Silver halide photographic material

Abstract

 A silver halide color photographic material is disclosed which contains at least one light-sensitive silver halide emulsion layer and a restrainer precursor-releasing compound represented by the following general formula (I) and an oil-soluble dye represented by the following general formula (A):



        A-X   (I)



in which A represents a group which releases X by a reaction with an oxidant of a developing agent and forms a compound which is soluble in processing solutions or is decolorized; and X represents a residue of a restrainer precursor;


in which X and Y each represents an electron attractive group or X and Y are combined together to form a ring; Ar represents a heterocyclic aromatic ring which is indole, furan, thiophene, coumarin or pyridine; L¹, L² and L³ each represents a methine group; and n represents 0, 1 or 2.

Description

FIELD OF THE INVENTION

[0001] This invention relates to a silver halide color photographic material, and more particularly to a silver halide color photographic material which has high sensitivity, gives an image of good quality, is excellent in preservability over time and provides a dye image having excellent fastness.

BACKGROUND OF THE INVENTION

[0002] Some compounds which release a restrainer precursor for development are disclosed in, for example, JP-A-58-160954 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-58-162949, JP-A-61-156127, JP-A-63-37350, J. Soc. Photogra. Sci. Technol. Japan, Vol. 52 (1989), No. 2, pp. 150-155 (Kida et al) and the substance 2AO-22 (Kida et. al.) of the annual lecture to the Photography Society of Japan in 1989.

[0003] However, when these compounds are used in conventional methods, restrainer compounds for development are finally released, photographic sensitivity is lowered, and a photographic material having high sensitivity can be hardly obtained, though color reproducibility and image quality such as graininess can be improved. Accordingly, there is a limit to the use of these compounds or the amount of these compounds which can be used.

[0004] Further, these compounds are not considered to be fully satisfactory with regard to improving image quality. Accordingly, there has been a demand to further improve image quality. Furthermore, there has been a great demand to improve the preservability of the photographic materials over time and the fastness of the dye image.

[0005] Dyes contained in photographic materials are used, for example, as filter dyes for controlling the spectral composition of incident light entering light-sensitive layers, as dyes in antihalation layers for preventing light from scattering, or as irradiation preventing dyes.

[0006] The dyes used for the above-described purposes must meet the following requirements:

(1) the dyes have proper spectral absorption according to the purpose of the use thereof;

(2) the dyes are photochemically inert. Namely, the dyes do not have any adverse effect on the performance of silver halide emulsions in a chemical sense, for example, the dyes do not cause a lowering in sensitivity, latent image fading or fogging; and

(3) the dyes are decolorized and dissolved out during the course of color development processing, and an undesired residual color is not left behind in the photographic materials after processing.

[0007] Many attempts have been made to find dyes which meet the above requirements. Some dyes have been proposed.

[0008] Somewhat similar dyes to those of the present invention are disclosed in JP-A-3-167546 and JP-A-3-144438. However, the dyes described in these prior patent specifications do not meet the above requirement (2), i.e., is not photochemically inert. Further, it has been found that the dyes have problems in that when the photographic materials are stored over a long period of time, fog is increased and sensitivity is lowered. Furthermore, it has been found that the dyes have problems in that decolorizability is poor, a residual color is formed, and the fastness of the dye image thereof is deteriorated.

SUMMARY OF THE INVENTION

[0009] Accordingly, an object of the present invention is to provide a silver halide color photographic material which has high sensitivity.

[0010] Another object of the present invention is to provide a silver halide color photographic material which is excellent in color reproducibility.

[0011] Still another object of the present invention is to provide a silver halide color photographic material which is excellent in stability over time.

[0012] A further object of the present invention is to provide a silver halide color photographic material which has good dye image fastness.

[0013] These and other objects of the present invention have been achieved by providing the following silver halide color photographic materials.

(1) A silver halide color photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer and containing at least one restrainer precursor-releasing compound represented by the following general formula (I) and at least one oil-soluble dye represented by the following general formula (A):



        A-X   (I)



wherein A represents a group which releases X by a reaction with an oxidant of a developing agent and forms a compound which is soluble in processing solutions or is decolorized; and X represents a group of a restrainer precursor;

wherein X and Y each represents an electron attractive group, or X and Y are combined together to form a five-membered or six-membered ring; Ar represents a heterocyclic aromatic ring which is a substituted or unsubstituted indole, furan, thiophene, coumarin or pyridine group; L¹, L² and L³ each represents a methine group; and n represents 0, 1 or 2.

(2) A silver halide color photographic material as described in (1) above, wherein the silver halide color photographic material contains at least one coupler represented by the following general formula (II) or (III):

wherein R₁ represents -CONR₄R₅, -SO₂NR₄R₅, -NHCOR₄, -NHCOOR₆, -NHSO₂R₆, -NHCONR₄R₅ or -NHSO₂NR₄R₅; R₂ represents a group which can be attached to the naphthalene ring; k represents an integer of 0 to 3; R₃ represents a substituent group; X represents a hydrogen atom or a group which is eliminated by a coupling reaction with an oxidant of an aromatic primary amine development agent; R₄ and R₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R₆ represents an alkyl group, an aryl group or a heterocyclic group; and when k is 2 or greater, the two or more R₂ groups may be the same or different or may be combined together to form a ring; or R₂ and R₃ or R₃ and X may be combined together to form a ring, or two or more members of the compounds may be bonded to each other at the position of R₁, R₂, R₃ or X through a bivalent or polyvalent group to form a dimer or a higher polymer;

wherein R¹ represents an alkyl group, an aryl group or a heterocyclic group; R² represents an aryl group; and Z represents a hydrogen atom or a group which is eliminated by coupling.

(3) A silver halide color photographic material as described in (1) or (2) above, wherein the gelatin coating amount of the layer containing the oil-soluble dye represented by general formula (A) is 1.5 g/m² or less.

DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention is illustrated in greater detail below.

[0015] First, the restrainer-releasing compounds of general formula (I) are described below.

[0016] More specifically, the compounds of general formula (I) according to the present invention may be represented by the following general formula (Ia) or (Ib):









wherein A represents a coupler group which releases (TIME)_a-DI or (TIME)_i-RED-DI by a coupling reaction with an oxidant of an aromatic primary amine developing agent and forms a compound which is soluble in processing solutions or is decolorized; TIME represents a timing group which releases DI or RED-DI by the cleavage between TIME and DI or RED-DI after being released from A by the coupling reaction; RED represents a group which releases DI by cleavage between RED and DI by a reaction with an oxidant of the developing agent after being released from A or TIME; DI represents a restrainer; a represents 1 or 2 and when a is 2, the two TIME groups may be the same or different; and i represents 0 or 1.

[0017] The coupler group (the residue of a coupler) represented by A is described.

[0018] When A represents a group of a yellow coupler, examples of A include pivalolyacetanilide type couplers, benzoylacetanilide type couplers, malondiester type couplers, malondiamide type couplers, dibenzoylmethane type couplers, benzthiazolylacetamide type couplers, malonestermonoamide type couplers, benzoxazolylacetamide type couplers, benzimidazolylacetamide type couplers, quinazoline-4-one-2-ylacetanilide type couplers and cycloalkanoylacetamide type couplers.

[0019] When A represents a group of a magenta coupler, examples of A include groups of 5-pyrazolone type couplers, pyrazole[1,5-a]benzimidazole type couplers, pyrazolo[1,5-b][1,2,4]triazole type couplers, pyrazolo[5,1-c][1,2,4]triazole type couplers, imidazo[1,2-b]pyrazole type couplers, pyrrole[1,2-b][1,2,4]triazole type couplers, pyrazolo[1,5-b]pyrazole type couplers and cyanoacetophenone type couplers.

[0020] When A represents a group of a cyan coupler, examples of A include the group of phenol type couplers, naphthol type couplers and 2,4-diphenylimidazole type couplers.

[0021] Further, A may be a coupler containing a phenyl group which does not leave behind substantially any dye image. Examples of the coupler groups of this type include of indanone type coupler groups and acetophenone type coupler groups.

[0022] Preferred examples of A include coupler groups represented by one of the following general formulas (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9) and (Cp-10). These couplers are preferred from the standpoint of a high coupling rate.






   In the above formulas, each free bond at the coupling position represents the position where the coupler group is attached to the group which is eliminated by coupling.

[0023] In the above formulas, each of R₅₁, R₅₂, R₅₃, R₅₄, R₅₅, R₅₆, R₅₇, R₅₈, R₅₉, R₆₀, R₆₁, R₆₂ and R₆₃ has preferably not more than 10 carbon atoms. It is preferred that the coupler group represented by A has at least one substituent group selected from the group consisting of -COOR₇₁, -SO₃H, -OH, -CONHR₇₂ and -SO₂NHR₇₂. Namely, it is preferred that at least one of R₅₁ and R₅₂ in general formula (Cp-1), at least one of R₅₁, R₅₂ and R₅₃ in general formula (Cp-2), at least one of R₅₄ and R₅₅ in general formula (Cp-3), at least one of R₅₆ and R₅₇ in general formulas (Cp-4) and (Cp-5), at least one of R₅₈ and R₅₉ in general formula (Cp-6), at least one of R₅₉ and R₆₀ in general formula (Cp-7), at least one of R₆₁ and R₆₂ in general formula (Cp-8) and at least one of R₆₃ groups in general formulas (Cp-9) and (Cp-10) has at least one substituent group selected from the group consisting of -COOR₇₁, -SO₃H, -OH, -CONHR₇₂ and -SO₂NHR₇₂. R₇₁ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl) or a phenyl group. These groups may be further substituted. R₇₂ represents a group of R₇₁, an acyl group (e.g., acetyl, propionyl, butyryl, trifluoroacetyl) or a sulfonyl group (e.g., methanesulfonyl, butanesulfonyl, benzenesulfonyl, p-chlorobenzenesulfonyl, p-nitrobenzenesulfonyl).

[0024] R₅₁ to R₆₃, b, d and e are described below. In groups described below, R₄₁ represents an alkyl group, an aryl group or a heterocyclic group; R₄₂ represents an aryl group or a heterocyclic group; and R₄₃, R₄₄ and R₄₅ each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R₅₁ has the same meaning as R₄₁; R₅₂ and R₅₃ each has the same meaning as R₄₃; and b represents 0 or 1. R₅₄ represents a group of R₄₁, R₄₁CON(R₄₃)-, R₄₁SO₂N(R₄₃)-, R₄₁N(R₄₃)-, R₄₁S-, R₄₃O- or R₄₅N(R₄₃)CON(R₄₄)-.

[0025] R₅₅ has the same meaning as R₄₁. R₅₆ and R₅₇ each represents a group of R₄₃, R₄₁S-, R₄₃O-, R₄₁CON(R₄₃)- or R₄₁SO₂N(R₄₃)-, and R₅₈ has the same meaning as R₄₁. R₅₉ represents a group of R₄₁, R₄₁CON(R₄₃)-, R₄₁OCON(R₄₃)-, R₄₁SO₂N(R₄₃)-, R₄₃N(R₄₄)CON(R₄₅)-, R₄₁O-, R₄₁S-, a halogen atom or R₄₁N(R₄₃)-; and d represents 0 to 3 and when d is 2 or greater, the two or more R₅₉ groups may be the same or different. R₆₀ has the same meaning as R₄₁. R₆₁ has the same meaning as R₄₃. R₆₂ represents a group of R₄₁, R₄₁CONH-, R₄₁OCONH-, R₄₁SO₂NH-, R₄₃N(R₄₄)-CONH-, R₄₃N(R₄₄)SO₂NH-, R₄₃O-, R₄₁S-, a halogen atom or R₄₁NH-. R₆₃ represents a group of R₄₁, R₄₃CON(R₄₄)-, R₄₃N(R₄₄)CO-, R₄₁SO₂N(R₄₃)-, R₄₃N(R₄₄)SO₂-, R₄₁SO₂-, R₄₃OCO-, R₄₃OSO₂-, a halogen atom, a nitro group, a cyano group or R₄₃CO-; and e represents an integer of 0 to 4. When e is 2 or greater, the two or more R₆₂ or R₆₃ groups may be the same or different.

[0026] The above-described alkyl group is a saturated or unsaturated, linear or cyclic, straight-chain or branched, or substituted or unsubstituted alkyl group having 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms. Typical examples of the alkyl group include methyl, cyclopropyl, isopropyl, n-butyl, t-butyl, i-butyl, t-amyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-octyl, 1,1,3,3-tetramethylbutyl and n-decyl.

[0027] The above-described aryl group is an aryl group having 6 to 20 carbon atoms, preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.

[0028] The above-described heterocyclic group is a heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms and at least one hetero-atom of nitrogen, oxygen and sulfur. It is preferably a three-membered to eight-membered substituted or unsubstituted heterocyclic group. Typical examples of the heterocyclic group include 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl, 1,3,4-thiadiazole-2-yl, 1,2,4-triazole-2-yl and 1-indolinyl.

[0029] The alkyl group, the aryl group and the heterocyclic group may be substituted. Typical examples of substituent groups for these groups include a halogen atom, a group of R₄₇O-, R₄₆S-, R₄₇CON(R₄₈)-, R₄₇N(R₄₈)CO-, R₄₆OCON(R₄₇)-, R₄₆SO₂N(R₄₇)-, R₄₇N(R₄₈)SO₂-, R₄₆SO₂-, R₄₇OCO-, R₄₇N(R₄₉)CON(R₄₈)-, R₄₇CONHSO₂-, R₄₇NHCONHSO₂-, R₄₆, R₄₇N(R₄₈)-, R₄₆COO-, R₄₇OSO₂-, a cyano group and a nitro group. R₄₆ represents an alkyl group, an aryl group or a heterocyclic group. R₄₇, R₄₈ and R₄₉ each represents an alkyl group, an aryl group, a heterocyclic group or a hydrogen atom. The alkyl group, the aryl group and the heterocyclic group are as defined above.

[0030] The preferred embodiments of R₅₁ to R₆₃, b, d and e are described below.

[0031] R₅₁ is preferably an alkyl group, an aryl group or a heterocyclic group. Preferably, R₅₂ and R₅₅ are each an aryl group. Preferably, R₅₃ is an aryl group when b is 1, and R₅₃ is a heterocyclic group when b is 0. R₅₄ is preferably a group of R₄₁CONH- or R₄₁N(R₄₃)-. Preferably, R₅₆ and R₅₇ are each an alkyl group, a group of R₄₁O- or R₄₁S-.

[0032] Preferably, R₅₈ is an alkyl group or an aryl group. In general formula (Cp-6), R₅₉ is preferably a chlorine atom, an alkyl group or a group of R₄₁CONH-; and d is preferably 1 or 2. Preferably R₆₀ is an aryl group. In general formula (Cp-7), R₅₉ is preferably a group of R₄₁CONH-; and d is preferably 1. Preferably, R₆₁ is an alkyl group or an aryl group. In general formula (Cp-8), e is preferably 0 or 1; and R₆₂ is preferably a group of R₄₁OCONH-, a group of R₄₁CONH- or a group of R₄₁SO₂NH-. It is preferred that R₆₂ is attached to the position-5 of the naphthol ring. In general formula (Cp-9), R₆₃ is preferably a group of R₄₁CONH-, a group of R₄₁So₂NH-, a group of R₄₁N(R₄₃)SO₂-, a group of R₄₁SO₂-, a group of R₄₁N(R₄₃)CO-, a nitro group or a cyano group; and e is preferably 1 or 2. In general formula (Cp-10), R₆₃ is preferably a group of R₄₃NCO-, a group of R₄₃OCO- or a group of R₄₃CO-; and e is preferably 1 or 2.

[0033] The restrainer represented by DI are described below.

[0034] Examples of the restrainer represented by DI include those described in Research Disclosure, Vol. 76, No. 17643 (December 1978), U.S. Patents 4,477,563, 5,021,332, 5,026,628, 3,227,554, 3,384,657, 3,615,506, 3,617,291, 3,733,201, 3,933,500, 3,958,993, 3,961,959, 4,149,886, 4,259,437, 4,095,984 and 4,782,012, U.K. Patent 1,450,479 and U.S. Patent 5,034,311. Preferred examples of DI include a heterocyclic thio group, a heterocyclic seleno group and a triazolyl group (e.g., monocyclic or fused ring type 1,2,3-triazolyl or 1,2,4-triazolyl). Particularly preferably, DI is tetrazolylthio, tetrazolylseleno, 1,3,4-oxadiazolylthio, 1,3,4-thiadiazolylthio, 1-(or 2-)benztriazolyl, 1,2,4-triazole-1-(or 4-)yl, 1,2,3-triazole-1-yl, 2-benzthiazolylthio, 2-benzoxazolylthio, 2-benzimidazolylthio and the derivatives thereof. Examples of the restrainer which can be preferably used in the present invention are groups represented by one of the following general formulas DI-1 to DI-6.


