A method for processing a silver halide color photograhic material

Abstract

 A method for continuously processing an imagewise exposed silver halide color photographic material with a :olor developer containing at least one aromatic primary amine color developing agent is disclosed, in which said color developer contains at least one compound selected from the group consisting of a compound represented by formula (I):

wherein R', R², and R³ each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; R⁴ represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrazino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted amino group; or R³ and R⁴ are taken together to form a heterocyclic group; X¹ represents a divalent group; and n represents 0 or 1, provided that when n is 0, R⁴ represents an alkyl group, an aryl group, or a heterocyclic group, and a compound represented by formula (II):

wherein R⁵ represents a substituted alkylene group; and R⁶, R⁷, R⁸, and R⁹, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,
and said color developer is replenished at a replenishment rate of from 20 to 120 mℓ per m² of the photographic material. The photographic material does not suffer from a variation of photographic characteristics when processed in continuous running even at a low replenishment rate of a color developer.

Description

FIELD OF THE INVENTION

[0001] This invention relates to a method for processing a silver halide color photographic material. More particularly, it relates to a method for processing a silver halide color photographic material at a markedly reduced replenishment rate of a color developer while preventing, even on continuous processing, a variation of photographic characteristics.

BACKGROUND OF THE INVENTION

[0002] In continuous processing of silver halide color photographic materials, reduction of the amount of a replenisher or replenishment rate greatly contributes toward saving of resources, control of environmental pollution, and reduction of cost. In particular, since a color developer is not only causative of environmental pollution due to its high BOD (biological oxygen demand) and COD (chemical oxygen demand) but also expensive, various studies have been conducted to establish a technique for reducing the amount of the replenisher.

[0003] Known techniques so far proposed in this connection include a method of using a photographic emulsion having a high silver chloride content to thereby considerably decrease the amount of an overflow of a color developer as disclosed in JP-A-61-70552 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), a method of using a specific coupler and processing the photographic material with a color developer having a high bromide content as disclosed in JP-A-53-146625 and JP-A-59-198454, and a method of using a silver iodobromide emulsion and a specific coupler as disclosed in JP-A-61-243453, JP-A-61-251851, JP-A-61-251852, and JP-A-61-261741.

[0004] However, any of these techniques is still unsatisfactory because a serious variation of photographic characteristics is induced or fog generates during continuous processing.

[0005] As long as a color developer is replenished in continuous processing at an ordinary rate of from about 180 to 1,000 m Um2, serious problems may not occur. However, if the replenishment rate is decreased to about 20 ml to 120 ml per m² as in the present invention, various disadvantages would become conspicuous such that the retension time of the color developer in a tank increases to accelerate deterioration of processing solution components, particularly a preservative (antioxidant) and a color developing agent (deteriorated due to oxidation); the processing solution components tend to be concentrated by evaporation; the pH of the processing solution is liable to decrease due to absorption of carbonic acid gas; and difficulty in precise control of replenishment results in variation of the composition of the processing solution in the tank.

[0006] That is, there has not yet been established a technique for processing which realizes great reduction of replenishment rate, while satisfying practical demands, without causing variation of photographic characteristics or undesired fog, even on continuous processing.

[0007] On the other hand, magenta couplers represented by formula (III):

wherein R10 represents a hydrogen atom or a substituent; X represents a hydrogen atom or a group releasable on coupling reaction with an oxidation product of an aromatic primary amine developing agent; Z_a, Z_b, and Z_c each represents a methine group, a substituted methine group, = N- or -NH-; one of the Z_a-Z_b bond and Z_b-Z_c bond is a double bond, with the other being a single bond; when the Z_b-Z_c bond is a carbon-carbon double bond, it may be a part of an aromatic ring; the formula (III) includes a dimer or a higher polymer formed at R₁₀ or X or at Z_a, Z_b or Z_c representing a substituted methine group, are known to produce an excellent hue as described in JP-A-59-162548, JP-A-60-43659, JP-A-59-171956, JP-A-60-172982, JP-A-60-33552, and U.S. Patent 3,061,432 and have been studied extensively.

[0008] It was proved, however, that the magenta couplers of formula (III) cause an increase of stains when color development is carried out at a low replenishment rate of a color developer. Although there were made several proposals to prevent such stains as disclosed in JP-A-49-11330, JP-A-50-57223, JP-A-56-85747, and JP-B-56-8346 (the term "JP-B" as used herein means an "unexamined published Japanese patent application"), sufficient effects have not yet been attained.

SUMMARY OF THE INVENTION

[0009] One object of this invention is to provide a method of processing at a considerably reduced rate of replenishment of a color developer.

[0010] Another object of this invention is to provide a method of processing which is less causative of a variation of photographic characteristics and of fog even when processing is carried out continuously.

[0011] It has now been found that the objects of this invention can be accomplished by a process for continuously processing an imagewise exposed silver halide color photographic material with a color developer containing at least one aromatic primary amine color developing agent, in which the color developer contains at least one compound selected from the group consisting of a compound represented by formula (I):

wherein R¹, R², and R³ each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, R⁴ represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrazino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocylic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted amino group; or R³ and R⁴ are taken together to form a heterocylic group; X' represents a divalent group; and n represents 0 or 1, provided that when n is 0, R4 represents an alkyl group, an aryl group, or a heterocylic group, and a compound represented by formula (II):

wherein R⁵ represents a substituted alkylene group; and R⁶, R⁷, R⁸, -and R⁹, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and the color developer is replenished at a replenishment rate of from 20 to 120 m per m² of the photographic material.

[0012] The method according to the present invention is preferably applied to processing of a silver halide color photographic material containing at least one of the above-described magenta couplers represented by formula (III).

[0013] In order to ensure the above-described effects of the invention, it is preferable to use a color developer which does not contain such a component (except for the color developing agent) that would exert great influences on photographic characteristics.

[0014] For instance, in case when a color developer is concentrated to have an increased content of bromine or iodine ion, which is usually present in a color developer as an antifoggant, the development rate of a silver halide emulsion is reduced, resulting in reduction of sensitivity or insufficient maximum density. Further, since the iodine ion, even in a small quantity, has an activity to intensify internal latent image, it sometimes causes serious fog. It is preferable accordingly that the color developer contains substantially no bromine or iodine ion.

[0015] Further, a sulfite ion, usually added as a preservative for various developing agents, reacts with an oxidation product of a color developing agent, thus becoming a competitor to couplers. The sulfite ion also serves as a solvent for a silver halide emulsion to give influences to the development rate or developability of maximum density and, as a result, causes a variation of photographic characteristics. Since the change of sulfite ion concentration thus results in significant variation of photographic characteristics, it is preferable in the present invention that the color developer contains substantially no sulfite ion.

[0016] It is furthermore preferred in the present invention that the color developer contains substantially no hydroxylamine not only because hydroxylamine becomes a competitor to couplers similarly to sulfite ion but also decomposition products of the hydroxylamine frequently influence silver developability.

DETAILED DESCRIPTION OF THE INVENTION

[0017] The compounds represented by formula (I), i.e., hydrazine analogues derived from hydrazines or hydrazides, are described in detail.

[0018] R¹, R², and R³ each represents a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having from 1 to 20 carbon atoms, e.g., methyl, ethyl, sulfopropyl, carboxybutyl, hydroxyethyl, cyclohexyl, benzyl, phenethyl), a substituted or unsubstituted aryl group (preferably having from 6 to 20 carbon atoms, e.g., phenyl, 2,5-dimethoxyphenyl, 4-hydroxyphenyl, 2-carboxypfienyl), or a substituted or unsubstituted heterocyclic group [preferably a 5- or 6-membered ring containing from 1 to 20 carbon atoms and at least one hetero atom, e.g., oxygen, nitrogen, and sulfur (e.g., pyridin-4-yl, N-acetylpiperidin-4-yl)].

[0019] R⁴ represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrazino group (e.g., hydrazino, methylhydrazino, phenylhydrazino),, a substituted or unsubstituted alkyl group (preferably containing from 1 to 20 carbon atoms, e.g., methyl, ethyl, sulfopropyl, carboxybutyl, hydroxyethyl, cyclohexyl, benzyl, t-butyl, n-octyl), a substituted or unsubstituted aryl group (preferably having from 6 to 20 carbon atoms, e.g., phenyl, 2,5-dimethoxyphenyl, 4-hydroxyphenyl, 2-carboxyphenyl, 4-sulfophenyl), a substituted or unsubstituted heterocyclic group [preferably a 5- or 6-membered ring containing from 1 to 20 carbon atoms and at least one hetero atom selected from oxygen, nitrogen, and sulfur (e.g., pyridin-4-yl, imidazolyl)], a substituted or unsubstituted alkoxy group (preferably having from 1 to 20 carbon atoms, e.g., methoxy, ethoxy, methoxyethoxy, benzyloxy, cyclohexyloxy, octyloxy), a substituted or unsubstituted aryloxy group (preferably having from 6 to 20 carbon atoms, e.g., phenoxy, p-methoxyphenoxy, p-carboxyphenoxy, p-sulfophenoxy), a substituted or unsubstituted carbamoyl group (preferably having from 1 to 20 carbon atoms, e.g., unsubstituted carbamoyl, N,N-diethylcarbamoyl, phenylcarbamoyl), or a substituted or unsubstituted amino group (preferably having up to 20 carbon atoms, e.g., amino, hydroxylamino, methylamino, hexylamino, methoxyethylamino, carboxyethylamino, sulfoethylamino, N-phenylamino, p-sul- fophenylamino).

