic group being optionally bound either directly or via a bonding group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, acylamino, carbamoyl, sulfonamido, sulfamoyl, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamido, sulfone and sulfonyloxy.
A silver halide photographic material according to claim 1 wherein the coupler residue represented by Cp in the general formula (I) is at least one member of the group consisting of the magenta coupler residues represented by the following general formulas (IV), (V), (VI) and (VII):

where R₃ and R₄ are each at least one member of the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group and a halogen atom, with the alkyl, cycloalkyl, aryl and heterocyclic group being optionally bound either directly or via a bonding group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, acylamino, carbamoyl, sulfonamido, sulfamoyl, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureiod, thioureido, thioamido, sulfone and sulfonyloxy.
A silver halide photographic material according to claim 1 wherein the coupler residue represented by Cp in the general formula (I) is at least one member of the group consisting of the cyan coupler residues represented by the following general formulas (VIII), (IX) and (X):
where R₃ and R₄ are each at least one member of the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group and a halogen atom, with the alkyl, cycloalkyl, aryl and heterocyclic group being optionally bound either directly or via a bonding group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, acylamino, carbamoyl, sulfonamido, sulfamoyl, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamido, sulfone and sulfonyloxy.
A silver halide photographic material according to claim 1 wherein the coupler residue represented by Cp in the general formula (I) is at least one of the coupler residues that are represented by the following general formulas (XI), (XII), (XIII) and (XIV) and which form a substantially colorless product:
where R₅ is at least one member of the group consisting of a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyloxy group and a heterocyclic group; X is an oxygen atom or =NR₆ (where R₆ is at least one member of the group consisting of an alkyl group, an aryl group, a hydroxyl group, an alkoxyl group and a sulfonyl group); and Z is the nonmetallic atomic group necessary to form a 5- to 7-membered carbon or hetero ring;
where R₅ is at least one member of the group consisting of a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyloxy group and a heterocyclic group; X is an oxygen atom or =NR₆ (where R₆ is at least one member of the group consisting of an alkyl group, an aryl group, a hydroxyl group, an alkoxyl group and a sulfonyl group); and R₇ is at least one member of the group consisting of an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, a heterocycloxy group, an alkylamino group, a dialkylamino group and an anilino group;
where R₈ and R₉ are each an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, a formyl group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, an ammoniumyl group or
(where A is the nonmetallic atomic group necessary to form, taken together with the nitrogen atom, a 5- to 7-membered hetero ring);
where R₁₀ is at least one member of the group consisting of an alkyl group, an aryl group, an anilino group, an alkylamino group and an alkoxy group; and B is an oxygen atom, a sulfur atom or a nitrogen atom.
A silver halide photographic material according to claim 1 wherein the timing group represented by TIME in the general formula (I) is at least one member selected from among the groups represented by the following general formulas (XV), (XVI) and (XVII):
where X is the atomic group necessary to form a benzene ring or a naphthalene ring; Y is -O-, -S- or
and R₁₁, R₁₂ and R₁₃ are each a hydrogen atom, an alkyl group or an aryl group;
where Y is -O-, -S- or
R₁₁, R₁₂ and R₁₃ are each a hydrogen atom, an alkyl group or an aryl group; R₁₄ is at least one member of the group consisting of a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group and a heterocyclic group; and R₁₅ is at least one member of the group consisting of a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an acid amido group, a sulfonamido group, a carboxyl group, an alkoxy carbonyl group, a carbamoyl group and a cyano group;
where Nu is a nucleophilic group having an oxygen atom, a sulfur atom or a nitrogen atom; E is an electrophilic group having at least one member selected from among a carbonyl group, a thiocarbonyl group, a phosphinyl group and a thiophosphinyl group; and X is a bonding group.
A silver halide photographic material according to claim 1 wherein the substituent represented by R₁ in the general formula (I) is represented by X-COOR₁₆ where X is a linkage group and R₁₆ is a substituent.
A silver halide photographic material according to claim 1 wherein the compound represented by the general formula (I) is used in an amount of 0.005 to 20 mol % of silver halide.
A silver halide photographic material according to claim 1 wherein the compound represented by the general formula (I) is used in an amount of 0.01 to 10 mol % of silver halide.
A silver halide photographic material according to claim 1 wherein the compound represented by the general formula (I) is incorporated in a silver halide emulsion layer.
A silver halide photographic material according to claim 1 wherein the compound represented by the general formula (I) is incorporated in a red-sensitive silver halide emulsion layer and/or a blue-sensitive silver halide emulsion layer.