   In the above formulas, R₁₁ represents a halogen atom (e.g., bromine atom, chlorine atom), an alkoxycarbonyl group (having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as methoxycarbonyl, isoamyloxycarbonylmethoxycarbonyl), an acylamino group (having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as hexaneamido, benzamido), a carbamoyl group (having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as N-butylcarbamoyl, N,N-diethylcarbamoyl, N-mesylcarbamoyl), a sulfamoyl group (having 0 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as N-butylsulfamoyl), an alkoxy group (having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methoxy, benzyloxy), an aryloxy group (having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as phenoxy, 4-methoxyphenoxy, naphthoxy), an aryloxycarbonyl group (having 7 to 21 carbon atoms, preferably 7 to 11 carbon atoms, such as phenoxycarbonyl), an alkoxycarbonylamino group (having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as ethoxycarbonylamino), a cyano group, a nitro group, an alkylthio group (having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methylthio, hexylthio), a ureido group (having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as N-phenylureido), an aryl group (having 6 to 10 carbon atoms, such a phenyl, naphthyl, 4-methoxyphenyl), a heterocyclic group (having 1 to 10 carbon atoms, a three-membered to twelve-membered, preferably five-membered or six-membered, monocyclic or fused ring type heterocyclic group having at least one hetero-atom of nitrogen, oxygen and sulfur, such as 2-pyridyl, 1-pyrrolyl, morpholino, indolyl), an alkyl group (having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a straight-chain, branched or cyclic saturated or unsaturated alkyl group, such as methyl, ethyl, butoxycarbonylmethyl, 4-methoxybenzyl, benzyl), an acyl group (having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as acetyl, benzoyl), an arylthio group (having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as phenylthio, naphthylthio), or an aryloxycarbonylamino group (having 7 to 11 carbon atoms, such as phenoxycarbonylamino). These groups may be further substituted. Examples of substituent groups include those already described above for R₁₁.

[0035] R₁₂ represents an aryl group (having 6 to 10 carbon atoms, such a phenyl, naphthyl, 4-methoxyphenyl, 3-methoxycarbonylphenyl), a heterocyclic group (having 1 to 10 carbon atoms, a three-membered to twelve-membered, preferably five-membered or six-membered, monocyclic or fused ring type heterocyclic group having at least one hetero-atom of nitrogen, oxygen and sulfur, such as 2-pyridyl, 1-pyrrolyl, morpholino, indolyl) or an alkyl group (having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a straight-chain, branched or cyclic saturated or unsaturated alkyl group, such as methyl, ethyl, butoxycarbonylmethyl, 4-methoxybenzyl, benzyl); f represents 1 to 4; g represents 0 or 1; h represents 1 or 2; V represents an oxygen atom, a sulfur atom or a group of -N(R₄₁)-; and R₄₁ is as defined above.

[0036] The group represented by TIME is described below.

[0037] The group represented by TIME may be any of bonding group which can release DI by cleavage between TIME and DI after TIME is released from A by cleavage between TIME and A during development. Examples of the group represented by TIME include groups which undergo the cleavage reaction of hemiacetal as described in U.S. Patents 4,146,396, 4,652,516 and 4,698,297; timing groups which cause a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction as described in U.S. Patents 4,248,962, 4,847,185 and 4,857,440; timing groups which cause a cleavage reaction by utilizing an electron transfer reaction as described in U.S. Patents 4,409,323 and 4,421,845; groups which cause a cleavage reaction by utilizing the hydrolysis reaction of iminoketals as described in U.S. Patent 4,546,078; and groups which cause a cleavage reaction by utilizing the hydrolysis reaction of esters as described in West German Patent Laid-Open No. 2,626,317. TIME is attached to A through a hetero-atom, preferably an oxygen atom, a sulfur atom or a nitrogen, which is contained as a member in TIME. Examples of TIME which can be preferably used in the present invention include groups represented by the following general formula (T-1), (T-2) or (T-3).



        *-W-(X=Y)_j-C(R₂₁)R₂₂-**   (T-1)





        *-W-CO**   (T-2)





        *-W-LINK-E-**   (T-3)



wherein the mark * represents the position where the group is attached to A in general formulas (Ia) and (Ib); the mark ** represents the position where the group is attached to DI or TIME when a is 2 in general formula (Ia) or the position where the group is attached to RED in general formula (Ib); W represents an a oxygen atom, a sulfur atom or a group of >N-R₂₃; X and Y each represents a methine group or a nitrogen atom; j represents 0, 1 or 2; and R₂₁, R₂₂ and R₂₃ each represents a hydrogen atom or a substituent group. X and Y each represents a substituted or unsubstituted methine group. When either X or Y or both X and Y are substituted, the substituents may be or may not be bonded to each other to form a cyclic structure. R₂₁, R₂₂ and R₂₃ may or may not be combined together to form a cyclic structure (e.g., a benzene ring, a pyrazole ring). In general formula (T-3), E represents an electrophilic group; and LINK represents a bonding group which sterically functions so as to allow an intramolecular nucleophilic substitution reaction between W and E to take place.

[0038] Specific examples of TIME represented by general formula (T-1) include the following groups:


   Specific examples of TIME represented by general formula (T-2) include the following groups:


   Specific examples of TIME represented by general formula (T-3) include the following groups:


   Specific examples of (TIME)_a where a is 2 in general formula (Ia) include the following groups:


   The group represented by RED in general formula (Ib) is described below.

[0039] RED is a group which releases DI after RED-DI is released from A or TIME by the cleavage between A or TIME and RED-DI and which is cross-oxidized by an oxidizing substance (e.g., the oxidant of the developing agent) present during development. Any group which releases DI by cleavage between RED and DI when oxidized can be used as RED. Examples of RED include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamidophenols, hydrazides and sulfonamidonaphthols. Specific examples of these groups include those described in JP-A-61-230135, JP-A-62-251746, JP-A-61-278852, U.S. Patents 3,364,022, 3,379,529, 4,618,571, 3,639,417 and 4,684,604 and J. Org. Chem., Vol. 29, page 588 (1964).

[0040] Of these groups, preferred examples of RED include hydroquinones, 1,4-naphthohydroquinones, 2 (or 4)-sulfonamidophenols, pyrogallols and hydrazides. Redox groups having a phenolic hydroxy group are attached to TIME when i is 1, or to A directly when i is 0, through the oxygen atom of the phenol group.

[0041] It is preferred that the compounds of general formula (Ia) or (Ib) have a nondiffusing group to fix the compounds of general formula (Ia) or (Ib) to the sensitive layers or non-sensitive layers containing them until silver halide photographic material containing the compounds of general formula (Ia) or (Ib) is developed. It is particularly preferred that TIME or RED has a nondiffusing group. Examples of the nondiffusing group which can be preferably used include an alkyl group having 8 to 32 carbon atoms, preferably 10 to 20 carbon atoms, and an aryl group substituted by at least one of an alkyl group (having 3 to 20 carbon atoms), an alkoxy group (having 3 to 20 carbon atoms) and an aryl group (having 6 to 20 carbon atoms).

[0042] Methods for synthesizing the compounds of general formula (Ia) or (Ib) are described in the patent specifications and the literature references cited for the illustration of TIME, RED and DI, in JP-A-61-156127, JP-A-58-160954, JP-A-58-162949, JP-A-61-249052, JP-A-63-37350, U.S. Patent 5,026,628 and European Patent Laid-Open No. 443,530A2.

[0043] Typical examples of the compounds of general formula (I) which can be used in the present invention include, but are not limited to, the following compounds:

[0044] The restrainer precursor-releasing compounds of general formula (I) according to the present invention may be used in any of the layers of the photographic material. Namely, the compounds may be used in any of the light-sensitive layers (the blue-sensitive emulsion layer, the green-sensitive emulsion layer, the red-sensitive emulsion layer and the donor layer having an interlayer effect and a different spectral sensitivity distribution from that of the principal light-sensitive layers) and the non-sensitive layers (e.g., the protective layers, the yellow filter layers, the interlayers, the antihalation layers) of the photographic materials. When a layer is composed of two or more layers having the same color sensitivity, the compounds may be added to any of the layer having the highest sensitivity, the layer having the lowest sensitivity and the layer having the intermediate sensitivity, or may be added to all layers. It is preferred that the compounds are added to the light-sensitive layers and/or the non-sensitive layers adjacent thereto.

[0045] The restrainer precursor-releasing compounds of general formula (I) are used in an amount of 5×10⁻⁴ to 2 g/m², preferably 1×10⁻³ to 1 g/m², more preferably 5×10⁻³ to 5×10⁻¹ g/m².

[0046] The restrainer precursor-releasing compounds of general formula (I) can be added to the photographic materials by any of conventional dispersion method depending on the type of the compound. For example, when the compounds are alkali-soluble, the compounds can be used in the form of an aqueous alkaline solution. The compounds may be dissolved in a water-miscible organic solvent, and the resulting solution may be used. Further, an oil-in-water dispersion method using high-boiling organic solvents or a solid dispersion method may be used.

[0047] The restrainer precursor-releasing compounds of general formula (I) may be used either alone or in a combination of two or more. Further, the same compound may be added to two or more layers. Furthermore, the compounds of general formula (I) may be used together with conventional restrainer-releasing compounds, conventional restrainer precursor-releasing compounds, or couplers described hereinafter and other additives. These compounds are appropriately chosen according to the performance required for the photographic materials.

[0048] The restrainer precursor-releasing compounds of general formula (I) according to the present invention release a restrainer precursor by a coupling reaction with oxidants of developing agents and at the same time, the mother nucleus (i.e., A in general formula (I)) thereof forms a dye.

[0049] The thus-formed dye flows into the processing solution during color development, or the dye is decolorized by bleaching as described in J. Soc. Photogra. Sci. Technol. Japan, Vol. 52 (1988), No. 2, pp. 150-155 (Kida et. al.) or the substance 2AO-22 (Kida et. al.) of the annual lecture to Photography Society of Japan in 1989. Accordingly, the dye formed is not left behind as a dye in the photographic material after color development.

[0050] The dye thus formed is liable to be dissolved or decolorized when A in general formula (I) has no nondiffusible group which makes immobile in the photogrpahic material. Further, the dye thus formed may be dissolved and simultaneously decolorized in a case that A in general formula (I) being, for example, a naphthol nucleus forms a dye to prepare a sulfite adduct at a 3-position of the naphthol nucleus by a nucleophilic reaction of sulfite ion in the processing solution and at the same time to be changed to a leuco substance itself, in which the leuco substance of sulfite adduct never returns to original dye in the succeeding oxidizing bath such as a bleaching bath.

[0051] Therefore, the restrainer precursor-releasing compounds of general formula (I) according to the present invention have an advantage in that the compounds can be used in any of the layers which constitute the photographic materials according to the performance required for the photographic materials, irrespective of whether the layer containing the compounds is a red-sensitive emulsion layer, a green-sensitive emulsion layer or a blue-sensitive emulsion layer. Further, since the dye formed is not left behind as a dye in the photographic material, the compounds do not have an adverse effect on color reproducibility, and often the fastness of the dye image is improved.

[0052] When the restrainer precursor-releasing compounds of general formula (I) together with the oil-soluble dyes of general formula (A) illustrated in greater detail hereinafter are used in photographic materials, color reproducibility and image quality such as sharpness can be further improved, and the preservability of the photographic materials can be improved. Further, photographic sensitivity and dye image fastness can be improved.

[0053] The oil-soluble dyes of general formula (A) which are used in the present invention are described in greater detail below.

[0054] The electron attractive groups represented by X and Y are groups having a Hammett's σ_p value of at least 0. Examples of the electron attractive groups represented by X and Y include a cyano group, an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, 2-hydroxyethoxycarbonyl, n-butoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl, 4-methoxyphenoxycarbonyl), a nitro group, an acyl group (e.g., acetyl, pivaloyl, benzoyl, 4-methoxybenzoyl, 4-methanesulfonamidobenzoyl, propionyl, 4-methoxy-3-methanesulfonamidobenzoyl, 1-methylcyclopropylcarbonyl, 1-ethylcyclopropylcarbonyl), a carbamoyl group [e.g., N-ethylcarbamoyl, N,N-dimethylcarbamoyl, morpholine-4-ylcarbonyl, N-(3-methanesulfonamidophenyl)carbamoyl], a sulfonyl group (e.g., benzenesulfonyl, p-toluenesulfonyl), a carboxyl group and a sulfamoyl group (e.g., sulfamoyl, N,N-dimethylsulfamoyl).

[0055] Examples of the five-membered ring formed by X and Y include 2-pyrazoline-5-ones [e.g., 3-ethoxycarbonyl-1-(4-acetylsulfamoyl)phenylpyrazolone, 3-ethoxycarbonyl-1-(4-propionylsulfamoyl)phenylpyrazolone, 3-methyl-1-(4-benzenesulfonamido)phenylpyrazolone, 3-(4-methanesulfonamido)phenyl-1-methylpyrazolone, 3-ethoxycarbonyl-1-(sulfolane-3-yl)pyrazolone, 3-methyl-1-(4-hydroxy-6-methylpyrimidine-2-yl)pyrazolone], 2-isoxazoline-5-ones (e.g., 3-t-butylisoxazolone, 3-methylisoxazolone, 3-(4-methoxy)phenylisoxazolone, 3-(4-benzenesulfonamido)phenylisoxazolone, 3-(4-toluenesulfonamido)phenylisoxazolone, 3-(4-methoxy-3-benzenesulfonamido)phenylisoxazolone, 3-{4-[3,5-bis(methoxycarbonyl)benzenesulfonamido]}phenylisoxazolone, 3-{4-(1-ethoxycarbonylpropanesulfonamido)}phenylisoxazolone, 3-(3-p-toluenesulfonamido)phenylisoxazolone), α,β-unsaturated butenolides (e.g., 3-cyano-4-(4-butanesulfonamido)phenyl-2,4-dihydro-2(4H)-furanone), β,γ-unsaturated butenolides (e.g., 4-phenyl-2,3-dihydro-2(3H)-furanone), oxazoline-5-one (e.g., 2-(4-butanesulfonamido)phenyloxazolone), 2-(4-methanesulfonamido)phenyloxazolone), 5-imidazolones (e.g., 1-ethyl-2-(4-methanesulfonamido)phenylimidazolone), indandiones (e.g., indandione, 5-benzenesulfonamidoindandione, 4-methanesulfonamidoindandione) and pyrazolidine-3,5-diones (e.g., 1,2-bis(4-acetylsulfamoyl)-phenylpyrazolidine-3,5-dione).

[0056] Examples of the six-membered ring formed by X and Y include barbituric acids (e.g., N,N'-diethylbarbituric acid, N-ethyl-N'-(4-methanesulfonamido)phenylbarbituric acid, N-methyl-N'-(4-methanesulfonylcarbonyl)phenylbarbituric acid, N-methyl-N'-(4-carboxy)phenylbarbituric acid), thiobarbituric acids (e.g., N,N'-diethylthiobarbituric acid), 1,2-dihydro-6-hydroxypyridine-2-ones (e.g., 3-cyano-1-(4-benzenesulfonamido)phenyl-4-methyl-6-hydroxypyridine, 3-carbamoyl-4-methyl-6-hydroxypyridone, 3-carbamoyl-1-(4-acetylsulfamoyl) phenyl-4-methyl-6-hydroxypyridone) and 3,4,5,7-tetrahydropyrazolo[3,4-b]pyridine-3,6-diones (e.g., 2-(4-acetylsulfamoyl)phenyl-4-methylpyrazolopyridinedione).

[0057] Examples of the five-membered heterocyclic ring represented by Ar include indoles [e.g., 1-(2-ethoxycarbonylethyl)indole, 1-(2-methoxyethoxycarbonylethyl)indole, 1-(2-acetoxyethoxycarbonylethyl)indole, 1-cyanoethylindole, 2-methyl-1-cyanoethylindole, 5-{3,5-bis(methoxycarbonyl)benzenesulfonamido}-1-methoxycarbonylmethylindole, 1-(2-p-toluenesulfonylcarbamoyl)ethylindole], furan-2-yl or furan-3-yl, thiophene-2-yl and thiophene-3-yl.