[0020] Substituents for R¹, R², R³, and R4 preferably include a halogen atom (chlorine, bromine) and hydroxyl, carboxyl, sulfo, amino, alkoxy, amido, sulfonamido, carbamoyl, sulfamoyl, alkyl, aryl, aryloxy, alkythio, arylthio, nitro, cyano, sulfonyl, and sulfinyl groups, each of which may be further substituted.

[0021] X¹ preferably represents a divalent organic group, such as -CO-, -S0₂-, and

. n is 0 or 1. When n is 0, R⁴ is selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocylic group. R' and R², or R³ and R⁴ may be taken together to form a heterocylic group.

[0022] When n is 0, it is preferable that at least one of R¹, R², R³, and R⁴ is a substituted or unsubstituted alkyl group, more preferably R¹, R², R³, and R4 each represents a hydrogen atom or a substituted or unsubstituted alkyl group, provided that all of them do not simultaneously represent a hydrogen atom, and most preferably R', R², and R³ each represents a hydrogen atom, and R⁴ represents a substituted or unsubstituted alkyl group; R' and R³ each represents a hydrogen atom and R² and R⁴ each represents a substituted or unsubstituted alkyl group; or R' and R² each represents a hydrogen atom, and R³ and R⁴ each represents a substituted or unsubstituted alkyl group, or R³ and R⁴ are taken together to form a heterocyclic group.

[0023] When n is 1, it is preferable that X¹ represents -CO-, R⁴ represents a substituted or unsubstituted amino group, and R¹, R², and R³ each represents a hydrogen atom or a substituted or unsubstituted alkyl group. n is preferably 0.

[0024] The alkyl group as represented by R¹, R², R³, or R⁴ preferably contains from 1 to 10 carbon atoms, and more preferably from 1 to 7 carbon atoms. Preferred substituents for the alkyl group include a hydroxyl group, a carboxyl group, a sulfo group, and a phosphono group. When the alkyl group has two or more substituents, they may be the same or different.

[0025] Included in the compounds of formula (I) are dimers, trimers and polymers formed at R¹, R², R³, or R⁴.

[0026] Specific examples of the compounds of formula (I) are shown below for illustrative purposes only but not for limitation.

[0027] Additional examples of the compounds of formula (I) are given in Japanese Patent Application Nos. 170756/86 (pp 11-24), 171682/86 (pp 12-22), and 173468/86 (pp 9-19) (corresponding to JP A-63-146041, JP-A-63-146042 and JP-A-63-146043, respectively).

[0028] Many of the compounds of formula (I) are available as commercial products. They can also be synthesized by general processes by referring to, e.g., Organic Syntheses, Coll. Vol. 2, 208-213, Jour. Amer. Chem. Soc., Vol. 36, 1747 (1914), Yukagaku, Vol. 24, 31 (1975), Jour. Org. Chem., Vol. 25, 44 (1960), Yakugaku Zasshi, Vol. 91, 1127 (1971), Organic Syntheses. Coll. Vol. 1, 450, Shin Jikken Kagaku Koza, Vol. 14, III, 1621-1628, Maruzen, Beil., Vol. 2, 559, ibid, Vol. 3, 117, E.B. Mohr et al., Inorg. Syn., Vol. 4, 32 (1953), F.J. Wilson and E.C. Pickering, J. Chem. Soc., Vol. 123, 394 (1923), N.J. Leonard and J.H. Boyer, J. Org. Chem., Vol. 15, 42 (1950), Organic Syntheses, Coll., Vol. 5, 1055, P.A.S. Smith, Derivatives of Hydrazine and Other Hydronitrogens Having -N-N- Bonds, 120-124 & 130-131, The Benjamin/Cummings Publishing Co. (1983), and S.R. Sandier and Waif Karo, Organic Functional Group Preparations, Vol. 1, 2nd Ed., 457.

[0029] The compound of formula (I) is usually used in an amount of from 0.01 to 50 g, preferably from 0.1 to 30 g, more preferably 0.5 to 10 g, per liter of a color developer.

[0030] The above-recited content of the compound of formula (I) is in the working developing solution. The replenisher for the color developer may have the same content of the compound of formula (I), or the compound of formula (I) may be stocked as a separate part and mixed on use.

[0031] The compound represented by formula (II) is described below in detail.

[0032] R⁵ represents a straight chain or branched alkylene group having at least one of and at least one kind of substituents selected from a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a sulfo group, a phosphono group, a sulfonyl group, a ureido group, an acyl group, an alkylthio group, an arylthio arouo. a carbamovl arouo. a sulfamovl arouo. an acvlamino group. a sulfonamido arouo. a haloaen atom. a cyano group, and a nitro group (e.g., 2-hydroxytrimethylene, 1-methoxypentamethylene). R⁶, R⁷, R⁸, and R⁹, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

[0033] Substituents for the alkyl or aryl group for R⁶, R⁷, R⁸, and R⁹ preferably include a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, an amino group, a sulfo group, a phosphono group, a suifonyl group, a ureido group, an acyl group, an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamido group, a halogen atom, a cyano group, and a nitro group. These substituents may further have two or more of and two or more kinds of substituents per alkyl or aryl moiety. Of the functional groups contained in formula (II), a carboxyl group, a phosphono group, and a sulfo group may be in the form of a salt with an alkali metal (e.g., sodium, potassium) or a cationic atom or group (e.g., NH₄^⊕, Ca^2⊕, and an amino group may be in the form of a salt with various acids (e.g., hydrochloric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid).

[0034] In formula (II), R⁵ preferably represents a hydroxyl-substituted alkylene group, an alkoxy-substituted alkylene group, an amino-substituted alkylene group, a sulfo-substituted alkylene group, and a ureido- substituted alkylene group. R⁶, R⁷, R⁸, and R⁹ each preferably represent a hydrogen atom, an unsubstituted alkyl group (e.g., methyl, ethyl, isopropyl), a hydroxyl-substituted alkyl group, an alkoxy-substituted alkyl group, a carboxyl-substituted alkyl group, and a sulfo-substituted alkyl group.

[0035] The total number of the carbon atoms contained in R⁵, R⁶, R⁷ R⁸, and R⁹ is preferably 30 or less, and more preferably 20 or less.

[0036] The compound of formula (II) is preferably added to a color developer in an amount of from 0.1 to 20 g, more preferably from 0.5 to 10 g, per liter.

[0037] Specific examples of the compound of formula (II) are shown below for illustrative purposes only but not fcr limitation.

[0038] 

[0039] The compounds of formula (II) are easily available as commercial products, or can be easily synthesized according to the processes described in Organic Synthesis I, 102, ibid, II, 154, 328 and 558, and ibid, III, 370 and 800.

[0040] The compound represented by formula (III) is described below in detail.

[0041] The terminology "dimer or higher polymer" as used in the definition of formula (III) means a bis-compound or polymer coupler comprising two or more of the moiety represented by formula (III). The polymer coupler includes a homopolymer solely comprising a monomer unit represented by formula (III), preferably a monomer unit having a vinyl group (hereinafter referred to as a vinyl monomer) and a copolymer of such a monomer and a non-color-forming ethylenically unsaturated monomer which does not undergo coupling with an oxidation product of an aromatic primary amine developing agent.

[0042] The compound of formula (III) is a 5-membered ring-5-membered ring condensed nitrogen-containing heterocyclic ring coupler whose chromophoric nucleus exhibits aromaticity isoelectric to a naphthalene ring, and has a chemical structure generally referred to as "azapentalene".

[0043] Preferred of the couplers of formula (III) are 1H-imidazo[1,2-b]pyrazoles, 1H-pyrazolo[1,5-b]pyrazoles, 1H- pyrazolo[5,1-c][1,2,4]triazoles, 1H-pyrazolo[1,5-b]-[1,2,4]triazoles, 1H-pyrazolo[1,5-d]tetrazoles, and 1H-pyrazolo[1,5-a]benzimidazoles, represented by the following formulae (Illa), (IIIb), (Illc), (IIId), (Ille), and (Illf), respectively. Particularly preferred of them are those of formulae (Illa), (IIIc), and (IIId):

[0044] In the above formulae (Illa) to (Illf), R₁₂, R₁₃, and R₁₄. each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycar- bonyiamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group; X represents a hydrogen atom, a halogen atom, a carboxyl group, or a group which is bonded to the carbon atom at the coupling position via an oxygen atom, a nitrogen atom or a sulfur atom and is releasable on coupling; or R₁₂, R₁₃, Ri4. or X represents a divalent group at which the compound is dimerized to form a bis-compound.

[0045] When the moiety represented by formulae (Illa) to (Illf) is in a vinyl monomer, R₁₂, R₁₃, and R₁₄ represent a mere bond or a linking group, via which the moiety and a vinyl group are linked.

[0046] More specifically, R₁₂, R13, and Ri4 each represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine), an alkyl group (e.g., methyl, propyl, isopropyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-amylphenoxy)propyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonylethyl, cyclopentyl, benzyl), an aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), a heterocyclic group (e.g., 2-furyl, 2-thienyl, 2-pyrimidinyl, 2 benzothiazolyi), a cyano group, an alkoxy group (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-phenoxyethoxy, 2-methanesulfonylethoxy), an aryloxy group (e.g., phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, a heterocyclic oxy group (e.g., 2-benzimidazx- olyloxy), an acyloxy group (e.g., acetoxy, hexadecanoyloxy), a carbamoyloxy group (e.g., N-phenylcar- bamoyloxy, N-ethycarbamoyloxy), a silyloxy group (e.g., trimethylsilyloxy), a sulfonyloxy group (e.g., dodecylsulfonyloxy), an acylamino group (e.g., acetamido, benzamido, tetradecanamido, a-(2,4-di-t-amylphenyl)butylamido, y-(3-t-butyl-4-hydroxyphenoxy)-butylamido, a-[4-(4-hydroxyphenylsulfonyl)phenoxy]-decanamido), an anilino group (e.g., phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5-[«-(3-t-butyl-4-hydroxyphenoxy)-dodecanamido]-anilino), a ureido group (e.g., phenylureido, N-butyl-N' -methylureido, methylureido, N,N-dibutylureido), an imido group (e.g., N-succinimido, 3-benzylhydantoinyl, 4-(2-ethylhexanoylamino)-phthalimido), a sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), a carbamoylamino group (e.g., carbamoylamino, N,N-dimethylcarbamoylamino), an alkylthio group (e.g., methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-(4-t-butylphenoxy)-propylthio), an arylthio group (e.g., phenylthio, 2-butoxy-5-t-octyl-phenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), a heterocyclic thio group (e.g., 2-benzothiazolylthio), an alkoxycarbonylamino group (e.g., methoxycarbonylamino, tetradecyloxycarbonylamino) an aryloxycarbonylamino group (e.g., phenoxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino), a sulfonamido group (e.g., methanesulfonamido, hexadecanesulfonamido, benzenesulfonamido, p-toluenesulfonamido, oc- tadecanesulfonamido, 2-methyloxy-5-t-butylbenzenesulfonamido), a carbamoyl group (e.g., N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl, N-[3-(2,4-di-t-amylphenoxy)propyl]carbamoyl), an acyl group (e.g., acetyl, (2,4-di-t-amylphenoxy)acetyl, benzoyl), a sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), a sulfonyl group (e.g., methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), a sulfinyl group (e.g., octanesulfinyl, dodecylsulfinyl, phenylsulfinyl), an alkoxycarbonyl group (e.g . , methoxycarbonyl, butyloxycarbonyl , dodecyloxycarbonyl, octadecyloxycar- bonyl), or an aryloxycarbonyl group (e.g., phenyloxycarbonyl, 3-pentadecylphenyloxycarbonyl).

[0047] X represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine, iodine), a carboxyl group, or a group containing an oxygen atom at which it is bonded (e.g., acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxy, 4- methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, a-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy), a group containing a nitrogen atom at which it is bonded (e.g., benzenesulfonamido, N-ethyltoluenesulfonamido, heptafluorobutaneamido, 2,3,4,5,6-pentafluorobenzamido, octanesulfonamido, p-cyanophenylureido, N,N-diethylsulfamoylamino, 1-piperidyl, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl, 1-benzylethoxy-3-hydantoinyl, 2N-1,1-dioxo-3(2H)-oxo-1,2-benzoisothiazolyl, 2-oxo-1.2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl, 3,5- diethyl-1,2,4-triazol-1-yl, 5- or 6-bromobenzotriazol-1-yl, 5-methyl-1,2,3,4-triazol-1-yl, benzimidazolyl, 3-benzyl-1-hydrantoinyl, 1-benzyl-5-hexadecyloxy-3-hydrantoinyl, 5-methyl-1-tetrazolyl, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), or a group bonded at the ionic atom thereof (e.g., phenylthio, '2-carboxyphenylthio, 2-butoxy-5-t-octylphenylthio, 4-methanesul- fonamidophenylthio, 2,5-dibutoxyphenylthio, 4-methanesulfonylphenylthio, 4-octanesulfonamidophenylthio, 2-butoxyphenylthio, 4-dodecyloxyphenylthio, 2-(2-hexanesulfonylethyl)-5-t-octylphenylthio, benzylthio, 2-cyanoethylthio, 1-ethoxycarbonyltridecylthio, 5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolylthio, 2-dodecyl- thio, 2-dodecylthio-5-thiophenylthio, 2-phenyl-3-dodecyl-1,2,4-triazolyl-5-thio).

[0048] The divalent group as represented by R₁₂,, Ri ₃, R₁₄, or X, at which a bis-compound is formed, includes a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10-decylene, -CH₂CH₂-0-CH₂CH₂-), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene,

and -NHCO-Ris-CONH- (wherein Ris represents a substituted or unsubstituted alkylene or phenylene group).

[0049] In the cases where the moiety represented by formulae (Illa) to (Illf) is contained in a vinyl monomer, the linking group as represented by R₁₂, R₁₃, or R₁₄ includes a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10-decylene, -CH₂CH₂OCH₂CH₂-), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, ),

-NHCO-, -CONH-, -0-, -OCO-, and an aralkylene group (e.g.,

and a combination of these linking groups.

[0050] The vinyl group in the vinyl monomer may have a substituent other than the moiety represented by formulae Illa) to (Illf). Preferred of such a substituent are a hydrogen atom, a chlorine atom, and a lower alkyl group having from 1 to 4 carbon atoms.

[0051] The non-color-forming ethylenically unsaturated monomer which does not undergo coupling with an oxidation product of an aromatic primary amine developing agent includes acrylic acid, a-chloroacrylic acid, a-alacrylic acid (e.g., methacrylic acid), and esters or amides of these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetonacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, β-hydroxymethacrylate), methylenebisacrylamide, vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g., styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone, sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g., vinyl ethyl ether), maleic acid, maleic anhydride, maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- or 4-vinylpyridine. These non-color-forming ethylenically unsaturated monomers may be used either individually or in combination of two or more thereof.

[0052] For specific examples of these couplers and processes for synthesizing them, the following references can be referred to: JP-A-59-162548 for the compounds of formula ilia); JP-A-60-43659 for the compounds of formula (Illb); JP-B-47-27411 for the compounds of formula (Illc); JP-A-59-171956 and JP-A-60-172982 for the compounds of formula (IIId); JP-A-60-33552 for the compounds of formula (IIIe); and U.S. Patent 3,061,432 for the compounds of formula (Illf).

[0053] To any of the compounds of formulae (IIIa) to (Illf) is applicable the ballast group having high color forming properties disclosed in JP-A-58-42045, JP-A-59-214854, JP-A-59-177553, JP-A-59-177544, and JP-A-59-177557.

[0054] Specific examples of the pyrazoloazole couplers which can be used in this invention are shown below for illustrative purposes only but not for limitation.

[0055] 

[0056] The coupler of formula (III) is used in an amount of from 2 x 10-³ to 5 x 10-' mol, preferably from 1 x 10-² to 5 x 10-' mol, per mol of silver in a silver halide emulsion layer.

[0057] For the purpose of satisfying various photographic characteristics required for photographic materials, two or more different kinds of the coupler of formula (III) may be incorporated into the same layer, or the coupler of the same kind may be incorporated into two or more layers.

[0058] A color developer which can be used in the present invention contains a known aromatic primary amine color developing agent, preferably a p-phenylenediamine derivative. Typical examples of the p-phenylenediamine developing agent are shown below.