[0058] Examples of the six-membered heterocyclic ring represented by Ar include coumarins (e.g., 7-diethylaminocoumarin-3-yl), pyridine-4-yl and pyridine-5-yl.

[0059] The methine group represented by L¹, L² and L³ may have one or more substituent groups [examples of the substituent groups include methyl, ethyl and cyano; and when n is 2 or 3, the groups may be crosslinked on the methine chain (e.g., neopentylidene, propylidene)]. However, an unsubstituted methine group is preferred.

[0060] The dyes represented by general formula (A) preferably do not have any carboxyl ion chromophore.

[0061] The dyes of general formula (A) which are used in the present invention are oil-soluble dyes. The term "oil-soluble dye" as used herein refers to dyes which are water-insoluble and have a solubility of 0.1 g or less in one liter of distilled water at 25°C.

[0062] Among the dyes of general formula (A), the dyes represented by the following general formula (A-1) are preferred:


wherein R²¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a ureido group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkylthio group, an arylthio group, an oxycarbonyl group, an acyl group, a carbamoyl group, a cyano group, an alkoxy group, an aryloxy group, an amino group or an amido group; Q represents -O- or -NR²²-; R²² represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R²³, R²⁴ and R²⁵ each represents a hydrogen atom, an alkyl group or an aryl group, or R²⁴ and R²⁵ may be combined together to form a six-membered ring; R²⁶ represents a hydrogen atom, an alkyl group, an aryl group or an amino group; and k is 0 or 1, provided that when Q is -NR²²-, R²⁴ and R²⁵ together form a six-membered fused ring.

[0063] The dyes of general formula (A-1) are described in greater detail below.

[0064] The alkyl group represented by R²¹ may be substituted, and is preferably an alkyl group having 1 to 8 carbon atoms. Preferred examples of the alkyl group include methyl, ethyl, propyl, t-butyl, n-butyl, 1-methylcyclopropyl, chloromethyl, trifluoromethyl and ethoxycarbonylmethyl.

[0065] The aryl group represented by R²¹ may be substituted and is preferably an aryl group having 6 to 13 carbon atoms. Preferred examples of the aryl group include phenyl, 4-methoxyphenyl, 4-acetylaminophenyl, 4-methanesulfonamidophenyl and 4-benzenesulfonamidophenyl.

[0066] The heterocyclic group represented by R²¹ is preferably 4-pyridyl, 4-hydroxy-6-methylpyrimidine-2-yl, 2-furyl, 3-pyrrolyl, 2-imidazolyl and 2-pyrrolidinyl.

[0067] The alkyl group represented by R²² may be substituted and is preferably an alkyl group having 1 to 18 carbon atoms. Preferred examples of the alkyl group include methyl, 2-cyanoethyl, 2-hydroxyethyl and 2-acetoxyethyl.

[0068] The arylyl group or the substituted arylyl group represented by R²² has preferably 6 to 22 carbon atoms. Preferred examples thereof include phenyl, 2-methoxy-5-ethoxycarbonylphenyl, 3,5-di(ethoxycarbonyl)phenyl, 4-di(ethoxycarbonylmethyl)aminocarbonylphenyl, 4-n-octyloxycarbonylphenyl, 4-butanesulfonamidocarbonylphenyl, 4-methanesulfonamidocarbonylphenyl, 3-sulfamoylphenyl, 4-methanesulfonamidophenyl, 4-methanesulfonamidosulfonylphenyl, 4-acetylsulfamoylphenyl, 4-propionylsulfamoylphenyl and 4-N-ethylcarbamoylsulfamoylphenyl.

[0069] Examples of the heterocyclic group represented by R²² include pyridyl, 4-hydroxy-6-methylpyrimidine-2-yl, 4-hydroxy-6-t-butylpyrimidine-2-yl and sulfolane-3-yl.

[0070] The alkyl group represented by R²³, R²⁴ and R²⁵ has preferably 1 to 6 carbon atoms and may be substituted. Examples of the alkyl group include methyl, ethyl and propyl, with methyl being particularly preferred.

[0071] The aryl group represented by R²³, R²⁴ and R²⁵ has preferably 6 to 13 carbon atoms and may be substituted. Particularly preferred is a phenyl group.

[0072] The six-membered ring formed by R²⁴ and R²⁵ may be a saturated or unsaturated ring or a saturated or unsaturated heterocyclic ring. However, a benzene ring is particularly preferred.

[0073] The alkyl group represented by R²⁶ may be substituted and is preferably an alkyl group having 1 to 18 carbon atoms. Preferred examples of the alkyl group include methyl, ethyl, ethoxycarbonylmethyl, t-butoxycarbonylmethyl, ethoxycarbonylethyl, dimethylaminomethyl, 2-cyanoethyl, 3-acetamidopropyl, 3-propionylaminopropyl, 3-benzenesulfonamidopropyl and 3-propanesulfonamidopropyl.

[0074] The aryl group represented by R²⁶ is preferably a phenyl group or a substituted phenyl group having 6 to 22 carbon atoms. Preferred examples of the aryl group include phenyl, 2-methoxy-5-ethoxycarbonylphenyl, 4-di(ethoxycarbonylmethyl)aminocarbonylphenyl, 4-n-octyloxycarbonylphenyl, 4-hydroxyethoxycarbonylphenyl, 4-propanesulfonamidophenyl, 4-butanesulfonamidocarbonylphenyl, 4-methanesulfonamidosulfonylphenyl and 4-acetylsulfamoylphenyl.

[0075] The amino group represented by R²⁶ is preferably a dialkylamino group such as dimethylamino or diethylamino.

[0076] It is preferred that the compounds of general formula (A-1) do not have any of a sulfo group, a carboxyl group and a carboxylate salt group as a substituent group.

[0077] It is preferred that the compounds of general formula (A-1) have a dissociable group other than those described above. Examples of the dissociable group which can be preferably used include a substituted sulfonylamino group (e.g., CH₃SO₂NH-, C₆H₅SO₂NH-), an acylsulfamoyl group, a sulfonylsulfamoyl group, a sulfonylcarbamoyl group and a carbamoylsulfamoyl group.

[0078] Specific examples of the compounds of general formula (A) which can be used in the present invention include, but are not limited to, the following compounds:










   The dyes of general formula (A) according to the present invention may be used in any of the layers of the photographic material. However, it is preferred that the dyes are added to the non-light-sensitive layers, particularly the non-light-sensitive layer which is adjacent to the blue-sensitive layer and is provided nearer the support.

[0079] The dyes of general formula (A) are used in an amount of 2×10⁻⁵ to 5×10⁻³ mol/m², preferably 5×10⁻⁵ to 2×10⁻³ mol/m².

[0080] The dyes may be used as a mixture of two or more thereof, or may be added to two or more layers.

[0081] The dyes of general formula (A) can be introduced into the photographic material by adding dispersion prepared by conventional dispersion methods. For example, the dyes are dissolved in a high-boiling organic solvent and/or a low-boiling organic solvent and may be finely dispersed in a hydrophilic colloid medium such as gelatin. Latex dispersion methods, dispersion methods using polymers and solid dispersion methods can be used.

[0082] Particularly, oil-in-water dispersion methods using high-boiling organic solvents are preferred.

[0083] In a preparation of oil-in-water dispersion, known surface active agent may be used. Preffered examples thereof include anion surface active agent, cation surface active agent, amphoteric surface active agent, non-ionic surface active agent and combination thereof. Of them, anion surface active agent or a combination of anion surface active agent and non-ionic surface active agent is most preferred.

[0084] When a dispersion is prepared by these dispersion methods, a dispersion of only the dyes of the present invention may be prepared, or a dispersion of a mixture of the dyes of the present invention and conventional dyes may be prepared. Further, the dispersion may contain other conventional additives such as anti-fogging agents, stabilizers, color mixing inhibitors, stain inhibitors, ultraviolet light absorbers, chemical sensitizing agents, sensitivity increasers, brighteners and dye image stabilizers according to performance required for the photographic material.

[0085] The gelatin coating weight of the layer containing the dye of general formula (A) used in the present invention is not more than 1.5 g/m², preferably not more than 1.2 g/m², but not less than 0.2 g/m², more preferably not more than 1.0 g/m², but not less than 0.3 g/m².

[0086] When the gelatin coating weight exceeds 1.5 g/m², the dissolving-out of the dyes from the photographic material or the decolorization of the dyes is retarded, and a lowering in the image quality due to a residual color occurs. In addition, the color development of the light-sensitive silver halide emulsion layer which is nearer from the support than the layer containing the dye is retarded, the amount of residual silver after processing is increased by the retardation of desilverization, or photographic characteristics and image quality are lowered.

[0087] The dyes of general formula (A) used in the present invention are effective in improving image quality, particularly color reproducibility. When the dyes of general formula (A) are used in combination with the restrainer precursor releasing compounds of general formula (I), color reproducibility can be further improved by an improvement in desilverizability. There is also improvement in the preservability of the photographic materials over time and in dye image fastness.

[0088] The compounds of general formula (II) are described in greater detail below.

[0089] R₁ represents -CONR₄R₅, -SO₂NR₄R₅, -NHCOR₄, -NHCOOR₆, -NHSO₂R₆, -NHCONR₄R₅ or -NHSO₂NR₄R₅; R₄, R₅ and R₆ independently represent a straight-chained, branched or cyclic alkyl group having 1 to 30 carbon atoms, which may contain unsaturated bonds, and may be substituted by groups defined for R₂, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, isopentyl, hexyl, octyl, dodecyl, hexadecyl, eicosyl; an aryl group having 6 to 30 carbon atoms, which may contain a condensed ring, and may be substituted by groups defined for R₂, such as phenyl, naphthyl; a heterocyclic group having 2 to 30 carbon atoms and comprising 3- to 8-membered monocyclic or condensed ring containing at least one hetero atom of N, O, S, P, Se and Te, such as 2-pyridyl, 2-furyl, 4-thienyl, pyrazole-1-yl, pyrrolyl, imidazole-1-yl, benzimidazole-1-yl, which may be substituted by groups defined for R₂. R₄ and R₅ may be a hydrogen atom.

[0090] R₂ represents a group (including an atom; the same applies hereinbelow) which can be attached to the naphthalene ring. Preferred examples of them include a substituted or unsubstituted, straight-chained, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which may contain unsaturated bonds, such as methyl, ethyl, propyl, isopropyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclohexyl and allyl; an aryl group having 6 to 10 carbon atoms, such as phenyl, naphthyl; a heterocyclic group having 1 to 10 carbon atoms and comprising 3- to 12-membered, preferably 5- or 6-membered monocyclic or condensed ring containing at least one hetero atom of N, O or S, e.g., 2-pyridyl, 1-pyrrolyl, indoryl, 1-imidazolyl; a carbonamido group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as acetamido, pivaloylamido, hexanamido, benzamido; a sulfonamido group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methanesulfonamido, butanesulfonamido, benzenesulfonamido, toluenesulfonamido; a carbamoyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as carbamoyl, N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-phenylcarbamoyl; a sulfamoyl group having 0 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as sulfamoyl, N-methylsulfamoyl, N,N-diethylsulfamoyl, N-decylsulfamoyl, n-mesylsulfamoyl; a ureido group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as ureido, N-butylureido, N,N-diethylureido, N-phenylureido; an acyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as acetyl, propinoyl, butyryl, benzoyl; an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, benzoyloxy; alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, octyloxy, dodecyloxy; an aryloxy group having 6 to 10 carbon atoms, such as phenoxy, naphthyloxy; an alkylthio group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methylthio, ethylthio, propylthio, butylthio, hexylthio, decylthio; an arylthio group having 6 to 10 carbon atoms, such as phenylthio, naphthylthio; an alkylsulfonyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methylsulfonyl, ethylsulfonyl isopentylsulfonyl, octylsulfonyl; an arylsulfonyl group having 6 to 10 carbon atoms, such as phenylsulfonyl, naphthylsulfonyl; a sulfamoylamino group having 0 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as N-methylsulfamoylamino, N,N-diethylsulfamoylamino, N-phenylsulfamoylamino; an alkoxycarbonylamino group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, butoxycarbonylamino; and an imido group having 1 to 10 carbon atoms, such as succinimido, phthalimido. The groups disclosed above may be substituted by a group defined for R₂. Typical examples of R₂ include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carbonyl group, an amino group, a sulfo group, a cyano group, an alkyl group, an aryl group, a heterocyclic group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, an acyl group, an acyloxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoylamino group, an alkoxycarbonylamino group, a nitro group and an imido group. When k represents an integer of 2, preferable groups as R₂ include dioxymethylene group and trimethlene group. (R₂)_k has 0 to 30 carbon atoms in total.

[0091] R₃ represents a substituent group and is preferably a group represented by the following general formula (II-1):



        R₇(Y)_m-   (II-1)



   In general formula (II-1), Y represents >NH, >CO or -SO₂-; m represents 0 or 1; R₇ represents a hydrogen atom; a straight-chained, branched or cyclic alkyl group having 1 to 30 carbon atoms, which may contain unsaturated bonds, and may be substituted by groups defined for R₂, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, isopentyl, hexyl, octyl, dodecyl, hexadecyl, eicosyl; an aryl group having 6 to 30 carbon atoms, which may contain a condensed ring, and may be substituted by groups defined for R₂, such as phenyl, naphthyl; a heterocyclic group having 2 to 30 carbon atoms and comprising 3- to 8-membered monocyclic or condensed ring containing at least one hetero atom of N, O, S, P, Se and Te, such as 2-pyridyl, 2-furyl, 4-thienyl, pyrazole-1-yl, pyrrolyl, imidazole-1-yl, benzimidazole-1-yl, which may be substituted by groups defined for R₂, -COR₈,


-OR₁₀,




-CO₂R₁₀,


-SO₂OR₁₀ or -SO₂R₁₀
wherein R₈ and R₉ have the same meaning as R₄ and R₅, and R₁₀ has the same meaning as R₆.

[0092] In R₁ and R₇, R₄ and R₅ in the group of -NR₄R₅, or R₈ and R₉ in the group of -NR₈R₉ may be combined together to form a nitrogen-containing heterocyclic ring (e.g., a pyrrolidine ring, a piperidine ring, a morpholine ring).

[0093] X represents a hydrogen atom or a group which is eliminated by a coupling reaction with an oxidant of an aromatic primary amine developing agent [hereinafter referred to as eliminatable group (including an eliminatable atom)]. Typical examples of the eliminatable group represented by X include a halogen atom, -OR₁₁, -SR₁₁,


-NHCOR₁₁,


a thiocyanate group and a heterocyclic group having 1 to 30 carbon atoms which is bonded to the coupling active site through a nitrogen atom (e.g., a succinimido group, a phthalimido group, a pyrazolyl group, a hydantoinyl group, a 2-benztriazolyl group). R₁₁ has the same meaning as R₆.

[0094] The above-described alkyl group may be a straight-chain, branched or cyclic alkyl group, and may have one or more unsaturated bonds and one or more substituent groups (examples of the substituent groups include a halogen atom, a hydroxyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyloxy group and an acyl group). Typical examples of the alkyl group include methyl, isopropyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, n-dodecyl, n-hexadecyl, 2-methoxyethyl, benzyl, trifluoromethyl, 3-dodecyloxypropyl and 3-(2,4-di-t-pentylphenoxy)propyl.

[0095] The above-described aryl group may be a fused ring type (e.g., a naphthyl group) or may have one or more substituent groups (examples of the substituent groups include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group and an arylsulfonyl group). Typical examples of the aryl group include phenyl, tolyl, pentafluorophenyl, 2-chlorophenyl, 4-hydroxyphenyl, 4-cyanophenyl, 2-tetradecyloxyphenyl, 2-chloro-5-dodecyloxyphenyl and 4-t-butylphenyl.