D-1: N,N-Diethyl-p-phenylenediamine

D-2: 2-Amino-5-diethylaminotoluene

D-3: 2-Amino-5-(N-ethyl-N-laurylamino)toluene

D-4: 4-[N-Ethyl-N-(β-hydroxyethyl)amino]aniline

D-5: 2-Methyl-4-(N-ethyl-N-(β-hydroxyethyl)amino]aniline

D-6: 4-Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]aniline

D-7: N-(2-Amino-5-diethylaminophenylethyl)methanesulfonamide

D-8: N,N-Dimethyl-p-phenylenediamine

D-9: 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline

D-10: 4-Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline

D-11: 4-Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline

[0059] The p-phenylenediamine derivative recited above may be in the form of a salt with sulfuric acid, hydrochloric acid, sulfurous acid, p-toluenesulfonic acid, etc.

[0060] The aromatic primary amine developing agent is used in a concentration of from about 0.1 g to about 20 g, preferably from about 0.5 g to about 10 g, per liter of the color developer.

[0061] If desired, the color developer may contain a sulfite type preservative, such as sulfites (e.g., sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite) and a carbonylsulfite adduct. However, it is preferable that the color developer contains substantially no sulfite ion for reasons stated above. The term "substantially no sulfite ion" as used herein means that the sulfite ion concentration in the color developer is no more than 5 x 10-³ mol, preferably of from zero up to 2 x 10-³ mol, per liter.

[0062] The color developer may contain other various preservatives in addition to the compound of formula (I), but, it is preferable that the color developer contains substantially no hydroxylamine preservative for reasons stated above. The term "substantially no hydroxylamine" as used herein means that the hydroxylamine concentration in the color developer is no more than 0.01 mol, preferably of from zero up to 0.005 mol, per liter.

[0063] If desired, the color developer may further contain various additives. For example, it is preferable to add hydroxamic acids disclosed in JP-A-63-43138, phenols disclosed in JP-A-63-44657, and JP-A-63-58443,a-hydroxyketones or a-aminoketones disclosed in JP-A-63-44656, and various sugars disclosed in JP-A-63-36244. In combination with these compounds, the color developer may also contain monoamines disclosed in JP-A-63-4235, JP-A-63-24254, JP-A-63-21647, JP-A-63-146040, JP-A-63-27841, and JP-A-63-25654, polyamines disclosed in Japanese Patent Application Nos. 164515/86, and 165621₁86, JP A-63-30845, JP-A-63-44655, and JP-A-63-26655, nitroxyl radicals described in JP-A-63-53551, alcohols described in JP-A-63-43140, and JP-A-63-53549, oximes described in JP-A-63-56654, and tertiary amines described in Japanese Patent Application No. 265149/86.

[0064] Further included in preservatives which may be added to the color developer if desired are various metals as described in JP-A-57-44148 and JP-A-57-53749, salicylic acid derivatives as described in JP-A-59-180588, alkanolamines as described in JP-A-54-3532, polyethyleneimines as disclosed in JP-A-56-94349, and aromatic polyhydroxy compounds as described in U.S. Patent 3,746,544. In particular, addition of the aromatic polyhydroxy compounds, trimethanolamine or the compounds disclosed in Japanese Patent Application No. 265149/86 is advantageous.

[0065] The color developer according to the present invention preferably has a pH of from 9 to 12, more preferably from 9 to 11.0. The color developer can contain conventionally known developer components.

[0066] It is recommended to use a buffering agent for maintaining the above-recited pH range. The buffering agent to be used includes carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycine salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrates, 2 amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, tris- hydroxyaminomethane salts, and lysine salts. Particularly preferred among them are carbonates, phosphates, tetraborates, and hydroxybenzoates because they exhibit good dissolution property and superior buffering activity in a high pH region of 9.0 or more, give no adverse influences on photographic performance properties, such as fog, when added to a color developer, and are cheap.

[0067] Specific but non-limiting examples of these preferred buffering agents are sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium tertiary phosphate, potassium tertiary phosphate, sodium secondary phosphate, potassium secondary phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

[0068] The amount of the buffering agent to be added to the color developer is preferably not less than 0.1 molit, more preferably from 0.1 to 0.4 mol/t.

[0069] The color developer can also contain various chelating agents as a suspension agent for calcium or magnesium or for improving stability of the color developer. The chelating agent to be used preferably include organic acid compounds, such as aminopolycarboxylic acids disclosed in JP-B-48-30496 and JP-B-44-30232; organic phosphonic acids disclosed in JP-A-56-97347, JP-B-56-39359, and West German Patent 2.227,639; phosphonocarboxylic acids disclosed in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-126241, and JP-A-55-659506; and the compounds disclosed in JP-A-58-195845, JP-A-58-203440 and JP-B-53-40900.

[0070] Specific but non-limiting examples of these chelating agents are nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydrox- yphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and N,N -(bis2-hydroxybenzyi)ethyfenediamine-N.N -diacetic acid.

[0071] These chelating agents may be used in combination of two or more thereof, if desired. The amount of the chelating agent to be added is determined so as to be enough to sequester or deactivate metallic ions in the color developer and usually ranges from about 0.1 to about 10 g per liter.

[0072] If desired, the color developer may contain an arbitrary development accelerator. However, from the standpoint of prevention of environmental pollution, convenience of the preparation of the developer, and prevention of color stain, it is desirable that the color developer contains substantially no benzyl alcohol as development accelerator. The term "substantially no benzyl alcohol" as used herein means that the content of benzyl alcohol in the color developer is no more that 2 ml per liter, and preferably nil.

[0073] The above-described compounds according to the present invention manifest their marked effects particulary when used in the processing with a color developer containing substantially no benzyl alcohol.

[0074] Other development accelerators which may be used in the present invention include thioether compounds as described in JP-B-37-16088, JP-B-37-5987, JP-B-38-7826, JP-B-44-12380, JP-B-45-9019 and U.S. Patent 3,813,247; p-phenylenediamine compounds as described in JP-A-52-49829 and JP-A-50-15554; quaternary ammonium salts as described in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429; amine compounds as described in U.S. Patents 2,494,903, 3,128,182, 4,230,796, and 3,253,919, JP-B-41-11431, and U.S. Patents 2,482,546, 2,596,926, and 3,582,346; polyalkylene oxides as described in JP-B-37-16088, JP-B-42-25201, U.S. Patent 3,128,183, JP-B-41-11431, JP-B-42-23883, and U.S. Patent 3,532,501; and, in addition, 1-phenyl-3-pyrazolidones, imidazoles, etc.

[0075] If desired, an arbitrary antifoggant can be added to the color developer. The antifoggant to be used includes alkali metal halides (e.g., potassium bromide, potassium iodide) and organic antifoggants, such as nitrogen-containing heterocyclic compounds (e.g., benzotriazole, 6-nitrobenzimidazole, 5-nitrosoindazole , 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethyl- benzimidazole, indazole, hydroxyazaindolizine, adenine).

[0076] However, the amount of these antifoggants, if added, is preferably minimized for reasons stated above. It is particularly desirable that the color developer contains substantially no bromine or iodine ion that gives great influences on photographic characteristics. The term "substantially no bromine or iodine ion" as used herein means that the concentration of a bromine ion or iodine ion is up to 2.5 x 10-³ mol/t, preferably up to 1 x 10-³ mol/t, or up to 3 x 10^-4 mol/t, preferably up to 1 x 10-^4. mol/t, respectively.

[0077] The color developer to be used in the present invention preferably contains a brightening agent, preferably 4,4'-diamino-2,2'-disulfostilbene compounds, in an amount of up to 5 g/t, preferably from 0.1 to 4 g/t.

[0078] If desired, various surface active agents, such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids, may also be added to the color developer.

[0079] The color development processing according to the present invention is carried out at a processing solution temperature of from 20 to 50 C, preferably from 30 to 40 C, for a period of from 20 seconds to 5 minutes, preferably from 0.5 to 2 minutes.

[0080] The color developer is replenished at a rate of from 20 to 120 mt, preferably 30 to 100 mℓ, per m² of the photographic material. When the quantity of the replenisher is 50 mℓ/m² or less, the overflow of the color developer can be substantially eliminated since the color developer is carried away together with the processed photographic materials or evaporated during processing.

[0081] Desilvering generally comprises a combination of bleach and fixation, a combination of fixation and blix, a combination of bleach and blix, or blix, and any of these systems may be used in this invention. In particular, the effects of the present invention can be taken full advantage of by reducing the time of desilvering, e.g., to 2 minutes or less, preferably between 15 and 60 seconds.

[0082] In a bleaching bath or blix bath, any conventional bleaching agent may be used. Particularly recommended bleaching agents are organic complex salts of iron (III), for example, complex salts with aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid), aminopolyphosphonic acids, phosphonocarboxylic acids, or organic phosphonic acids; organic acids (e.g., citric acid, tartaric acid, malic acid); persulfates; and hydrogen peroxide.

[0083] Among them, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapidness of processing and prevention of environmental pollution. Specific examples of the aminopolycarboxylic acids, aminopolyphosphonic acids or organic phosphonic acids or salts thereof which are useful for preparing the organic complex salts of iron (III) are ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid, as well as their salts with sodium, potassium, lithium or ammonium.

[0084] Preferred of these iron (III) complex salts are iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid because of their high bleaching capacity.

[0085] These ferric ion complex salts may be used in the form of a complex salt from the first; or the ferric ion complex may be formed in situ from a ferric salt (e.g., ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate, ferric phosphate) and a chelating agent (e.g., aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid). In the latter case, the chelating agent may be used in excess. Of the iron complexes, aminopolycarboxylic acid-iron complexes are preferred, the amount thereof ranging from 0.01 to 1.0 mol/t, preferably from 0.05 to 0.50 mol/t.

[0086] The bleach bath, blix bath and/or their prebathes may contain various bleaching accelerators, such as compounds having a mercapto group or a disulfide bond as described in U.S. Patent 3,893,858, German Patent 1,290,812, JP-A-53-95630, and Research Disclosures, No. 17129 (Jul., 1978); thiourea compounds as described in JP B-45-8506, JP-A-52-20832, JP-A-53-32735, and U.S. Patent 3,706,561; and halides of an iodine or bromine ion. The above-enumerated compounds are advantageous because of their excellent bleaching capacity.

[0087] p The bleach or blix bath may further contain a rehalogenating agent, such as bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride) and iodides (e.g., ammonium iodide). If desired, they may furthermore contain one or more of organic or inorganic acids or alkali metal or ammonium salt thereof which have buffering activity (e.g., boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid) or a corrosion inhibitor (e.g., ammonium nitrate, guanidine,.

[0088] The blix bath or fixer contains one or more of conventional fixing agents, i.e., water-soluble silver halide solvents, such as thiosulfates (e.g., sodium thiosulfate, ammonium thiosulfate); thiocyanates (e.g., sodium thiocyanate, ammonium thiocyanate); thioether compounds (e.g., ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol); and thiourea. A special blix bath containing the fixing agent in combination with a large quantity of a halide (e.g., potassium iodide) as disclosed in JP-A-55-155354 can also be employed. In the present invention, use of the thiosulfates, particularly ammonium thiosulfate, is preferred.

[0089] A recommended amount of the fixing agent in the fixer is from 0.3 to 2 mol/t, preferably from 0.5 to 1.0 mol! t. The blix bath or fixer preferably has a pH of from 3 to 10, more preferably from 5 to 9.

[0090] The blix bath may further contain other various additives, such as brightening agents, defoaming agents, surface active agents, and organic solvents (e.g., polyvinylpyrrolidone, methanol).

[0091] The blix bath or fixer contains, as a preservative, a sulfite ion-releasing compound such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite), and metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite). The sulfite preservative is added in an amount of from about 0.02 to 0.50 mol/t, preferably from 0.04 to 0.40 mol/t, on a sulfite ion conversion. It is usual to use the sulfite as a preservative, but other preservatives, e.g., ascorbic acid, a carbonyl-bisulfurous acid adduct, and a carbonyl compound, may also be added.

[0092] If desired, the blix bath or fixer may further contain other additives, such as a buffering agent, a brightening agent, a chelating agent, a defoaming agent, and an antifungal agent.

[0093] In the processing of the present invention, the desilvering by fixation or blix is generally followed by washing and/or stabilization.

[0094] The quantity of water for washing is selected from a broad range depending on the characteristics of the photographic material (for example, the kind of components used, e.g., couplers),, the end use of the photographic material, the temperature of water, the number of washing tanks (the number of stages), the washing system (a counter current system or a direct current system), and other various factors. For example, the relationship between the number of washing tanks and the quantity of water in a multi-stage counter current system can be decided according to the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pp. 248-253 (May, 1955). The number of stages in a multi-stage counter current system is usually 2 to 6, and preferably 2 to 4.

[0095] According to the multi-stage counter current system, since the requisite quantity of water can be greatly decreased, for example, to 0.5 ti_M² to 1 Um2 or even less, the effects of the present invention are remarkably produced. However, this system tends to allow bacteria to grow in the tank due to the increased retension time of water, resulting in deposition of the scum onto the photographic material. In order to solve this problem, the method of reducing calcium and magnesium in water as disclosed in JP-A-62-288838 can be effectively applied to the present invention. It is also effective to use isothiazolone compounds or thiabenzazoles as described in JP-A-57-8542; chlorine type bactericides (e.g., chlorinated sodium isocyanurate) as described in JP-A-61- 120145; benzotriazoles as described in JP-A-61-267761 (corresponding to European Patent 204197A); a copper ion; and bacteriocides described in Hiroshi Horiguchi, Bokin Bobaizai no Kagaku, Eisei Gijutsukai (ed.), Biseibutsu no Genkin, Sakkin, Bobai Gijutsu, and Nippon Bokin Bobai Gakkai (ed.), Bokin Bobaizai Jiten.

[0096] The washing water can further contain a surface active agent as a wetting agent or a chelating agent (e.g., EDTA) as a water softener.

[0097] The above-described washing step may be followed by or substituted by treatment with a stabilizing bath. The stabilizing bath to be used contains compounds having functions to stabilize the photographic image, for example, aldehyde compounds (e.g., formalin), buffering agents for adjusting the film to a pH suitable for dye stabilization, or ammonium compounds. The above-enumerated various bactericides or antifungal agents can also be used for preventing growth of bacteria in the bath or imparting antifungal properties to the processed photographic material.

[0098] The stabilizing bath may further contain a surface active agent, a brightening agent, and a hardening agent.

[0099] In the case where the photographic material is subjected to stabilization directly from the desilvering processing, any of the known techniques described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be applied.

[0100] It is also preferable to use a chelating agent, e.g., 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

[0101] In the present invention, so-called rinsing solution may be used as washing water or stabilizing bath after desilvering.

[0102] During the washing or stabilization step, the pH of the processing solution is kept between 4 and 10, preferably between 5 and 8. The temperature, though varying depending on the end use and characteristics of the photographic material and the like, usually ranges from 15 to 45 C, preferably from 20 to 40 C. The processing time is arbitrary, but the effects of the present invention become significant with the time being shorter. A preferred time is from 0.5 to 4 minutes, more preferably from 0.5 to 2 minutes. The smaller the quantity of a replenisher, the better the results obtained in terms of running cost, reduction of a waste liquid, ease on handling, and manifestation of the effects of the present invention. More specifically, a recommended quantity of the replenisher is set at 0.5 to 50 times, preferably 3 to 40 times, the amount per unit area which has been carried over from the prebath. Alternatively, a recommended quantity of the replenisher is 1 t or less, preferably 500 m or less, per m² of the photographic material. The replenishment may be effected either continuously or intermittantiy.

[0103] The processing solution which has been used for washing and/or stabilization may be recycled to the prebath. In one embodiment, the overflow of washing water, which is reduced by a multi-stage counter current system, is made to flow into the blix bath (i.e., the prebath), while replenishing the blix bath with a concentrated solution, to thereby reduce the amount of waste liquid.

[0104] The method of the present invention can be applied to any type of photographic processing. For example, the method is applicable to processing of color papers, color reversal papers, color direct positive light-sensitive materials, color positive films, color negative films, color reversal films, and so on. In particular, application to color papers and color reversal papers is suitable.

[0105] The silver halide color photographic materials which are subject to the processing method of the present invention will be described below.

[0106] It is essential that the photographic material contains various color couplers. The terminology "color couplers" as used herein means compounds capable of coupling with an oxidation product of an aromatic primary amine developing agent to form a color. Useful color couplers typically include naphthol or phenol compounds as cyan couplers; pyrazolone or pyrazoloazole compounds as magenta couplers; and open- chain or heterocyclic ketomethylene compounds as yellow couplers. Specific examples of these cyan, magenta, and yellow couplers are described in patents cited in Research Disclosure (RD), 17643, VII-D (Dec., 1978) and ibid, 18717 (Nov., 1979).

[0107] It is preferable that the color couplers to be incorporated into the photographic material have a ballast group or are polymerized and are thereby non-diffusing. Two-equivalent color couplers in which the coupling site is substituted with a releasable group are preferred to four-equivalent color couplers in which the coupling site is substituted with a hydrogen atom because the requisite silver coverage can be reduced, thereby producing greater effects of the present invention accordingly.

[0108] Couplers which produce a dye showing moderate diffusion, colorless compound forming couplers, so-called DIR couplers capable of releasing a developing inhibitor on coupling reaction, or couplers capable of releasing a development accelerator on coupling reaction may also be used.