[0096] The above-described heterocyclic group is a three-membered to eight-membered monocyclic or fused ring type heterocyclic group having at least one heteroatom of O, N, S, P, Se and Te and may have one or more substituent groups (examples of the substituent groups include a halogen atom, a carboxyl group, a hydroxyl group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group and an arylsulfonyl group). Typical examples of the heterocyclic group include 2-pyridyl, 4-pyridyl, 2-furyl, 4-thienyl, benztriazole-1-yl, 5-phenyltetrazole-1-yl, 5-methylthio-1,3,4-thiadiazole-2-yl and 5-methyl-1,3,4-oxadiazole-2-yl.

[0097] The preferred embodiments of formula (I) of the present invention are described below.

[0098] Preferably, R₁ is -CONR₄R₅ or -SO₂NR₄R₅. Specific examples thereof include carbamoyl, N-n-butylcarbamoyl, N-n-dodecylcarbamoyl, N-(3-n-dodecyloxypropyl)carbamoyl, N-cyclohexylcarbamoyl, N-[3-(2,4-di-t-pentylphenoxy)propyl]carbamoyl, N-hexadecylcarbamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl, N-(3-dodecyloxy-2-methylpropyl)carbamoyl, N-[3-(4-t-octylphenoxy)propyl]carbamoyl, N-hexadecyl-N-methylcarbamoyl, N-(3-dodecyloxypropylsuofamoyl and N-[4-(2,4-di-t-pentylphenoxy)butyl]sulfamoyl. Particularly preferably, R₁ is -CONR₄R₅.

[0099] (R₂)_k where k=1 is preferred, and the case where k=0 is most preferred. Preferably, R₂ is a halogen atom, an alkyl group (e.g., methyl, isopropyl, t-butyl, cyclopentyl), a carbonamido group (e.g., acetamido, pivalinamido, trifluoroacetamido, benzamido), a sulfonamido group (e.g., methanesulfonamido, toluenesulfonamido) or a cyano group.

[0100] Preferably, R₃ is the case where m=0 in general formula (II-1). More preferably, R₃ is the case where R₇ in general formula (II-1) is -COR₈ [e.g., formyl, acetyl, trifluoroacetyl, 2-ethylhexanoyl, pivaloyl, benzoyl, pentafluorobenzoyl, 4-(2,4-di-t-pentylphenoxy)butanoyl], -COOR₁₀ [e.g., methoxycarbonyl, ethoxycarbonyl, isobutoxycarbonyl, 2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl, 2-methoxyethoxycarbonyl] or -SO₂R₁₀ [e.g., methylsulfonyl, n-butylsulfonyl, n-hexadecylsulfonyl, phenylsulfonyl, p-tolylsulfonyl, p-chlorophenylsulfonyl, trifluoromethylsulfonyl]. Particularly preferably, R₇ is -COOR₁₀. The groups R₈ and R₁₀ are as defined above.

[0101] Preferably, X is a hydrogen atom, a halogen atom, -OR₁₁ in which R₁₁ has 1 to 10 carbon atoms, preferably represents a straight or branched alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, i-propyl, t-butyl, n-hexyl; and an aryl group having 6 to 10 carbon atoms which may include a condensed ring, such as phenyl, naphthyl; the alkyl group and aryl group being capable of having at least one substituent disclosed for the group of R₂ [e.g., an alkoxy group such as ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-(2-hydroxyethoxy)-ethoxy, 2-methylsulfonylethoxy, ethoxycarbonylmethoxy, carboxymethoxy, 3-carboxypropoxy, N-(2-methoxyethyl)-carbamoylmethoxy, 1-carboxytridecyloxy, 2-methanesulfonamidoethoxy, 2-(carboxymethylthio)ethoxy, 2-(1-carboxytridecylthio)ethoxy; an aryloxy group such as 4-cyanophenoxy, 4-carboxyphenoxy, 4-methoxyphenoxy, 4-t-octylphenoxy, 4-nitrophenoxy, 4-(3-carboxypropaneamido)-phenoxy, 4-acetamidophenoxy], or -SR₁₁ [e.g., an alkylthio group such as carboxymethylthio, 2-carboxyethylthio, 2-methoxyethylthio, ethoxycarbonylmethylthio, 2,3-dihydroxypropylthio, 2-(N,N-dimethylamino)ethylthio; an arylthio group such as 4-carboxyphenylthio, 4-methoxyphenylthio, 4-(3-carboxypropaneamido)phenylthio]. Particularly preferably, X is a hydrogen atom, a chlorine atom, an alkoxy group or an alkylthio group.

[0102] The couplers of general formula (II) may be in the form of a bis compound attached through R₁, R₂, R₃ or X. Two or more members of the couplers of general formula (II) may be bonded to each other through a bivalent or polyvalent group at the position of R₁, R₂, R₃ or X to form a dimer or a higher polymer. In this case, the number of carbon atoms of the substituent groups may be outside the range of the number of carbon atoms defined above.

[0103] When the couplers of general formula (II) form polymers, typical examples of the polymers include the homopolymers and copolymers of addition-polymerizable ethylenically unsaturated compounds having a group of a cyan dye forming coupler (cyan color forming monomers) preferably represented by the following general formula (II-2):



        -(Gi)_gi-(Hj)_hj-   (II-2)



   In general formula (II-2), Gi is a repeating unit derived from a color forming monomer and is a group represented by the following general formula (II-3); Hj is a repeating unit derived from a non-color forming monomer; i is a positive integer; j is 0 or a positive integer; gi is percentage by weight of Gi; hj is percentage by weight of Hj; and when i or j is 2 or greater, Gi or Hj is composed of two or more repeating units.


   In general formula (II-3), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom; A represents -CONH-, -COO- or a substituted or unsubstituted phenylene group; B represents a bivalent group having carbon atoms at both terminals, such as a substituted or unsubstituted alkylene group, a substituted or unsubstituted phenylene group or a substituted or unsubstituted oxydialkylene group; L represents -CONH-, -NHCONH-, -NHCOO-, -NHCO-, -OCONH-, -NH-, -COO-, -OCO-, -CO-, -O-, -SO₂-, -NHSO₂- or -SO₂NH-; a, b and c each represents 0 or 1; and Q represents a cyan coupler formed by removing one hydrogen atom from R₁, R₂, R₃ or X in the compound of general formula (II).

[0104] Examples of the non-color forming ethylenically unsaturated monomer which provides the repeating unit Hj and does not couple with the oxidants of the aromatic primary amine developing agents during development include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acids (e.g., methacrylic acid) and amides and esters derived from these acrylic acid compounds (e.g., acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, β-hydroxyethyl methacrylate), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g., styrene and derivatives thereof, vinyltoluene, divinylbenzene, vinylacetophenone, sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g., vinyl ethyl ether), maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- or 4-vinylpyridine.

[0105] Of these compounds, acrylic esters, methacrylic esters and maleic esters are particularly preferred.

[0106] The non-color forming ethylenically unsaturated monomers may be used in a combination of two or more thereof. For example, a combination of methyl methacrylate and butyl methacrylate, a combination of butyl acrylate and styrene, a combination of butyl methacrylate and methacrylic acid, or a combination of methyl acrylate and diacetone acrylamide may be used.

[0107] The ethylenically unsaturated monomers to be copolymerized with the vinyl monomers corresponding to the compounds of general formula (II-3) are chosen so that they have a good effect on the form (e.g., solid, liquid, micell) of the resulting copolymers, the physical properties and/or chemical properties such as solubility (e.g., solubility in water or organic solvents) of the copolymers, the compatibility of the copolymers with binders such as gelatin in photographic colloid compositions, the flexibility and thermal stability thereof, the coupling reactivity thereof with the oxidants of the developing agents, the nondiffusibility thereof in photographic colloid. The resulting copolymers may be in the form of a random copolymer or a specific sequence copolymer (e.g., a block copolymer, an alternating copolymer).

[0108] The cyan polymer couplers used in the present invention usually have a number-average molecular weight of thousands to millions. However, oligomer couplers having a number-average molecular weight of 5,000 or less can be used.

[0109] The cyan polymer couplers used in the present invention may be oleophilic polymers which are soluble in organic solvents (e.g., ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone, dibutyl phthalate, tricresyl phosphate), hydrophilic polymers which are miscible with hydrophilic colloid such as an aqueous gelatin solution, or polymers having a structure and a property such that the micell thereof can be formed in hydrophilic colloid.

[0110] It is preferred that oleophilic non-color forming ethylenically unsaturated monomers (e.g., acrylic esters, methacrylic esters, maleic esters, vinylbenzenes) are mainly used as comonomers to obtain the oleophilic polymer couplers which are soluble in the organic solvents.

[0111] The oleophilic polymer couplers obtained by polymerizing a vinyl monomer component providing the coupler unit of general formula (II-3), dissolved in the organic solvents may be prepared by emulsifying and dispersing an organic solvent solution of the coupler in the form of a latex in an aqueous gelatin solution, or may be directly prepared by an emulsion polymerization method.

[0112] The method for emulsifying and dispersing the oleophilic polymer couplers in the form of a latex in an aqueous gelatin solution is described in U.S. Patent 3,451,820. Emulsion polymerization can be carried out by using the method described in U.S. Patents 4,080,211 and 3,370,952.

[0113] It is preferred that hydrophilic non-color forming ethylenically unsaturated monomers such as N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide, 3-sulfonatopropyl acrylate, sodium styrenesulfonate, potassium styrenesulfinate, acrylamide, methacrylamide, acrylic acid, methacrylic acid, N-vinyl-pyrrolidone and N-vinylpyridine are used as comonomers to obtain the hydrophilic polymer couplers which are soluble in neutral or alkaline water.

[0114] The hydrophilic polymer couplers in the form of an aqueous solution can be added to coating solutions, or the hydrophilic polymer couplers may be dissolved in a mixed solution of water and a water-miscible organic solvent, such as a lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexanone, ethyl lactate, dimethylformamide or dimethylacetamide, and the resulting solution may be added. Further, the polymer couplers are dissolved in an aqueous alkaline solution or an alkaline water-containing organic solvent, and the resulting solution may be added. Furthermore, a small amount of a surfactant may be added.

[0115] Specific examples of the substituent groups in general formula (II) include the following groups, and specific examples of the cyan couplers of general formula (II) include the following compounds:

Specific Examples of R₁

[0116] 




wherein A is


the same applies hereinbelow.

Specific Examples of R₂

[0117] 

Specific Examples of R₃ NH-

[0118] 

Specific Examples of X

[0119] 

Specific Examples of Cyan Couplers of General Formula (II)

[0120] 












   In the above formulas of the cyan couplers II C-1 to II C-55, A represents


represents a cyclohexyl group;


represents a cyclopentyl group; and -C₈H₁₇-t represents

[0121] Examples of other cyan couplers of general formula (II) and/or the synthesis methods of these compounds are described in U.S. Patent 4,690,889, JP-A-60-237448, JP-A-61-153640, JP-A-61-145557, JP-A-63-208042, JP-A-64-31159 and West German Patent 3,823,049A.

[0122] It is preferred from the standpoint of further improving sharpness and desilverizability that a small amount of a high-boiling organic solvent is used in the dispersion of the cyan couplers of general formula (II) as described in JP-A-62-269958.

[0123] More specifically, the high-boiling organic solvent is used in a ratio by weight of the solvent to the cyan coupler of general formula (II) of 0.3 or less, preferably 0.1 or less.

[0124] The cyan couplers of general formula (II) may be used in combination of two or more thereof. When a layer is composed of two or more layers having the same color sensitivity, but different light sensitivity, it is preferred that a two equivalent type cyan coupler is added to the layer having the highest sensitivity, and a four equivalent type cyan coupler is added to the layer having the lowest sensitivity. It is preferred that either one or both is/are added to other layer having the same color sensitivity.

[0125] The phenol cyan couplers of general formula (III) are described in greater detail below.

[0126] In general formula (III), R¹ represents a straight-chain, branched or cyclic alkyl group having 1 to 36 carbon atoms, preferably 4 to 30 carbon atoms in total which may be substituted, an aryl group having 6 to 36 carbon atoms, preferably 12 to 30 carbon atoms in total which may be substituted or a heterocyclic group having 2 to 36 carbon atoms, preferably 12 to 30 carbon atoms in total. The term "heterocyclic group" as used herein refers to a five-membered to seven-membered heterocyclic group having at least one hetero-atom of N, O, S, P, Se and Te as a member of the ring, which may be a fused ring. Examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 4-pyrimidyl, 2-imidazolyl and 4-quinolyl. Examples of substituent groups for R¹ include a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfo group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an imido group, an amino group, a ureido group, an alkoxycarbonylamino group and a sulfamoylamino group (these substituent groups are hereinafter referred to as substituent group A). Preferred examples of the substituent group include an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group and an imido group.

[0127] In general formula (III), R² represents an aryl group having 6 to 36 carbon atoms, preferably 6 to 15 carbon atoms. The aryl group may be a fused ring and may be substituted by one or more substituent groups selected from the group consisting of the above-described substituent group A. Preferred examples of the substituent groups include a halogen atom (F, Cl, Br, I), a cyano group, a nitro group, an acyl group (e.g., acetyl, benzoyl), an alkyl group (e.g., methyl, t-butyl, trifluoromethyl, trichloromethyl), an alkoxy group (e.g., methoxy, ethoxy, butoxy, trifluoromethoxy), an alkylsulfonyl group (e.g., methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), an arylsulfonyl group (e.g., phenylsulfonyl, p-tolylsulfonyl, p-chlorophenylsulfonyl), an alkoxycarbonyl group (e.g., methoxycarbonyl, butoxycarbonyl), a sulfonamido group (e.g., methanesulfonamido, trifluoromethanesulfonamido, toluenesulfonamido), a carbamoyl group (e.g., N,N-dimethylcarbamoyl, N-phenylcarbamoyl) and a sulfamoyl group (e.g., N,N-diethylsulfamoyl, N-phenylsulfamoyl).

[0128] Preferably, R² is a phenyl group having at least one substituent group selected from the group consisting of a halogen atom, a cyano group, a sulfonamido group, an alkylsulfonyl group, an arylsulfonyl group and a trifluoromethyl group. More preferably, R² is 4-cyanophenyl, 4-cyano-3-halophenyl, 3-cyano-4-halophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halophenyl, 4-alkylsulfonyl-3-alkoxyphenyl, 3-alkoxy-4-alkylsulfonylphenyl, 3,4-dihalophenyl, 4-halophenyl, 3,4,5-trihalophenyl, 3,4-dicyanophenyl, 3-cyano-4,5-dihalophenyl, 4-trifluoromethylphenyl or 3-sulfonamidophenyl. Particularly preferably, R² is 4-cyanophenyl, 3-cyano-halophenyl, 4-cyano-3-halophenyl, 3,4-dicyanophenyl or 4-alkylsulfonylphenyl.

[0129] In general formula (III), Z represents a hydrogen atoms or a coupling-off group which is eliminated by a coupling reaction with an oxidant of an aromatic primary amine developing agent during development. Examples of the coupling-off group include a halogen atom, a sulfo group, an alkoxy group having 1 to 36 carbon atoms, preferably 1 to 24 carbon atoms, an aryloxy group having 6 to 36 carbon atoms, preferably 6 to 24 carbon atoms, an acyloxy group having 2 to 36 carbon atoms, preferably 2 to 24 carbon atoms, an alkylsulfonyl group having 1 to 36 carbon atoms, preferably 1 to 24 carbon atoms, an arylsulfonyl group having 6 to 36 carbon atoms, preferably 6 to 24 carbon atoms, an alkylthio group having 1 to 36 carbon atoms, preferably 2 to 24 carbon atoms, an arylthio group having 6 to 36 carbon atoms, preferably 6 to 24 carbon atoms, an imido group having 4 to 36 carbon atoms, preferably 4 to 24 carbon atoms, a carbamoyloxy group having 1 to 36 carbon atoms, preferably 1 to 24 carbon atoms and a heterocyclic group having 1 to 36 carbon atoms, preferably 2 to 24 carbon atoms which is bonded to the coupling active site through a nitrogen atom (e.g., pyrazolyl, imidazolyl, 1,2,4-triazole-1-yl, tetrazolyl). These groups (excluding a halogen atom and a sulfo group) may be substituted by one or more substituent groups selected from the group consisting of substituent group A. Preferably, Z is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic thio group. Particularly preferably, Z is a hydrogen atom, a chlorine atom, an alkoxy group or an aryloxy group.

[0130] Specific examples of R¹, R² and Z in general formula (III) include the following groups:

Example of R¹

[0131] 

Example of R²

[0132] 

Example of Z

[0133] 






   In the above formulas, A to Z and a to f are the consecutive numbers of the specific examples of R¹.