[0109] The yellow couplers which can be used in the present invention typically include oil-protected type acylacetamide couplers. Specific examples thereof are described in U.S. Patents 2,407,210, 2,875,057, and 3,265,506. As stated above, 2-equivalent yellow couplers are preferred. The 2-equivalent yellow couplers typically include those having oxygen atom linked releasing groups as described in U.S. Patents 3,408,194, 3,447,928, 3,933,501, and 4,022,620 and those having nitrogen atom linked releasing groups as described in JP-B-58-10739, U.S. Patents 4,401,752 and 4,326,024, RD 18053 (Apr., 1979), British Patent 1,425,020, West German Patent Application (OLS) Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812. a-Pyvaloylacetanilide couplers are excellent in dye fastness, particularly to light. a-Benzoylacetanilide couplers are excellent in color density.

[0110] The magenta couplers which can be used in this invention include oil-protected type indazolone or cyanoacetyl couplers, and preferably pyrazoloazole couplers, such as 5-pyrazolone couplers and pyrazolotriazole couplers. Of the 5-pyrazolone couplers, those in which the 3-position is substituted with an arylamino group or an acylamino group are preferred in view of hue and density of the color developed. Typical examples of such 5-pyrazolone couplers are described in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896, and 3,936,015. Preferred releasable groups for the 2-equivalent 5-pyrazolone couplers include nitrogen atom linked releasing groups as disclosed in U.S. Patent 4,310,619 and arylthio groups as disclosed in U.S. Patent 4,351,897. 5-Pyrazolone couplers having the ballast group disclosed in European Patent 73,636 provide high densities.

[0111] Pyrazoloazole couplers which are particularly preferred in the present invention include pyrazoloben- zimidazoles as described in U.S. Patent 3,369,879, and more preferably pyrazoio[5,1-d][1,2,4]triazoies as described in U.S. Patent 3,725,067; pyrazolotetrazoles as described in RD 24220 (Jun., 1984); and pyrazolopyrazoles as described in RD 24230 (Jun., 1984). From the viewpoint of freedom from undesired side absorption of yellow and light-fastness of the developed dye, the imidazolo[1,2-d]pyrazoles disclosed in European Patent 119,741 are preferred. The pyrazolo[1,5-b][1,2,4]triazoles disclosed in European Patent 119,860 are particularly preferred.

[0112] The cyan couplers which can be used in the present invention include oil-protected type naphthol and phenol couplers. Typical and preferred examples thereof are naphthol couplers as disclosed in U.S. Patent 2.474,293, and 2-equivalent naphthol couplers having oxygen atom linked releasing groups as disclosed in U.S. Patents 4,052,212, 4,146,396, 4,228,233, and 4,296,200. Specific examples of the phenol couplers are given in U.S. Patents 2.369,929, 2,801,171, 2,772,162, and 2,895,826. Cyan couplers providing a dye resistant to moisture and heat are preferably used in this invention. Typical examples of such cyan couplers include phenol cyan couplers having an alkyl group containing 2 or more carbon atoms at the m-position of the phenol nucleus as disclosed in U.S. Patent 3,772,002, 2,5-diacylamino-substituted phenol couplers as disclosed in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, and Japanese Patent Application No. 42671_/83, and phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position as disclosed in U.S. Patents 3,446,622, 4,333,999, 4,451,559, and 4,427,767.

[0113] The 2-equivalent cyan, magenta, or yellow couplers which are preferred for use in the present invention particularly from the standpoint of minimizing changes of photographic characteristics, such as gradation, can be represented by the following formulae (IV) or (V); (VI); or (VII); respectively.

[0114] In formulae (IV) and (V) representing cyan couplers, R₂₁, R₂₄, and R₂₅ each represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aromatic amino group, or a substituted or unsubstituted heterocyclic amino group; R₂₂ represents a substituted or unsubstituted aliphatic group; R₂₃ and R₂₆ each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aliphatic oxy group, or a substituted or unsubstituted acylamino group; or R₂₂ and R₂₃, or R₂s and R₂₆ are taken together to form a 5- to 7-membered ring; and Y, and Y₂ each represents a halogen atom, or a group which is released upon coupling reaction with an oxidation product of a developing agent; or R₂₁, R₂₂, R₂₃, Yi, R₂₄, R₂₅, R₂₆, or Y₂ represents a mere bond or a divalent linking group to form a dimer or higher polymer.

[0115] In formula (VI) representing magenta couplers, R₂₇ represents a group capable of substituting a benzene ring; R₂₈ represents a halogen atom, an alkoxy group, or an alkyl group; R₂₉ represents a substituted or unsubstituted phenyl group; and Y₃ has the same meaning as Y₁ or Y₂ in formulae (IV) or (V); and n is 1 or 2; or R₂₇, R₂₈, R₂₉, or Y₃ represents a mere bond or a divalent linking group to form a dimer or higher polymer.

[0116] In formula (VII) representing yellow couplers, Q represents a substituted or unsubstituted N-phenylcarbamoyl group; and Y_s has the same meaning as Y₁ or Y₂ in formulae (IV) or (V); or Q or Y_s represents a mere bond or a divalent linking group to form a dimer or a higher polymer.

[0117] The term "aliphatic group" as used herein means a straight chain or branched or cyclic alkyl, alkenyl or alkynyl group.

[0118] In formulae (IV) to (VII), the releasable group as represented by Yi, Y₂, Y₃, or Ys includes a group connecting the coupling active carbon atom and an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic, aromatic or heterocyclic sulfonyl group, or an aliphatic, aromatic or heterocyclic carbonyl group via an oxygen atom, a nitrogen atom, a sulfur atom, or a carbon atom; a halogen atom; an aromatic azo group; etc. The aliphatic, aromatic or heterocyclic groups contained in these releasable groups may be substituted with one or more substituents, which may be the same or different, selected from those acceptable for R₂₁ (hereinafter described). The substituent(s) may further be substituted with the substituent acceptable for R₂₁.

[0119] Specific examples of these coupling releasable groups are a halogen atom (e.g., fluorine, chlorine, bromine), an alkoxy group (e.g., ethoxy dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), an aryloxy group (e.g., 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), an acyloxy group (e.g., acetoxy, tetradecanoyloxy, benzoyloxy), an aliphatic or aromatic sulfonyloxy group (e.g., methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (e.g., dichloroacetylamino, hep- tafluorobutyrylamino), an aliphatic or aromatic sulfonamido group (e.g., methanesulfonamino, p-toluenesul- fonylamino), an alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycar- bonyloxy group (e.g., phenoxycarbonyloxy), an aliphatic, aromatic or heterocyclic thio group (e.g., ethylthio, phenylthio, tetrazolylthio), a carbamoylamino group (e.g., N-methylcarbamoylamino, N-phenylcar- bamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (e.g., imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), an imido group (e.g., succinimido, hydantoinyl), and an aromatic azo group (e.g., phenylazo), each of which may be substituted with substituents selected from those acceptable for R21. In addition, the couplers having a releasable group bonded via a carbon atom include bis-type couplers obtained by condensating 4-equivalent couplers with aldehydes or ketones.

[0120] The releasable groups may contain a photographically useful group acting as a development inhibitor, a development accelerator, or the like.

[0121] Preferred combinations of releasable groups in the respective formula will be described later.

[0122] The cyan couplers of formula (IV) and (V) can be synthesized by known processes. For example, the cyan couplers of formula (IV) are synthesized by the processes described in U.S. Patents 2,423,730 and 3,772,002, and the cyan couplers of formula (V) are synthesized by the processes of U.S. Patents 2.895,826, 4,333,999, and 4,327,173.

[0123] In formulae (IV) and (V), R₂₁, R24, and R_2s each preferably represents an aliphatic group having from 1 to 36 carbon atoms, or an aromatic, heterocyclic, aromatic amino or heterocyclic amino group having from 6 to 36 carbon atoms, each of which may be substituted with a substituent(s) preferably having up to 24 carbon atoms, more preferably up to 12 carbon atoms, e.g., an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkenyloxy group, an acyl group, an ester group, an amido group, a sulfamido group, an imido group, a ureido group, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic thio group, a hydroxyl group, a cyano group, a carboxyl group, a nitro group, a sulfo gorup, and a halogen atom.

[0124] The terminology "aliphatic group" as used herein means a saturated or unsaturated, and straight chain, branched, or cyclic aliphatic hydrocarbon group and includes an alkyl group, an alkenyl group, and an alkynyl group. Typically included therein are methyl, ethyl, butyl, dodecyl, octadecyl, eicosyl, isopropyl, t-butyl, t-octyl, t-dodecyl, cyclohexyl, cyclopentyl, allyl, vinyl, 2-hexadecenyl, and propargyl.

[0125] R₂₂ preferably represents an aliphatic group having from 1 to 20 carbon atoms, which may be substituted with a substituent(s) selected from those enumerated above for R₂₁.

[0126] R₂₃ and R₂₆ preferably represents a hydrogen atom, a halogen atom, an aliphatic group having from 1 to 20 carbon atoms, an aliphatic oxy group having from 1 to 20 carbon atoms, or an acylamino group having from 1 to 20 carbon atoms. The aliphatic, aliphatic oxy, or acylamino group may be substituted with a substitutent(s) selected from those enumerated above for R₂₁.

[0127] R₂₂ and R₂₃ in formula (IV) and R₂₅ and R₂₆ in formula (V) may be taken together to form a 5- to 7- membered ring.

[0128] The compounds of formulae (IV) and (V) include dimerized or polymerized couplers formed at one or more of R₂₁, R₂₂, R₂₃, and Y, in formula (IV) or at one or more of R₂₃, R₂₅, R₂₆, and Y₂ in formula (V) independently or in cooperation. In the dimerized coupler, the group at which it is formed represents a mere bond or a divalent linking group (e.g., an alkylene group, an arylene group, an ether group, an ester group, an amido group, etc., or a combination of these divalent groups). In the oligomer or polymer coupler, the groups at which it is formed are preferably in the polymer main chain or bonded to the polymer main chain vra a divalent group, such as those described above. The polymer coupler may be either a homopolymer of the coupler derivative or a copolymer comprising such a coupler derivative and other non-color-forming ethylenically unsaturated monomer(s) (e.g., acrylic acid, methacrylic acid, methyl acrylate, n-butylacrylamide, β-hydroxymethacrylate, vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride, N-vinylpyrrolidone).

[0129] R₂₁ in formula (IV) and R_2s in formula (V) each more preferably represents a substituted or unsubstituted alkyl or aryl group. The substituent for the alkyl group preferably includes a substituted or unsubstituted phenoxy group (the substituent therefore preferably includes an alkyl group, an alkoxy group, a halogen atom, a sulfonamido group, and a sulfamido group) and a halogen atom. The aryl group preferably includes a phenyl group substituted with at least one of a halogen atom, an alkyl group, a sulfonamido group, and an acylamino group.

[0130] R24 in formula (V) more preferably represents a substituted alkyl group or a substituted or unsubstituted aryl group. The substituent for the alkyl group preferably includes a halogen atom. The aryl group preferably includes a halogen atom. The aryl group preferably includes a phenyl group susbtituted with at least one of a halogen atom and a sulfonamido group.

[0131] R₂₂ in formula (IV) more preferably represents a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, and most preferably an alkyl group having from 2 to 4 carbon atoms. The substituent for the alkyl group preferably includes an alkyl or aryloxy group, an acylamino group, an alkyl or arylthio group, an imido group, a ureido group, and an alkyl or arylsulfonyl group.

[0132] R₂₃ in formula (IV) more preferably represents a hydrogen atom, a halogen atom (fluorine or chlorine being particularly preferred), or an acylamino group, with a halogen atom being the most preferred.

[0133] R₂₆ in formula (V) more preferably represents a hydrogen atom, an alkyl or alkenyl group having up to 20 carbon atoms, and most preferably a hydrogen atom.

[0134] In formula (V), it is preferable that R₂sand R₂₆ are taken together to form a 5- or 6-membered nitrogen-containing heterocyclic ring.

[0135] In formulae (IV) and (V), Y₁ and Y₂ each preferably represents a halogen atom, more preferably a chlorine atom.

[0136] The cyan couplers of formula (IV) and (V) may be used either individually or in combinations of two or more thereof.

[0137] Specific and preferred examples of the cyan couplers of formulae (IV) and (V) are shown below.

[0138] 

[0139] The magenta couplers represented by formula (VI) are disclosed in JP-A-60-262161 and JP-A-60-238832.

[0140] In formula (VI), R₂₉ represents a phenyl group, preferably a substituted phenyl group having one or more substituents selected from a halogen atom, an alkyl group (preferably having from 1 to 5 carbon atoms), an alkoxy group (preferably having from 1 to 5 carbon atoms), an aryloxy group, an alkoxycarbonyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfonamido group, and an acylamino group. A preferred substituent is a halogen atom, and particularly a chlorine atom.

[0141] The coupling releasable group as represented by Y₃ specifically includes a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, and a group represented by formula:

wherein Z represents an atomic group comprising atoms selected from carbon, oxygen, nitrogen and sulfer atoms, which is necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring in cooperation with the nitrogen atom.

[0142] R₂₃ represents a halogen atom, an alkoxy group (preferably having from 1 to 5 carbon atoms), or an alkyl group (preferably having from 1 to 5 carbon atoms), preferably a halogen atom. and more preferably a chlorine atom.

[0143] R₂₇ is a group capable of substituting the benzene ring, and n is 1 or 2. When n is 2, the two R₂₇ groups may be the same or different. The group as represented by R₂₇ includes a halogen atom,



and

wherein R , R", and R , which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. Preferred of these groups are R CONH-, R'SO₂NH-, and

[0144] Specific examples of the magenta couplers of formula (VI) include those disclosed in JP-A-60-262161 with compound Nos. of M-1 through M-37 and those disclosed in JP A-60-238832 with compound Nos. of M-1 through M-34, as well as mixtures of two or more of these compounds. Preferred among them are the compounds listed below and the compounds used in the working examples hereinafter given.

[0145] With respect to the yellow couplers represented by formula (VII), descriptions of JP-A-63-11939 can be referred to. In formula (VII), the substituent or substituents, which may be the same or different, for the phenyl nucleus of the N-phenylcarbamoyl group as represented by Q can be selected from those enumerated for the aromatic groups as represented by R₂₁.

[0146] A preferred N-phenylcarbamoyl group for Q includes those represented by formula (VII-A):

wherein G₁ represents a halogen atom or an alkoxy group; G₂ represents a hydrogen atom, a halogen atom, or a substituted or unsubstitutued alkoxy group; and R₃₄ represents a substituted or unsubstituted alkyl group.

[0147] In formula (VII-A), substituents for the alkoxy group (G₂) or the alkyl group (R₃₄) typically include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a dialkylamino group, a heterocyclic group (e.g., N-morpholino, N-piperidino, 2-furyl), a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, a sulfo group, and an alkoxycarbonyl group.

[0148] The releasable group as represented by Y_s preferably include those represented by formulae (X) to (XVI)

wherein R₄₀ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.



wherein R₄.₁ and R₄₂, which may be the same or different, each represents a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsufinyl group, a carboxyl group, a sulfo group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted heterocyclic group.

wherein W₁ represents a non-metallic atom group necessary for forming a 4- to 6-membered ring together with the moiety

[0149] Of the releasable groups of formula (XIII), preferred are those represented by formulae (XIV) to (XVI):





wherein R₄₃ and R₄₄ each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxyl group; R₄._s, R₄₆, and R₄₇ each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group; and W₂ represents an oxygen atom or a sulfur atom.

[0150] The yellow couplers of formula (VII) can be synthesized in accordance with the processes described, e.g., in JP A-54-48541, JP-B-58-10739, U.S. Patent 4,326,024, and Research Disclosure No. 18053.

[0151] Specific and preferred examples of the yellow couplers of formula (VII) are shown below.

[0152] In the present invention, 4-equivalent couplers may also be used in combination, if desired. Further, couplers which produce a dye having moderate diffusibility may be used in combination to improve graininess. Examples of such diffusible dye forming couplers are described in U.S. Patent 4,366,237 and British Patent 2,125,570 as for magenta couplers; and in European Patent 96,570 and West German Patent Application (OLS) No. 3,234,533 as for yellow, magenta, and cyan couplers.

[0153] The above-described dye forming couplers and other special couplers may be in the form of a polymer inclusive of a dimer. Typical examples of polymerized dye forming couplers are described in U.S. Patents 3,451.820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent 2,102,173 and U.S. Patent 4,367,282.

[0154] In order to satisfy various characteristic requirements of the light-sensitive materials, two or more different kinds of the couplers described above may be incorporated into one layer, or the coupler of one kind may be incorporated into two or more layers.

[0155] A standard amount of the color coupler to be used ranges from 0.001 to 1 mol per mol of light-sensitive silver halide. A preferred amount is from 0.01 to 0.5 mol as to yellow couplers; from 0.003 to 0.3 mol as to magenta couplers; and from 0.002 to 0.3 mol as to cyan couplers, each per mol of silver halide.

[0156] The couplers can be incorporated into the light-sensitive material by various known dispersion methods. Examples of high-boiling organic solvents to be used in an oil-in-water dispersion method are described, e.g., in U.S. Patent 2,322,027. A latex dispersion method, its effects, and specific examples of latices to be used for impregnation are described in U.S. Patent 4,199,363 and West German Patent Publication Nos. 2,541,174 and 2,541,230.