[0134] Specific examples of the cyan couplers of general formula (III) include the following compounds.

[0135] The cyan couplers of general formula (III) can be synthesized, for example, by the methods described in JP-A-56-65134, JP-A-61-2757, JP-A-63-159848, JP-A-63-161450, JP-A-63-161451, JP-A-1-254956 and U.S. Patent 4,923,791.

[0136] When the cyan coupler of general formula (II) and the cyan coupler of general formula (III) are used in combination in the present invention, the ratio of the cyan coupler of general formula (II) to the cyan coupler of general formula (III) may be widely varied. Namely, the cyan coupler of general formula (II) and the cyan coupler of general formula (III) may be used in a ratio by mol of from 99.9:0.1 to 0.1:99.9.

[0137] The cyan couplers of general formulas (II) and (III) are used in a total amount of 1×10⁻³ to 2 mol, preferably 1×10⁻² to 1 mol, more preferably 2×10⁻² to 0.5 mol per mol of silver halide when they are used in a light-sensitive layer. When the couplers are used in a non-light-sensitive layer, the couplers are used in a combined amount of 1×10⁻³ to 1 mol, preferably 2×10⁻³ to 5×10⁻¹ mol, more preferably 5×10⁻³ to 2×10⁻¹ mol per mol of silver halide in the light-sensitive layer adjacent to the non-sensitive layer.

[0138] The cyan couplers of general formulas (II) and (III) used in the present invention can be introduced into the photographic materials by any conventional dispersion method. However, an oil-in-water dispersion method is preferred as is described hereinafter in the general explanation of introduction of couplers used in the present invention into the photograhic material.

[0139] The photographic material of the present invention may comprise a support having thereon at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer. There is no particular limitation with regard to the number of silver halide emulsion layers and non-sensitive layers and the order of the layers. In a typical embodiment, the photographic material of the present invention is a silver halide photographic material comprising a support having thereon at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity, but different light sensitivity. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any one of blue light, green light and red light. In a multi-layer silver halide color photographic material, the arrangement of unit light-sensitive layers is generally made in the order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the side of the support. However, the arrangement may be made in the reverse order to that described above depending on purpose. Between layers having the same color sensitivity, there may be interposed a layer having a different light sensitivity.

[0140] A non-light-sensitive layer such as an interlayer may be provided between the silver halide light-light-sensitive layers, or a non-sensitive layer may be provided as the uppermost layer or the lowermost layer.

[0141] The interlayer may contain couplers, DIR compounds, etc., as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037, JP-A-61-20038, and conventional color mixing inhibitors.

[0142] Each unit light-sensitive layer comprising a plurality of silver halide emulsion layers may have a two-layer structure composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent 1,121,470 or U.K. Patent 923,045. The two-layer structure is preferred in the present invention. Usually, it is preferred that these layers are arranged so that light sensitivity is lowered toward the support. A non-light-sensitive layer may be provided between the silver halide emulsion layers. Further, the low-sensitivity emulsion layer may be provided on the side which is farther away from the support, and the high-sensitivity emulsion layer may be provided on the side which is nearer the support as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543.

[0143] More specifically, the arrangement of the emulsion layers can be made in the order of the low-sensitivity blue-sensitive layer (BL)/the high-sensitivity blue-sensitive layer (BH)/the high-sensitivity green-sensitive layer (GH)/the low-sensitivity green-sensitive layer (GL)/the high-sensitivity red-sensitive layer (RH)/the low-sensitivity red-sensitive layer (RL), in order of BH/BL/GL/GH/RH/RL, or in order of BH/BL/GH/GL/RL/RH from the side which is farthest away from the support.

[0144] The arrangement may be made in the order of the blue-sensitive layer/GH/RH/GL/RL from the side which is farthest away from the support as described in JP-B-55-34932 (the term "JP-B" as used herein means an "examined Japanese patent publication"). The arrangement may be made in the order of the blue-sensitive layer/GL/RL/GH/RH from the side which is farthest away from the side which is farthest away from the support as described in JP-A-56-25738 and JP-A-62-63936.

[0145] The unit light-sensitive layer may have a three-layer structure composed of three layers having different light sensitivity wherein the upper layer is a silver halide emulsion layer having the highest light sensitivity, the intermediate layer is a silver halide emulsion layer having lower light sensitivity than that of the upper layer, and the lower layer is a silver halide emulsion layer having lower light sensitivity than that of the intermediate layer so that light sensitivity is lowered in order toward the support as described in JP-B-49-15495. Even when the unit light-sensitive layer is composed of three layers having different light sensitivity, the arrangement of the three layers having the same color sensitivity, but different light sensitivity, may be made in the order of the intermediate-sensitivity emulsion layer/the high-sensitivity emulsion layer/the low-sensitivity emulsion layer from the side which is farther away from the support.

[0146] In another embodiment, the arrangement may be made in order of the high-sensitivity emulsion layer/the low-sensitivity emulsion layer/the intermediate-sensitivity emulsion layer or in order of the low-sensitivity emulsion layer/the intermediate-sensitivity emulsion layer/the high-sensitivity emulsion layer. Further, when a four or more layer structure is used, various arrangements can be made as described above.

[0147] It is preferred that a donor layer (CL) having an interlayer effect and a different spectral sensitivity distribution from that of the principal light-sensitive layer (e.g., BL, GL, RL) as described in U.S. Patents 4,663,271, 4,705,744 and 4,707,436, JP-A-62-160448 and JP-A-63-89850 is provided adjacent to or in the vicinity of the principal light-sensitive layer to improve color reproducibility.

[0148] Various layer structures and arrangements can be appropriately chosen according to the purpose of the photographic materials as described above.

[0149] The silver halide which can be preferably used in the photographic emulsion layers of the photographic materials used in the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide, each having a silver iodide content of about 30 mol% or lower. Particularly preferred is silver iodobromide or silver iodochlorobromide having a silver iodide content of about 2 to about 10 mol%.

[0150] The silver halide grains in the photographic emulsions may have a regular crystal form such as a cubic, octahedral or tetradecahedral form, an irregular crystal form such as a spherical or platy form, a crystal form having a defect such as a twinning plane, or a composite form of these crystal forms.

[0151] With regard to the grain size thereof, the silver halide grains may range from fine grains having a grain size of about 0.2 µm or smaller to larger-size grains having a grain size of about 10 µm (in terms of the diameter of a circle having an area equal to the projected area of the grain). Either a polydisperse emulsion and a monodisperse emulsion may be used.

[0152] The silver halide photographic emulsions used in the present invention can be prepared, for example, by the methods described in Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion Preparation and Types"; Research Disclosure No. 18716 (November 1979), page 648; Research Disclosure No. 307105 (November 1989), pp. 863-865; P. Glafkides, Chimie et Physique Photographique (Paul Montel 1967); G.F. Duffin, Photographic Emulsion Chemistry (Focal Press 1966); and V.L. Zelikman et al., Making and Coating Photographic Emulsion (Focal Press 1964).

[0153] Monodisperse emulsions described in U.S. Patents 3,574,628 and 3,655,394 and U.K. Patent 1,413,748 can be preferably used.

[0154] Tabular grains having an aspect ratio of 3 or more can be used in the present invention. The tabular grains can be easily prepared by the methods described in Gutoff, Photographic Science and Engineering, Vol. 14, pp. 248-257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520, and U.K. Patent 2,112,157.

[0155] The crystal structure of the grain may be uniform or different in the halogen composition between the interior of the grain and the surface layer thereof. The crystal may have a laminar structure. Silver halides having different halogen compositions may be bonded to each other by epitaxial growth. Silver halide may be joined to a compound such as silver rhodanide or lead oxide other than silver halide. A mixture of grains having various crystal forms may be used.

[0156] The emulsions may be any of a surface latent image type wherein a latent image is predominantly formed on the surface of the grain and an internal latent image type wherein a latent image is predominantly formed in the interior of the grain. However, the emulsions must be a negative type. The internal image type may be a core/shell type internal latet image type emulsion described in JP-A-63-264740. A method for preparing the core/shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of the grain varies depending on processing conditions, but is preferably in the range of 3 to 40 nm, particularly preferably 5 to 20 nm.

[0157] The silver halide emulsions are usually subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in these stages are described in Research Disclosure No. 17643, ibid., No. 18716 and ibid., No. 307105. Places where the additives are described are listed in Table described hereinafter.

[0158] A mixture of two or more light-sensitive silver halide emulsions having different characteristics in at least one of the grain size, the grain size distribution, the halogen composition, the grain form and sensitivity from each other can be used in the same layer of the photographic material of the present invention.

[0159] Silver halide grains where the surface of the grain is fogged as described in U.S. Patent 4,082,553, silver halide grains where the interior of the grain is fogged as described in U.S. Patent 4,626,498 and JP-A-59-214852, and colloidal silver can be preferably used in the light-sensitive silver halide emulsion layers and/or the substantially non-light-sensitive hydrophilic colloid layers. The term "silver halide grains where the interior or surface of the grain is fogged" as used herein refers to silver halide grains which can be uniformly (non-imagewise) developed, irrespective of the unexposed area and exposed area of the photographic material. Methods for preparing the silver halide grains where the interior or surface of the grain is fogged are described in U.S. Patent 4,626,498 and JP-A-59-214852.

[0160] Silver halide which forms the internal nuclei of the core/shell type silver halide grains wherein the interiors of the grains are fogged may be one having the same halogen composition or a different halogen composition. Any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used as the silver halide wherein the interiors or surfaces of the grains are fogged. The fogged silver halide grains have a mean grain size of 0.01 to 0.75 µm, particularly preferably 0.05 to 0.6 µm, though there is no particular limitation with regard to the grain size. Further, there is no particular limitation with regard to the grain form thereof, and the grains may have a regular form. Furthermore, polydisperse emulsions may be used, but monodisperse emulsions (at least 95% (in terms of the weight of the grains or the number of the grains) of the silver halide grains are composed of grains having a grain size of within the mean grain size ±40%] are preferred.

[0161] It is preferred that non-light-sensitive fine silver halide grains are used in the present invention. The term "non-light-sensitive fine silver halide grains" as used herein refers to silver halide grains which are not sensitive to light during imagewise exposure for obtaining a dye image and are substantially not developed in the subsequent processing. It is preferred that the non-sensitive grains are previously not fogged.

[0162] The fine silver halide grains have a silver bromide content of 0 to 100 mol% and may optionally contain silver chloride and/or silver iodide. The fine silver halide grains having a silver iodide content of 0.5 to 10 mol% are preferred.

[0163] The fine silver halide grains have a mean grain size (the diameter of the grain is defined as the diameter of a circle having an area equal to the projected area of the grain, and the average diameter of the grains is preferred to as the mean grain size) of preferably 0.01 to 0.5 µm, more preferably 0.02 to 0.2 µm.

[0164] The fine silver halide grains can be prepared in the same manner as in the preparation of the light-sensitive silver halide grains. It is not necessary that the surfaces of the silver halide grains are chemically-sensitized or spectrally-sensitized. However, it is preferred that conventional stabilizers such as triazole, azaindene, benzthiazolium or mercapto compounds or zinc compounds are added hereto before the grains are added to coating solutions. Colloidal silver can be advantageously contained in a layer containing the fine silver halide grains.

[0165] The coating weight of silver in the photographic materials of the present invention is preferably 6.0 g/m² or less, most preferably 4.5 g/m² or less.

[0166] Conventional photographic additives which can be used in the present invention are described in the aforesaid three Research Disclosure (RD), and places where the additives are described are listed below:

Additive	RD17643	RD18716	RD307105
1 Chemical sensitizing agent	page 23	right column of page 648	page 866
2 Sensitivity increaser		right column of page 648
3 Spectral sensitizing agent, super-sensitizing agent	pages 23 to 24	right column of page 648 to right column of page 649	pages 866 to 868
4 Brightening agent	page 24	right column of page 647	page 868
5 Anti-fogging agent, stabilizer	pages 24 to 25	right column of page 649	pages 868 to 870
6 Light absorber, filter dye, UV light absorber	pages 25 to 26	right column of page 649 to left column of page 650	page 873
7 Stain inhibitor	right column of page 25	lift column to right column of page 650	page 872
8 Dye image stabilizer	page 25	left column of page 650	page 872
9 Hardening agent	page 26	left column of page 651	pages 874 to 875
10 Binder	page 26	left column of page 651	pages 873 to 874
11 Plasticizer, lubricant	page 27	right column of page 650	page 876
12 Coating aid, surfactant	pages 26 to 27	right column of page 650	pages 875 to 876
13 Antistatic agent	page 27	right column of page 650	pages 876 to 877
14 Matting agent			pages 878 to 879

[0167] It is preferred that compounds capable of reacting with formaldehyde to fix it (as described in U.S. Patents 4,411,987 and 4,435,503) are added to the photographic materials to prevent photographic performance from deteriorating because of formaldehyde gas.

[0168] It is preferred that the mercapto compounds described in U.S. Patents 4,740,454 and 4,788,132, JP-A-62-18539 and JP-A-1-283551 are contained in the photographic materials of the present invention.

[0169] It is also preferred that the photographic materials of the present invention contain compounds which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver formed by development as described in JP-A-1-106052.

[0170] Further, it is preferred that the photographic materials of the present invention contain dyes dispersed by the methods described in PCT-WO88/04794 and published PCT application (in Japan) No. 1-502912 or dyes described in European Patent 317,308A, U.S. Patent 4,420,555 and JP-A-1-259358, in addition to the dyes of general formula (I).

[0171] Various color couplers can be used in the present invention. Specific examples of the color couplers are described in the patent specification cited in the aforesaid Research Disclosure No. 17643, VII-C to G and ibid., No. 307105, VII-C to G.

[0172] Yellow couplers which can be preferably used include those described in U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752 and 4,248,961, JP-B-58-10739, U.K. Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968, 4,314,023 and 4,511,649 and European Patent 249,473A.

[0173] Magenta couplers which can be preferably used include 5-pyrazolone compounds and pyrazoloazole compounds. Magenta couplers described in U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 2420 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Patents 4,500,630, 4,540,654 and 4,556,630 and PCT-WO88/04795 are particularly preferred.

[0174] Cyan couplers which can be used include those described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Patent Laid-Open No. 3,329,729, European Patents 121,365A and 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212 and 4,296,199 and JP-A-61-42658, in addition to the couplers of general formulas (II) and (III). Further, the pyrazoloazole couplers described in JP-A-64-553, JP-A-64-554, JP-A-64-555 and JP-A-64-556 and imidazole couplers described in U.S. Patent 4,818,672 can be used.

[0175] Typical examples of dye forming polymer couplers are described in U.S. Patents 3,451,820, 4,080,211, 4,367,282, 4,409,320 and 4,576,910, U.K. Patent 2,102,137 and European Patent 341,188A.

[0176] Preferred examples of couplers whose developed dye has appropriate diffusibility are described in U.S. Patent 4,366,237, U.K. Patent 2,125,570, European Patent 96,570 and West German Patent Laid-Open No. 3,234,533.

[0177] Preferred examples of colored couplers for correcting unwanted absorption of developed dyes include those described in Research Disclosure No. 17643, Item VII-G, ibid., No. 307105, Item VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258 and U.K. Patent 1,146,368. Further, there can be preferably used couplers for correcting unwanted absorption of developed dyes by a fluorescent dye released during coupling as described in U.S. Patent 4,774,181 and couplers having a dye precursor group, as an eliminatable group, capable of forming a dye by the reaction with the developing agent as described in U.S. Patent 4,777,120.

[0178] Compounds which release a photographically useful group by coupling can be preferably used in the present invention. DIR couplers which release a restrainer include those described in the patent specifications cited in the aforesaid RD No. 17643, Item VII-F and RD No. 307105, Item VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350, and U.S. Patents 4,248,962 and 4,782,012, in addition to the compounds of general formula (I).

[0179] Bleaching accelerator-releasing couplers described in RD No. 11449, RD No. 24241 and JP-A-61-201247 are effective in shortening processing time in a processing stage having a bleaching ability. Particularly, when the couplers are added to the photographic materials containing the aforesaid tabular silver halide grains, the effect thereof is remarkable.

[0180] Preferred examples of couplers which release imagewise a nucleating agent or a development accelerator during development include those described in U.K. Patents 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840. Further, compounds which release a fogging agent, a development accelerator or a silver halide solvent by a redox reaction with the oxidants of the developing agents, described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-45687, can be preferably used.

[0181] Examples of other compounds which can be used in the present invention include competitive couplers described in U.S. Patent 4,130,427; polyequivalent type couplers described in U.S. Patents 4,283,472, 4,338,393 and 4,310,618; DIR redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds and DIR redox-releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252; couplers which release a dye whose color is restored to the original color after elimination described in European Patents 173,302A and 313,308A; ligand-releasing couplers described in U.S. Patent 4,555,477; leuco dye-releasing couplers described in JP-A-63-75747; and fluorescent dye-releasing couplers described in U.S. Patent 4,774,181.

[0182] The couplers used in the present invention can be introduced into the photographic materials by conventional dispersion methods.

[0183] Examples of high-boiling organic solvents used in oil-in-water dispersion methods are described in U.S. Patent 2,322,027. Specific examples of the high-boiling organic solvents having a boiling point of not lower than 175°C under atmospheric pressure which can be used in the oil-in-water dispersion methods include phthalic esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl)phthalate), phosphoric or phosphonic esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tri-decyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphate), benzoic esters (e.g., 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate), amides (e.g., N,N-diethyldecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (e.g., isostearyl alcohol, 2,4-di-t-amylphenol), aliphatic carboxylic acid esters (e.g., bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (e.g., N,N-dibutyl-2-butoxy-5-t-octylaniline) and hydrocarbons (e.g., paraffin, dodecylbenzene, diisopropylnaphthalene). Further, organic solvents having a boiling point of not lower than about 30°C, preferably not lower than 50°C, but not higher than about 160°C can be used as co-solvents. Typical examples of the co-solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

[0184] Examples of the stages and effects of latex dispersion methods and impregnating latexes are described in U.S. Patent 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

[0185] It is preferred that various antiseptic or antifungal agents such as phenethyl alcohol and 1,2-benzisothiazoline-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941 are added to the color photographic materials of the present invention.

[0186] The present invention can be applied to various color photographic materials. Typical examples of the color photographic materials to which the present invention is applicable include general-purpose and movie color negative films, reversal color films for slides and TV, color paper, color positive films and reversal color paper.

[0187] Suitable supports which can be used in the present invention are described in, for example, the aforesaid RD No. 17643 (page 28), RD No. 18716 (right column of page 647 to left column of page 648) and RD No. 307105 (page 879).

[0188] The sum total of the thickness of the entire hydrophilic colloid layers on the emulsion layer side of the photographic material of the present invention is preferably 28 µm or less, more preferably 23 µm or less, still more preferably 18 µm or less, particularly preferably 16 µm or less. The layer swelling rate T½ is preferably 30 seconds or less, more preferably 20 seconds or less. The layer thickness is a value obtained by making the measurement under moisture conditioning at 25°C and 55% RH for 2 days. The layer swelling rate T½ can be measured by conventional method in the art, for example, by using a swellometer of a type described in A. Green, Photographic Science and Engineering, Vol. 19, No. 2, pp. 124-129. The layer swelling rate T½ is defined as a time taken until the swollen rate reaches ½ of the saturate layer thickness when 90% of the maximum swollen layer thickness attained by conducting processing with a color developing solution at 30°C for 3¼ minutes is referred to as the saturated layer thickness.

[0189] The layer swelling rate T½ can be controlled by adding a hardening agent to gelatin as a binder or by varying conditions with time after coating. The swollen ratio is preferably 150 to 400%. The swollen ratio can be calculated from the maximum swollen layer thickness under the above conditions by the following formula.





   It is preferred that the photographic materials of the present invention are provided with a hydrophilic colloid layer (called a back layer) having a dry layer thickness of 2 to 20 µm in total at the opposite side to the side having emulsion layers. It is preferred that the back layer contains the above-described light absorber, filter dye, ultraviolet light absorber, antistatic agent, hardening agent, binder, plasticizer, lubricant, surfactant, etc. The swollen ratio of the back layer is preferably 150 to 500%.

[0190] The color photographic materials of the present invention can be processed by the conventional methods described in the aforesaid RD No. 17643 (pages 28 to 29), RD No. 18716 (left column to right column of page 651) and RD No. 307105 (pages 880 to 881).

[0191] The color developing solutions used in processing the photographic materials of the present invention are preferably aqueous alkaline solutions containing aromatic primary amine color developing agents as the principal ingredients. Aminophenol compounds are useful as the color developing agents, but p-phenylenediamine compounds are preferred. Typical examples of the p-phenylenediamine compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-ethyl-N-(2-hydroxypropyl)aniline, 4-amino-3-ethyl-N-ethyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-propyl-N-(3-hydroxypropyl)aniline, 4-amino-3-propyl-N-methyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-methyl-N-(4-hydroxybutyl)aniline, 4-amino-3-methyl-N-ethyl-N-(4-hydroxybutyl)aniline, 4-amino-3-methyl-N-propyl-N-(4-hydroxybutyl)aniline, 4-amino-3-ethyl-N-ethyl-N-(3-hydroxy-2-methylpropyl)aniline, 4-amino-3-methyl-N,N-bis(4-hydroxybutyl)aniline, 4-amino-3-methyl-N,N-bis(5-hydroxypentyl)aniline, 4-amino-3-methyl-N-(5-hydroxypentyl)-N-(4-hydroxybutyl)aniline, 4-amino-3-methoxy-N-ethyl-N-(4-hydroxybutyl)aniline, 4-amino-3-ethoxy-N,N-bis(5-hydroxypentyl)aniline, 4-amino-3-propyl-N-(4-hydroxybutyl)aniline and salts thereof such as sulfate, hydrochloride and p-toluenesulfonate. Of these compounds, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-ethyl-N-(4-hydroxybutyl)aniline and their hydrochlorides, p-toluenesulfonates and sulfates are particularly preferred. These compounds may be used in a combination of two or more thereof depending on the purpose.

[0192] Generally, the color developing solutions contain pH buffering agents such as alkali metal carbonates, borates and phosphates and restrainers such as chlorides, bromides, iodides, benzimidazoles, benzthiazoles or mercapto compounds or anti-fogging agents. If desired, the color developing solutions may optional-ly contain preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazides (e.g., N,N-biscarboxymethylhydrazine), phenylsemicarbazides, triethanolamine and catecholsulfonic acid; organic solvents such as ethylene glycol and diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines; color forming couplers; competitive couplers; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; tackifiers; and chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids,- alkylphosphonic acids and phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid and ethylenediamine-di(o-hydroxyphenylacetic acid) and salts thereof.

[0193] Generally, when reversal processing is to be conducted, black-and-white development is first carried out and color development is then carried out. Black-and-white developing solutions may contain conventional developing agents such as dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone) and aminophenols (e.g., N-methyl-p-aminophenol). These developing agents may be used either alone or in combination of two or more.

[0194] The pH of the color developing solutions and the black-and-white developing solutions is generally in the range of 9 to 12. The replenishment rate of these developing solutions varies depending on the type of the color photographic materials, but is usually not more than 3 ℓ per m² of the photographic material. The replenishment rate can be reduced to 500 ml or less when the concentration of bromide ion in the replenisher is reduced. When the replenishment is to be reduced, it is desirable that the contact area of the processing solutions with air in the bath is reduced to prevent the solution from being evaporated or oxidized by air.

[0195] The contact area of the processing solutions with air in the bath can be represented by an opening ratio defined below.








   The opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. Examples of methods for reducing the opening ratio include a method wherein a cover such as a floating cover is provided on the surface of the photographic processing solution in the bath; a method using a movable cover as described in JP-A-1-82033; and a slit processing method described in JP-A-63-216050. It is preferred that the reduction of the opening ratio is applied to both the color development stage and the black and white development stage as well as to all of the subsequent stages such as bleaching, bleaching-fixing, fixing, rinsing and stabilizing stages. The replenishment rate can be reduced by using a means for inhibiting the accumulation of bromide ion in the developing solutions.

[0196] The color development time is usually set between 2 and 5 minutes. When the color developing agents are used at a higher concentration under higher temperature and higher pH conditions, the processing time can be further shortened.

[0197] After color development, the photographic emulsion layer is generally bleached. Bleaching may be carried out simultaneously with fixing (bleaching-fixing treatment), or they are separately carried out. After bleaching, a bleaching-fixing treatment may be conducted to expedite processing. Bleaching-fixing may be conducted by a bleaching-fixing bath composed of two consecutive baths. Fixing may be conducted before the bleaching-fixing treatment. After the bleaching-fixing treatment, bleaching may be conducted according to purpose. Examples of bleaching agents include compounds of polyvalent metals such as iron(III), peracids, quinones and nitro compounds. Typical examples of the bleaching agents include organic complex salts of iron(III) such as complex salts of aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, etc.) citric acid, tartaric acid, malic acid, etc. Among them, ion(III) complex salts of aminopolycarboxylic acids such as (ethylenediaminetetraacetato)iron(III) complex and 1,3-diaminopropanetetraacetato)iron(III) complex are preferred from the viewpoints of rapid processing and prevention of environmental pollution. Further, iron(III) complex salts of aminopolycarboxylic acids are useful for bleaching solutions and bleaching-fixing solutions. The pH of the bleaching solutions containing the iron(III) complex salts of the aminopolycarboxylic acids and the bleaching-fixing solutions containing said iron(III) complex salts is generally in the range of 4.0 to 8. A lower pH may be used to expedite processing.

[0198] If desired, the bleaching solution, the bleaching-fixing solution and the prebath thereof may contain bleaching accelerators. Examples of the bleaching accelerators include compounds having mercapto group or disulfide group described in U.S. Patent 3,893,858, West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426 and Research Disclosure No. 17129 (July 1978); thiazolidine derivatives described in JP-A-50-140129; thiourea derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735 and U.S. Patent 3,706,561; iodides described in West German Patent 1,127,715 and JP-A-58-16235; polyoxyethylene compounds described in West German Patents 996,410 and 2,748,430; polyamine compounds described in JP-B-45-8836; compounds described in JP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940; and bromide ions. Among them, the compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a high accelerating effect. Particularly, the compounds described in U.S. Patent 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are preferred. Further, the compounds described in U.S. Patent 4,552,834 are preferred. These bleaching accelerators may be incorporated into the photographic materials. These bleaching accelerators are particularly effective in conducting the bleaching-fixing of the color photographic materials for photographing.

[0199] It is preferred that the bleaching solution and the bleaching-fixing solution contain organic acids in addition to the above-described compounds to prevent bleach stain from being formed. The organic acids which can be preferably used are compounds having a dissociation constant (pKa) of 2 to 5. Specific examples of the compounds include acetic acid, propionic acid and hydroxy-acetic acid.

[0200] Fixing agents which can be used in the fixing solution and the bleaching-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and many iodides. Thiosulfates are generally used. Particularly, ammonium thiosulfate is most widely used. Further, a combination of thiosulfates with thiocyanates, thioether compounds or thioureas can be preferably used. Examples of preservatives which can be preferably used in the fixing solution and the bleaching-fixing solution include sulfites, bisulfites, carbonyl bisulfite adducts and sulfinic acid compounds described in European Patent 294,769A. Further, it is preferred that the fixing solution and the bleaching-fixing solution contain aminopolycarboxylic acids or organic phosphonic acids to stabilize the solution.

[0201] It is preferred that compounds having a pKa of 6.0 to 9.0, preferably imidazole compounds such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methyl imidazole in an amount of 0.1 to 10 mol/ℓ are added to the fixing solution and the bleaching-fixing solution to adjust the pH.

[0202] It is preferred that the total time in the desilverization stage is as short as possible, so long as a failure in desilverization does not occur. The desilverization time is preferably 1 to 3 minutes, more preferably 1 to 2 minutes. The desilverization temperature is 25 to 50°C, preferably 35 to 45°C. When desilverization is carried out in the preferred temperature range, the desilverization rate can be improved, and stain can be effectively prevented from being formed after processing.

[0203] It is preferred that stirring in the desilverization stage is carried out as intensely as possible. Specific examples of methods for carrying out stirring intensely include a method wherein a jet stream of the processing solution is allowed to collide with the emulsion layer surface of the photographic material as described in JP-A-62-183460; a method wherein a stirring effect is increased by a rotary means as described in JP-A-62-183461; a method wherein while the emulsion layer surface is brought into contact with a wiper blade provided in the processing solution, the photographic material is transferred to thereby form a turbulent flow, thus improving a stirring effect; and a method wherein the circulating flow rate of the entire processing solution is increased. These means for improving the stirring effect are effective in conducting the stirring of any of the bleaching solution, the bleaching-fixing solution and the fixing solution. It is believed that an improvement in stirring accelerates the feed of the bleaching agent and the fixing agent into the emulsion layers and as a result, the desilverization rate is increased. The above-described means for improving stirring is particularly effective when the bleaching accelerators are used. The desilverization accelerating effect can be greatly increased, and a problem with regard to fixing inhibition caused by the bleaching accelerators can be solved.

[0204] It is preferred that automatic processors used in the processing of the photographic materials of the present invention are provided with a photographic material-conveying means described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191258. The conveying means enables the amount of the processing solution brought over from the prebath into the subsequent bath to be greatly reduced, and an effect of preventing the performance of the processing solution from being deteriorated is high as described in the aforesaid JP-A-60-191257. This effect is particularly effective in shortening the processing time in each stage or in reducing the replenishment rate of each replenisher.

[0205] Usually, the silver halide color photographic materials of the present invention are subjected to a washing and/or stabilization stage after desilverization. The amount of rinsing water in the washing stage widely varies depending on the characteristics (e.g., depending on materials used such as couplers) of the photographic materials, the use, the temperature of rinsing water, the number of rinsing tanks (the number of stages), the replenishing system (countercurrent, direct flow) and other conditions. The relationship between the amount of water and the number of rinsing tanks 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, p. 248-253 (mat 1955).

[0206] According to the multi-stage countercurrent system described in the above literature reference, the amount of rinsing water can be greatly reduced. However, there is caused a problem that the residence time of water in the tanks is prolonged and as a result, bacteria are grown and the resulting suspended matter is deposited on the photographic material. A method for reducing calcium ion and magnesium ion described in JP-A-62-288838 can be effectively used for the color photographic materials of the present invention to solve the above-mentioned problem. Further, isothiazolone compounds, thiabendazoles, chlorine-containing microbicides such as sodium chlorinated isocyanurate and benztriazoles described in JP-A-57-8542, and microbicides described in Chemistry of Antimicrobial Antifungal Agent, written by Hiroshi Horiguchi (published by Sankyo Shuppan 1986 written in Japanese), Sterization, Disinfection, Antifungal Technique, edited by Sanitary Technique Society (published by Kogyo Gijutsu Kai 1982 written in Japanese) and Antibacterial and Antifungal Encyclopaedia, edited by Antimicrobial Antifungal Society of Japan (1986 written in Japanese) can be used.

[0207] The pH of rinsing water in the treatment of the photographic materials of the present invention is in the range of 4 to 9, preferably 5 to 8. The temperature of rinsing water and washing time vary depending on the characteristics of the photographic materials, use, etc., but the temperature and time of washing are generally 15 to 45°C for 20 seconds to 10 minutes, preferably 25 to 40°C for 30 seconds to 5 minutes. The photographic materials of the present invention may be processed directly with stabilizing solutions in place of rinsing water. Such stabilizing treatment can be carried out by the conventional methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345.

[0208] The stabilizing treatment subsequent to rinsing may be conducted. In an embodiment thereof, the stabilizing treatment is used as the final bath for the color photographic materials for photographing. An example thereof includes a stabilizing bath containing a dye stabilizer and a surfactant. Examples of the dye stabilizer include aldehydes such as formaldehyde and glutaric aldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. The stabilizing bath may contain various chelating agents and antifungal agents.

[0209] Overflow solution from the replenishment of rinsing water and/or stabilizing can be reused in other stages such as the desilverization stage.

[0210] It is preferred that when each processing solution is concentrated by evaporation in the processing using automatic processors, water is added thereto to correct the concentration of each processing solution.

[0211] The color developing agents may be incorporated in the silver halide color photographic materials of the present invention for the purpose of simplifying and expediting processing. It is preferred that precursors for the color developing agents are used for the incorporation thereof in the photographic materials. Examples of the precursors include the indoaniline compounds described in U.S. Patent 3,342,597; the Schiff base type compounds described in U.S. Patent 3,342,599 Research Disclosure No. 14850 and ibid., No. 15159; the aldol compounds described in Research Disclosure No. 13924; the metal complex salts described in U.S. Patent 3,719,492; and the urethane compounds described in JP-A-53-135628.

[0212] If desired, 1-phenyl-3-pyrazolidones may be incorporated into the silver halide color photographic materials of the present invention to accelerate color development. Typical examples of the compounds include those described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

[0213] In the present invention, various processing solutions are used at a temperature of 10 to 50°C. Generally, a temperature of 33 to 38°C is used. However, it is possible that higher temperature is used to accelerate processing and to shorten processing time, while lower temperature is used to improve image quality and stability of the processing solutions.

[0214] When the silver halide color photographic materials of the present invention are applied to film units equipped with a lens described in JP-B-2-32615 and JP-B-U-3-39784 (the term "JP-B-U" as used herein means an "examined Japanese utility model publication"), the effect of the present invention is more remarkable.

[0215] The present invention is now illustrated in greater detail by reference to the following examples which, however, are not to be construed as limiting the invention in any way.

EXAMPLE 1

[0216] The following layers having the following compositions were coated on a cellulose triacetate film support having a subbing layer to prepare a multi-layer photographic material as Sample No. 101.

Composition of Light-Sensitive Layer

[0217] Following abbreviations for main ingredients are used for brevity's sake.

ExC:

Cyan Coupler

ExM:

Magenta Coupler

ExY:

Yellow Coupler

ExS:

Sensitizing Dye

UV :

Ultraviolet Light Absorber

HBS:

High-Boiling Organic Solvent

H :

Hardening Agent for Gelatin

   Numerals for the ingredients represent coating weight (g/m²). The amounts of silver halide emulsions are represented by the coating weight in terms of silver. The amounts of sensitizing dyes are represented by moles per one mole of silver halide in the same layer.

Sample No. 101

[0218] 

First Layer (antihalation layer)
Black Colloidal Silver (in terms of silver)	0.18
Gelatin	1.40
ExM-1	0.18
ExF-1	2.0×10⁻³
HBS-1	0.20

Second Layer (interlayer)
Emulsion G (in terms of silver)	0.065
2,3-Di-t-pentadecylhydroquinone	0.18
ExC-1	0.020
UV-1	0.060
UV-2	0.080
UV-3	0.10
HBS-1	0.10
HBS-2	0.020
Gelatin	1.04

Third Layer (low-sensitivity red-sensitive emulsion layer)
Emulsion A (in terms of silver)	0.25
Emulsion C (in terms of silver)	0.25
ExS-1	4.5×10⁻⁴
ExS-2	1.5×10⁻⁵
ExS-3	4.5×10⁻⁴
IIC-7	0.17
IIC-34	0.030
IIIC-2	0.11
ExC-2	0.0050
ExC-4	0.0050
ExC-5	0.020
Cpd-2	0.025
HBS-1	0.10
HBS-4	0.10
Gelatin	0.87

Fourth Layer (intermediate-sensitivity red-sensitive emulsion layer)
Emulsion D (in terms of silver)	0.80
ExS-1	3.0×10⁻⁴
ExS-2	1.2×10⁻⁵
ExS-3	4.0×10⁻⁴
IIC-7	0.15
ExC-1	0.060
IIIC-2	0.12
ExC-4	0.0010
ExC-5	0.025
Cpd-2	0.023
HBS-1	0.10
HBS-5	0.050
Gelatin	0.75

Fifth Layer (high-sensitivity red-sensitive emulsion layer)
Emulsion E (in terms of silver)	1.40
ExS-1	2.0×10⁻⁴
ExS-2	1.0×10⁻⁵
ExS-3	3.0×10⁻⁴
IIC-7	0.043
IIC-34	0.040
IIIC-2	0.063
ExC-3	0.020
ExC-5	0.007
Cpd-2	0.050
HBS-1	0.22
HBS-2	0.10
Gelatin	1.20

Sixth Layer (interlayer)
Cpd-1	0.10
HBS-1	0.50
Gelatin	1.10

Seventh Layer (low-sensitivity green-sensitive emulsion layer)
Emulsion A (in terms of silver)	0.17
Emulsion C (in terms of silver)	0.17
ExS-4	4.0×10⁻⁵
ExS-5	1.8×10⁻⁴
ExS-6	6.5×10⁻⁴
ExS-8	8.0×10⁻⁴
ExS-10	3.0×10⁻⁴
ExM-1	0.010
ExM-2	0.33
ExM-3	0.086
Comparative Coupler (1)	0.015
HBS-1	0.30
HBS-3	0.010
HBS-5	0.10
Gelatin	0.73

Eighth Layer (intermediate-sensitivity green-sensitive emulsion layer)
Emulsion D (in terms of silver)	0.80
ExS-4	2.0×10⁻⁵
ExS-5	1.4×10⁻⁴
ExS-6	5.4×10⁻⁴
ExS-9	7.0×10⁻⁴
ExS-10	2.5×10⁻⁴
ExM-2	0.16
ExM-3	0.045
Comparative Coupler (1)	0.01
Comparative Coupler (2)	0.030
HBS-1	0.10
HBS-3	8.0×10⁻³
HBS-4	0.10
Gelatin	0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer)
Emulsion E (in terms of silver)	1.25
ExS-4	3.7×10⁻⁵
ExS-5	8.1×10⁻⁵
ExS-6	3.2×10⁻⁴
ExS-8	2.5×10⁻⁴
ExS-9	2.5×10⁻⁴
Comparative Coupler (3)	0.020
ExM-1	0.015
ExM-4	0.040
ExM-5	0.019
Cpd-3	0.020
HBS-1	0.25
HBS-2	0.10
Gelatin	1.20

Tenth Layer (yellow filter layer)
Yellow Colloidal Solver (in terms of silver)	0.010
Cpd-1	0.16
HBS-1	0.15
HBS-5	0.10
Gelatin	0.65

Eleventh Layer (low-sensitivity blue-sensitive emulsion layer)
Emulsion C (in terms of silver)	0.25
Emulsion D (in terms of silver)	0.40
ExS-7	8.0×10⁻⁴
ExY-1	0.030
ExY-2	0.55
ExY-3	0.25
ExY-4	0.020
ExC-4	0.01
HBS-1	0.25
HBS-5	0.10
Gelatin	1.30

Twelfth Layer (high-sensitivity blue-sensitive emulsion layer)
Emulsion F (in terms of silver)	1.38
ExS-7	3.0×10⁻⁴
ExY-2	0.10
ExY-3	0.10
HBS-1	0.070
HBS-4	0.030
Gelatin	0.86

Thirteenth Layer (first protective layer)
Emulsion G (in terms of silver)	0.20
UV-4	0.11
UV-5	0.17
HBS-1	5.0×10⁻²
Gelatin	1.00

Fourteenth Layer (second protective layer)
H-1	0.40
B-1 (diameter 1.7 µm)	5.0×10⁻²
B-2 (diameter 1.7 µm)	0.10
B-3	0.10
S-1	0.20
Gelatin	1.20

[0219] Further, each layer contained W-1 to W-3, B-4 to B-6, F-1 to F-17, an iron salt, a lead salt, a gold salt, a platinum salt, an iridium salt and a rhodium salt to improve preservability, processability, pressure resistance, antifungal and antimicrobial properties, antistatic properties and coatability.

[0220] In Table 1,

(1) Emulsions A to F were reduction-sensitized during the preparation of the grains by using thiourea dioxide and thiosulfonic acid according to Examples of JP-A-2-191938;

(2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of sodium thiocyanate and spectral sensitizing dyes described in each light-sensitive layer according to Examples of JP-A-3-237450;

(3) the tabular grains were prepared by using low-molecular gelatin according to Examples of JP-A-1-158426; and

(4) the tabular grains and the regular crystal grains having a grain structure showed that dislocation lines as described in JP-A-3-237450 were observed through a high-pressure electron microscope.

Comparative Coupler (1)

[0221] 

Comparative Coupler (2)

[0222] 

Comparative Coupler (3)

[0223] 


   The following samples were also prepared.

Sample No. 102

[0224] Sample No. 102 was prepared in the same manner as Sample No. 101, except that an equimolar amount of Compound (25) of general formula (I) according to the present invention was used in place of Comparative Coupler (1) used in the seventh layer (green-sensitive layer) of Sample No. 101, an equimolar amount of each of Compounds (25) and (22) of the present invention was used in place of each of Comparative Couplers (1) and (2) used in the eight layer of Sample No. 101, and an equimolar amount of Compound (30) of the present invention was used in place of Comparative Compound (3) used in the ninth layer of the sample 101.

Sample Nos. 103 and 104

[0225] Sample No. 103 was prepared in the same manner as Sample No. 101, except that Dye D-22 of general formula (A) according to the present invention was used in place of yellow colloidal silver used in the tenth layer (yellow filter layer) of Sample No. 101. Similarly, Sample No. 104 was prepared in the same manner as in the preparation of Sample No. 102 except that Dye D-22 was used in place of yellow colloidal silver used in the 10th layer (yellow filter layer) of Sample No. 102. In the preparation of the Sample Nos. 103 and 104, Dye D-22 was used in a coating weight of 4.0×10⁻⁴ mol/m². The dye was used as a dispersion in HBS-1 and HBS-5. HBS-1 and HBS-5 were used in an equal coating weight.

Sample Nos. 105 to 114

[0226] Sample Nos. 105 to 114 were prepared in the same manner as Sample Nos. 104, except that an equimolar amount of each of the compounds of general formula (I) shown in Tables 2 and 3 below was used in place of each of Compound (25) used in the seventh layer, Compounds (25) and (22) used in the eighth layer and Compound (30) used in the tenth layer of Sample No. 104.

Sample Nos. 115 to 118

[0227] Sample Nos. 115 to 118 were prepared in the same manner as Sample No. 104, except that an equimolar amount of each of the dyes of general formula (A) shown in Table 4 below was used in place of Dye 22 used in the tenth layer (yellow filter layer) of Sample No. 104.

Sample Nos. 119 to 120

[0228] Sample Nos. 119 and 120 were prepared in the same manner as Sample No. 104, except that the gelatin coating weight (0.65 g/m²)of the tenth layer (yellow filter layer) of the sample 104 was reduced to 0.50 g/m² and 0.40 g/m², respectively, as shown in Table 9 below.

Sample No. 121

[0229] Sample No. 121 was prepared in the same manner as in the preparation of Sample No. 104 except that an equimolar amount of the following Comparative Dye (1) was used in place of Dye D-22 of general formula (A) used in the tenth layer (yellow filter layer) of the Sample No. 104.

Comparative Dye (1): Compound (13) described in JP-A-3-144438

[0230] 

[0231] The thus-prepared Sample Nos. 101 to 121 were subjected to the following color development, and the following performances thereof were examined.

(1) Photographic Characteristics

[0232] The samples were subjected to gradation exposure to white light (color temperature of light source: 4800°K) and then to color development. The density of each sample was measured. The logarithmic value of the reciprocal of the exposure amount providing a density of (the minimum density + 0.2) was determined from the characteristic curve of the magenta density and referred to as the sensitivity. The sensitivity of Sample No. 101 was referred to as the standard, and the difference (ΔS_G) between the standard and the sensitivity of each of other samples was determined.

(2) Preservability of Photographic Material with time

[0233] Each sample was divided into two groups. One group was stored at 5°C and 30% RH for 5 days, and another group was stored at 50°C and 80% RH for 5 days. After completion of the storage, these samples were subjected to gradation exposure to white light and then to color development. Subsequently, the sensitivity of each sample was measured in the same manner as described above (1). The sensitivity of each sample stored at 5°C and 30% RH was referred as the standard. The difference (ΔS₁) between the standard and the sensitivity of each sample stored at 50°C and 80% RH was determined.

(3) Dye Image Fastness

[0234] The magenta density of each sample processed after gradation exposure to white light was measured. Subsequently, the samples ware stored at 60°C and 70% RH for 30 days, and the density of each sample was again measured. The density of each sample after completion of the test in the exposure amount providing a density of (the minimum density of the magenta density before the commencement of the test + 1.5) was read. A value by percentage obtained by dividing the value obtained by subtracting the minimum density from the read value, by the density of 1.5 was determined and referred to as the dye image residual ratio (D%).

(4) Color Reproducibility (Color Turbidity)

[0235] The samples were subjected to gradation exposure to light through a green color separation filter, and then to color development. The G density and B density of the magenta dye image of each sample processed were measured. The B density in the exposure amount providing a density of (the minimum density of the G density + 2.0) was determined. A value obtained by subtracting the B density in the minimum density area from the above determined B value was referred to as color turbidity which was used as a measure of the evaluation of color reproducibility. A smaller value means that color turbidity is lower and color reproducibility is better.

[0236] The color development used in this Example is shown below. Processing was made such that after imagewise exposure to light, the samples were continuously processed until the amount of the replenisher of the color developing solution reached three times the capacity of the tank. After this processing, the samples were tested to examine their performance.

[0237] The following processing stages and processing solutions were used.

Processing Stage
Stage	Processing Time	Processing Temperature	Replenishment Rate*	Tank Capacity
Color development	3 min 5 sec	38.0°C	600 ml	17 ℓ
Bleaching	50 sec	38.0°C	140 ml	5 ℓ
Bleaching-fixing	50 sec	38.0°C	-	5 ℓ
Fixing	50 sec	38.0°C	420 ml	5 ℓ
Rinse	30 sec	38.0°C	980 ml	3.5 ℓ
Stabilization (1)	20 sec	38.0°C	-	3 ℓ
Stabilization (2)	20 sec	38.0°C	560 ml	3 ℓ
Drying	1 min 30 sec	60°C

* Replenishment rate being per m² of the photographic material

[0238] The flow of the stabilizing solution was a countercurrent system of from (2) to (1). All of the overflow solution of rinsing water was introduced into the fixing bath. The replenishment of the bleaching-fixing bath was made in the following manner. The upper part of the bleaching bath and the upper part of the fixing bath in the automatic processor were provided with a notch so that all of the overflow solution produced by feeding the replenishers to the bleaching bath and the fixing bath was allowed to flow into the bleaching-fixing bath. The amount of the developing solution brought into the bleaching stage, that of the bleaching solution brought into the bleaching-fixing stage, that of the bleaching-fixing solution brought into the fixing bath and that of the fixing solution brought into the rinsing stage 65 ml, 50 ml, 50 ml and 50 ml, respectively, each amount being m² of the photographic material. Cross-over time was 6 seconds each time. The cross-over time was included in the processing time of the pre-stage.

[0239] The processing solutions had the following compositions.

Color Developing Solution

[0240] 

	Tank Solution (g)	Replenisher (g)
Diethylenetriaminepentaacetic Acid	2.0	2.0
1-Hydroxyethylidene-1,1-diphosphonic Acid	3.3	3.3
Sodium Sulfite	3.9	5.1
Potassium Carbonate	37.5	39.0
Potassium Bromide	1.4	0.4
Potassium Iodide	1.3 mg	-
Hydroxylamine Sulfate	2.4	3.3
2-Methyl-4-[N-ethyl-N-(β-hydroxy)amino]aniline Sulfate	4.5	6.0
Water to make	1.0 liter	1.0 liter
pH	10.05	10.15

Bleaching Solution

[0241] 

	Tank Solution (g)	Replenisher (g)
Ammonium 1,3-Diaminopropanetetraacetato Ferrate Monohydrate	130	195
Ammonium Bromide	70	105
Ammonium Nitrate	14	21
Hydroxyacetic Acid	50	75
Acetic Acid	40	60
Water to make	1.0 liter	1.0 liter
pH (adjusted with ammonia water)	4.4	4.4

Bleaching-Fixing Solution (Tank Solution)

[0242] A mixed (15:85 by volume) solution of the above bleaching solution (tank solution) and the above fixing solution (tank solution) with a pH of 7.0.

Fixing Solution

[0243] 

	Tank Solution (g)	Replenisher (g)
Ammonium Sulfite	19	57
Aqueous Solution of	280 ml	840 ml
Ammonium Thiosulfate (700 g/ℓ)
Imidazole	15	45
Ethylenediaminetetraacetic Acid	15	45
Water to make	1.0 liter	1.0 liter
pH (adjusted with ammonia water and acetic acid)	7.4	7.45

Rinsing Water

[0244] Tap water was passed through a mixed bed column packed with an H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm & Hass Co.) and an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the concentration of each of calcium ion and magnesium ion to 3 mg/ℓ or less. Subsequently, sodium dichlorinated isocyanurate (20 mg/ℓ) and sodium sulfate (150 mg/ℓ) were added thereto. The pH of the solution was in the range of 6.5 to 7.5.

Stabilizing Solution

[0245] Tank solution and replenisher being the same.

	Amount (g)
Sodium p-Toluenesulfinate	0.03
Polyoxyethyl p-Monononylphenyl Ether(an average degree of polymerization: 10)	0.2
Disodium Ethylenediaminetetraacetate	0.05
1,2,4-Triazole	1.3
1,4-Bis(1,2,4-triazole-1-ylmethyl)piperazine	0.75
Water to make	1.0 liter
pH	8.5

[0246] The results obtained are shown in Tables 2 to 4 below.

[0247] It is apparent from the results shown in Tables 2 to 4 that Sample Nos. 104 to 120 containing the restrainer precursor-releasing compounds of general formula (I) and the dyes of general formula (A) according to the present invention have high photographic sensitivity and are excellent in long-term preservability, dye image fastness and color reproducibility in comparison with comparative Sample Nos. 101 to 103 and 121.

[0248] Even when the restrainer precursor-releasing compounds of general formula (I) according to the present invention are compounds having the mother nuclei of naphthol type cyan couplers or open chain ketomethylene type yellow couplers, it can be seen from the results of Sample Nos. 104 to 120 of the present invention and comparative Sample Nos. 101 and 103 that yellow absorption density in the magenta dye image is low, color turbidity is low, and color reproducibility is superior. It can also be seen from a comparison between Sample Nos. 101 and 103 or sample Nos. 102 to 104 that when the yellow colloidal silver used in the yellow filter layer is replaced by the dye of general formula (A) according to the present invention, the photographic sensitivity of the green-sensitive emulsion layer can be greatly increased. Comparative Sample No. 121 shows performances which are nearly equal to those of the Sample Nos. 104 to 120 in terms of sensitivity, dye image fastness and color reproducibility, but comparative Sample No. 121 is inferior in long-term preservability and is insufficient in performance.

[0249] Further, it can be seen from the results of the Sample Nos. 101 to 103 and those of Sample No. 104 that when the restrainer precursor-releasing compounds of general formula (I) and the dyes of general formula (A) according to the present invention are used in combination, an effect of improving the above-described performances is high in comparison with the case where either the restrainer precursor-releasing compounds of general formula (I) or the dyes of general formula (A) is used alone. Furthermore, when Sample No. 104 (gelatin coating weight in the yellow filter layer being 0.65 g/m²) is compared with Sample Nos. 119 and 120 prepared in the same manner as in the preparation of Sample No. 104, except that the gelatin coating weights in the yellow filter layer are reduced to 0.50 g/m² and 0.40 g/m², respectively, it can be seen that good performance can be retained without having an adverse effect on the above-described performance, even when the gelatin coating weight in the yellow filer layer is reduced.

[0250] The amount of residual silver of Sample Nos. 101 to 120 processed as described above after exposure to light were examined by X-ray fluorometry. It was found that the amount of residual silver in Sample Nos. 104 to 120 containing the dyes of general formula (A) according to the present invention is smaller than that of residual silver in Sample Nos. 101 and 102, and is small even in comparison with Sample No. 103.

EXAMPLE 2

[0251] Sample Nos. 201 to 205 were prepared in the same manner as Sample No. 120 of Example 1, except that an equimolar amount of each of the cyan couplers of general formulas (II) and (III) shown in Table 5 below was used in place of each of the cyan couplers IIC-7, IIC-34 and IIIC-2 used in the third to fifth layers (red-sensitive emulsion layers) of Sample No. 120 of Example 1.

[0252] Similarly, Sample No. 206 was prepared in the same manner as Sample No. 120 of Example 1, except that an equimolar amount of each of the following comparative couplers (a) to (c) as shown in Table 5 below was used in place of each of the cyan couplers IIC-7, IIC-34 and IIIC-2 used in the third to fifth layers (red-sensitive emulsion layers) of Sample No. 120 of Example 1.

[0253] Comparative couplers (a) to (c) are shown below.

Coupler (a)

[0254] 

Coupler (b)

[0255] 

Coupler (c)

[0256] 


   The thus-prepared Sample Nos. 201 to 206 together with Sample No. 120 were subjected to the following color development. In the same manner as in Example 1, the performances of the cyan dye image were examined. After running processing was carried out, the performances were examined in the same manner as in Example 1.

Processing Stage
Stage	Processing Time	Processing Temperature	Replenishment Rate*	Tank Capacity
Color development	3 min 15 sec	38°C	22 ml	10 ℓ
Bleaching	3 min 00 sec	38°C	25 ml	20 ℓ
Rinse	30 sec	24°C	1200 ml	10 ℓ
Fixing	3 min 00 sec	38°C	25 ml	10 ℓ
Rinse (1)	30 sec	24°C	countercurrent piping system of from (2) to (1)	10 ℓ
Rinse (2)	30 sec	24°C	1200 ml	10 ℓ
Stabilization	30 sec	38°C	25 ml	10 ℓ
Drying	4 min 20 sec	55°C

* Replenishment rate being per 1 m long by 35 mm wide.

[0257] The processing solutions had the following compositions.

Color Developing Solution

[0258] 

	Tank Solution (g)	Replenisher (g)
Diethylenetriaminepentaacetic Acid	1.0	1.1
1-Hydroxyethylidene-1,1-diphosphonic Acid	3.0	3.2
Sodium Sulfite	4.0	4.4
Potassium Carbonate	30.0	37.0
Potassium Bromide	1.4	0.3
Potassium Iodide	1.5 mg	-
Hydroxylamine Sulfate	2.4	2.8
4-[N-Ethyl-N-β-hydroxyethylamino]-2-methylaniline Sulfate	4.5	6.2
Water to make	1.0 liter	1.0 liter
pH	10.05	10.15

Bleaching Solution

[0259] 

	Tank Solution (g)	Replenisher (g)
Sodium Ethylenediaminetetraacetato Ferrate Trihydrate	100.0	120.0
Disodium Ethylenediaminetetraacetate	10.0	11.0
3-Mercapto-1,2,4-triazole	0.08	0.09
Ammonium Bromide	140.0	160.0
Ammonium Nitrate	30.0	35.0
Ammonia Water (27%)	6.5 ml	4.0 ml
Water to make	1.0 liter	1.0 liter
pH	6.0	5.7

Fixing Solution

[0260] 

	Tank Solution (g)	Replenisher (g)
Disodium Ethylenediaminetetraacetate	0.5	0.7
Ammonium Sulfite	20.0	22.0
Aqueous Solution of Ammonium Thiosulfate (700 g/ℓ)	290.0 ml	320.0 ml
Water to make	1.0 liter	1.0 liter
pH	6.7	7.0

Stabilizing Solution

[0261] 

	Amount (g)
Tank solution and replenisher being the same.
Sodium p-Toluenesulfinate	0.03
Polyoxyethylene p-Monononylphenyl Ether (an average degree of polymerization: 10)	0.2
Disodium Ethylenediaminetetraacetate	0.05
1,2,4-Triazole	1.3
1,4-Bis(1,2,4-triazole-1-yl-methyl)piperazine	0.75
Water to make	1.0 liter
pH	8.5

[0262] The results obtained are shown in Table 5 below.

[0263] It is apparent from the results shown in Table 5 that Sample Nos. 120 and 201 to 205 containing the cyan couplers of general formula (II) or (III) are superior in photographic sensitivity, long-term preservability and dye image fastness to Sample No. 206 containing the couplers (a) to (c) other than the couplers of general formula (II) or (III), though Sample Nos. 120 and 201 to 205 are equal to or slightly inferior to Sample No. 206 in terms of color turbidity. Accordingly, it can be seen from the results shown in Table 5 that the cyan couplers of general formula (II) or (III) can be advantageously used.

EXAMPLE 3

[0264] Sample Nos. 101 to 120 prepared in Example 1 and Sample Nos. 201 to 206 prepared in Example 2 were processed in the same manner as in Example 1, except than an equimolar amount of 4-amino-3-methyl-N-ethyl-N-(4-hydroxypropyl)aniline sulfate was used in place of the color developing agent, 2-methyl-4-[N-ethyl-N-(β-hydroxyethylamino]aniline sulfate, used in the color developing solution in the color development of Example 1, and the color developing time was shortened from 3½ minutes to 2½ minutes. In the same manner as in Example 1, the magenta dye image of Sample Nos. 101 to 121 and the cyan dye image of Sample Nos. 201 to 206 were examined.

[0265] Further, MTF measurement patterns were exposed to white light, and MTF value providing a density of (the minimum density of magenta dye image obtained by processing + 1.5) was measured according to the method described in James, The Theory of the Photographic Process, 4th Ed, (Macmillan) to examine sharpness.

[0266] The results obtained are shown in Tables 6 and 7 below.

[0267] The results shown in Table 6 and 7 show that Sample Nos. 104 to 120 and 201 to 206 containing the compounds of general formula (I) and the dyes of general formula (A) according to the present invention are excellent in photographic sensitivity, long-term preservability, dye image fastness, color turbidity and sharpness in comparison with comparative Sample Nos. 101 to 103 and 121.

[0268] When the results obtained above are compared with those obtained in Example 1, the performances in terms of sensitivity, dye image fastness and color turbidity are made better by changing the color developing agent and shortening the color development time. Further, it can be confirmed that the samples processed in this Example are excellent in sharpness in comparison with the samples processed in Example 1.

[0269] The cyan couplers show a similar tendency to the results obtained in Example 2. It can be seen that the couplers of general formula (II) or (III) according to the present invention give favorable results in photographic sensitivity and dye image fastness when the results of Sample Nos. 201 to 205 are compared with those of Sample No. 206.

EXAMPLE 4

[0270] Film units equipped with a lens were prepared from Sample Nos. 101, 104, 108, 114 and 120 prepared in Example 1 and Sample No. 206 prepared in Example 2 according to the methods described in JP-B-2-32615 and JP-B-U-3-39784.

[0271] The photographs of various objects were taken under the same conditions by using these six film units equipped with a lens, and subjected to color development by using the automatic processor FP-56B AL (manufactured by Fuji Photo Film Co., Ltd.). Subsequently, printing was made on Fuji Color paper, super FA, Type II by using Fuji minilaboratory champion printer processor FA-140 manufactured by Fuji Photo Film Co., Ltd. (Cp-43FA was used for color development).

[0272] The patterns obtained by printing from the six samples were observed. It could be confirmed that the prints obtained from the five samples of Sample Nos. 104, 108, 114, 120 and 206 according to the present invention showed that the chroma of the colors of the objects was improved, the definitions of the fine portions of the objects were superior, and the image quality of the prints was improved in comparison with the print obtained from Sample No. 101.

[0273] Further, when the color negatives processed after photographing were stored at 60°C and 70% RH over a long period of time, it could also be confirmed that the fading of the magenta dye image was low, and dye image fastness was superior.

[0274] Other samples prepared in Examples 1 and 2 were tested in the same manner as described above, and it could be confirmed that similar results to those described above were obtained by the samples of the present invention.

EXAMPLE 5

[0275] The samples prepared in Examples 1 and 2 were processed in the same manner as in Example 1, except that the amount of the color developing agent, 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline sulfate, in the color developing solution used for the color development was 8.0 g (the amount thereof in the replenisher was 15.0 g), that of potassium bromide was 7.0 g (0 g in the replenisher), that of diethylenetriaminepentaacetic acid in the replenisher was 4.0 g, that the pH of the replenisher was 12.2, that the amount of the replenisher was reduced to 80 ml/m², and that the processing temperature was 40°C.

[0276] Sample Nos. 104 to 120 and 201 to 206 according to the present invention showed that the good results of the magenta dye image in terms of any of sensitivity, dye image fastness, color turbidity and long-term preservability could be obtained as in Example 1 in comparison with comparative Sample Nos. 101 to 103 to 121.

[0277] It will be understood from the above disclosure that the silver halide color photographic materials containing the restrainer precursor-releasing compounds of general formula (I) and the dyes of general formula (A) according to the present invention provide high photographic sensitivity and enable dye image fastness, color turbidity, sharpness, desilverizability and long-term preservability to be improved. Accordingly, a silver halide color photographic material having high sensitivity, high image fastness, high image quality and improved long-term preservability can be provided.

[0278] While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims

1. A silver halide color photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer and containing at least one restrainer precursor-releasing compound represented by the following general formula (I) and at least one oil-soluble dye represented by the following general formula (A):



        A-X   (I)



wherein A represents a group which releases X by a reaction with an oxidant of a developing agent and forms a compound which is soluble in processing solutions or is decolorized; and X represents a group of a restrainer precursor;

wherein X and Y each represents an electron attractive group, or X and Y are combined together to form a five-membered or six-membered ring; Ar represents a heterocyclic aromatic ring which is a substituted or unsubstituted indole, furan, thiophene, coumarin or pyridine group; L¹, L² and L³ each represents a methine group; and n represents 0, 1 or 2.

2. The silver halide color photographic material as in claim 1, wherein said silver halide color photographic material contains at least one coupler represented by the following general formula (II) or (III):

wherein R₁ represents -CONR₄R₅, -SO₂NR₄R₅, -NHCOR₄, -NHCOOR₆, -NHSO₂R₆, -NHCONR₄R₅ or -NHSO₂NR₄R₅; R₂ represents a group which can be attached to the naphthalene ring; K represents an integer of 0 to 3; R₃ represents a substituent group; X represents a hydrogen atom or a group which is eliminated by a coupling reaction with an oxidant of an aromatic primary amine developing agent; R₄ and R₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R₆ represents an alkyl group, an aryl group or a heterocyclic group; when k is 2 or greater, the two or more R₂ groups may be the same or different or may be combined together to form a ring; R₂ and R₃ or R₃ and X may be combined together to form a ring; or two or more members of the compounds may be bonded to each other through a bivalent or polyvalent group at the position of R₁, R₂, R₃ or X to form a dimer or a higher polymer;

wherein R¹ represents an alkyl group, an aryl group or a heterocyclic group; R² represents an aryl group; Z represents a hydrogen atom or a group which is eliminated by coupling.

3. The silver halide color photographic material as in claim 1, wherein the gelatin coating weight of the layer containing the oil-soluble dye of general formula (A) is 1.5 g/m² or less.

4. The silver halide color photographic material as in claim 2, wherein the gelatin coating weight of the layer containing the oil-soluble dye of general formula, (A) is 1.5 g/m² or less.

5. The silver halide color photographic material as in claim 2, wherein the coupler is one represented by formula (II).

6. The silver halide color photographic material as in claim 2, wherein the coupler is one represented by formula (III).

7. The silver halide color photographic material as in claim 1, wherein the dye according to formula (A) is present in a non-light-sensitive layer which is located adjacent to a blue-sensitive layer and between the blue-sensitive layer and the support.

8. The silver halide color photographic material as in claim 5, wherein R₁ is -CONR₄R₅ in which R₄ and R₅ may be the same or different and each represents an alkyl group of 1 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms or a heterocyclic group of 2 to 30 carbon atoms.

9. The silver halide color photographic material as in claim 5, wherein k=0.

10. The silver halide color photographic material as in claim 2, wherein the material comprises both a coupler represented by formula (II) and a coupler represented by formula (III).

11. The silver halide color photographic material as in claim 1, wherein the oil-soluble dye of general formula (A) is a dye represented by the following general formula (A-1):

wherein R²¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a ureido group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkylthio group, an arylthio group, an oxycarbonyl group, an acyl group, a carbamoyl group, a cyano group, an alkoxy group, an aryloxy group, an amino group or an amido group; Q represents -O- or -NR²²-; R²² represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R²³, R²⁴ and R²⁵ each represents a hydrogen atom, an alkyl group or an aryl group, or R²⁴ and R²⁵ may be combined together to form a six-membered ring; R²⁶ represents a hydrogen atom, an alkyl group, an aryl group or an amino group; and k is 0 or 1, provided that when Q is -NR²²-, R²⁴ and R²⁵ together form a six-membered fused ring.