[0157] The silver halide emulsion to be used in the light-sensitive material may have any halogen composition, such as silver iodobromide, silver bromide, silver chlorobromide, and silver chloride. In the case where color papers or the like photographic materials are subjected to rapid processing or photographic processing is performed at a low replenishment rate as in the present invention, it is preferable to use a silver chlorobromide emulsion or silver chloride emulsion having a silver chloride content of 60 mol % or higher, and particularly of from 80 to 100 mol %.

[0158] The individual silver halide grains may have either a homogeneous phase or a heterogeneous phase, such as a core-shell structure or a layered structure having a fused structure, or a combination of these phases.

[0159] A mean grain size distribution of the silver halide grains may be either narrow or broad, but it is preferable to use a so-called monodisperse emulsion whose grain size distribution curve has a coefficient of variation (a quotient obtained by dividing a standard deviation by a mean size, expressed by per cent) within 20%, and particularly within 15%.

[0160] In order to obtain desired gradation, two or more monodisperse silver halide emulsions (preferably having the above-recited coefficient of variation) differing in mean grain size can be incorporated into one layer or into separate layers having substantially the same color sensitivity. Further, two or more polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be incorporated into one layer or separately incorporated into two or more layers.

[0161] The silver halide grains may have a regular crystal form, e.g., a cubic form, an octahedral form, a rhombic dodecahedral form, a tetradecahedral form, and a combination thereof; an irregular crystal form, e.g., a spherical form; or a composite form thereof. An emulsion comprising tabular grains, particularly an emulsion comprising tabular grains having an aspect ratio of from 5 to 8 or even more in a proportion of at least 50% based on the projected area of the total grains, can also be used. An emulsion comprising a mixture of grains having various crystal forms as described above may be used.

[0162] The emulsions may be either surface latent image type emulsion wherein a latent image is formed mainly on the surface of grains therein or internal latent image type emulsion wherein a latent image is formed mainly in the interior of grains therein.

[0163] The silver halide emulsions to be used can be prepared by known processes as disclosed, e.g.,' in Research Disclosure, Vol. 176, No. 17643, I, II, and III (Dec., 1978).

[0164] The emulsion to be used in the present invention is usually subjected to physical ripening, chemical ripening, and spectral sensitization. Additives which can be used in these steps and other photographically useful additives which can be used in the present invention are described in Research Disclosure, Vol. 176, No. 17643 (Dec., 1979) and ibid, Vol. 187, No. 18716 (Nov., 1979) as tabulated below.

[0165] The photographic materials comprise the abovedescribed emulsion layers provided on a commonly employed flexible support, such as a plastic film (e.g., cellulose nitrate, cellulose acetate, polyethylene terephthalate) and paper, or a rigid support, such as glass. For the details of the support and coating technique, Research Disclosure, Vol. 176, No. 17643, XV (p.27) and XVII (p.28) (Dec., 1978) can be referred to.

[0166] In the present invention, a reflective support is used advantageously. The reflective support functions to enhance reflecting properties to thereby make a dye image formed on the silver halide emulsion layer clearer. Such a reflective support includes a support coated with a hydrophobic resin having dispersed therein a reflecting substance (e.g., titanium oxide, zinc oxide, calcium carbonate, calcium sulfate) and a support made of a hydrophobic resin having dispersed therein such a reflecting substance.

[0167] The present invention is now illustrated in greater detail by way of the following examples, but it should be understood that the present invention is not deemed to be limited thereto. In these examples, all the percents and ratios are by weight unless otherwise specified.

EXAMPLE 1

[0168] A multi-layer color paper having the following layer structure was prepared by coating these layers in the order listed on a paper support having a polyethylene laminate on both sides thereof. The polyethylene layer on the side to be coated with a 1st layer contained a white pigment (Ti0₂) and a bluing dye. The resulting sample was designated as Sample A.

[0169] The method of preparing the coating compositions was as follows, taking the composition for the first layer for instance.

Preparation of Coating Composition:

[0170] To a mixture of 19.1 g of yellow coupler (ExY-2) and 4.4 g of dye image stabilizer (Cpd-2) were added 27.2 m ℓ of ethyl acetate and 7.7 m ℓ (8.0 g) of high-boiling organic solvent (Solv-1 ) to form a solution. The solution was emulsified and dispersed in 185 m of a 10% gelatin aqueous solution containing 8 m of a 10% sodium dodecylbenzenesulfonate aqueous solution. The resulting dispersion was mixed with emulsions EM7 and EM8, and the gelatin concentration was adjusted so as to have the composition for the first layer.

[0171] Each of the 1st to 7th layers further contained a sodium salt of 1-oxy-3,5-dichloro-s-triazine as a gelatin hardening agent and Cpd-1 as a thickener.

Layer Structure:

1st Layer (Blue-Sensitive Layer):

[0172] 

2nd Layer (Color Stain Preventing Layer):

[0173] 

3rd Layer (Green-Sensitive Layer):

4th Layer (Ultraviolet Absorbing Layer):

[0174] 

5th Layer (Red-Sensitive Layer):

6th Layer (Ultraviolet Absorbing Layer):

[0175] 

7th Layer (Protective Layer):

[0176] In addition, Cpd-12 and Cpd-13 were used as anti-irradiation dyes. Each layer furthermore contained Alkanol XC (a trade name of Du Pont), a sodium alkylbenzenesulfonate, a succinic ester, and Magefacx F-120 (a trade name of Dai-Nippon Ink & Chemicals, Inc.) as dispersing agent or coating aid, and Cpd-14 and Cpd-15 as stabilizer for silver halide.

[0177] Data of the emulsions used in Sample A are shown in Table 1 below.

[0178] The compounds used in sample A are as follows.

Solv-1: Dibutyl phthalate

Solv-2: Trioctyl phosphate

Soiv-3: Trinonyl phosphate

Soiv-4: Tricresyl phosphate

[0179] Sample A was exposed to light through an optical wedge and then processed under conditions shown in Table 2 using processing solutions having the following formulations. The processing was carried on for 75 days at a rate of 2 m²/day (hereinafter referred to as Running Test I) or for 10 days at a rate of 15 m²/day (hereinafter referred to as Running Test II).

Color Developer A:

[0180] 

Colour Developer B:

[0181] 

Blix Bath: (The tank solution and the replenisher had the same formulation)

Washing Water:

[0182] Deionized water having a calcium or magnesium content of not more than 3 ppm was used.

[0183] Each of the processed sample obtained at the very beginning of the processing and that obtained at the end was determined for their yellow minimum densities, yellow sensitivities, and yellow maximum densities to calculate the respective change (ADs _min , ΔS_B, and ADs _max ). The change of sensitivity was expressed in terms of a change of exposure amount which provided a density of 0.6 (AlogE). The results obtained are shown in Table 3.

[0184] It is obvious from Table 3 that the samples processed with a color developer containing the conventional preservative suffer from a considerable variation of photographic characteristics with the progress of running. Such a variation is particularly outstanding when the samples were processed with Color Developer B which was replenished at a reduced rate (Run Nos. 3 to 7). This tendency is observed irrespective of whether the rate of processing is high (Running Test II) or low (Running Test I).

[0185] To the contrary, the variation of photographic characteristics as observed in the comparative runs can be minimized when processing was carried out at a low replenishment rate according to the present invention. Difference of processing rate by no means makes the variation larger as can be seen by comparing Run Nos. 8 and 9 or Run Nos. 11 and 12. Further, it was confirmed that better results can be obtained when the color developer contains no sulfite ion.

EXAMPLE 2

[0186] Samples B to G were prepared in the same manner as for Sample A of Example 1, except for altering the kind of couplers used as indicated in Table 4.

[0187] The couplers shown in Table 4 had the following chemical formulae:

[0188] Each of Samples A to G was exposed to light through an optical wedge and then processed in the same manner as in Run Nos. 7, 8, or 11 of Example 1. Gradation of yellow B), magenta (G), and cyan (R) of each of the processed sample obtained in the beginning of the processing and that obtained at the end of the processing were measured, and the respective change was calculated. The gradation is a difference of density between the density of 0.5 and the density at a logE point higher by 0.3 than the logE providing the density of 0.5 in the D-logE curve. The results obtained are shown in Table 5 below.

[0189] The results of Table 5 reveal that the variation of photographic characteristics (gradation) can be minimized when processing was carried out according to the method of the present invention (Run Nos. 8 and 11). This effect is particularly remarkable in those samples wherein the couplers preferred in the present invention were used (Samples A, B, C and D).

EXAMPLE 3

[0190] Sample C of Example 2 was imagewise exposed to light and then subjected to continuous processing under conditions shown in Table 6 using processing solutions whose formulations are described below.

Color Developer:

[0191] 

Blix Bath: (The tank solution and the replenisher had the same formulation)

[0192] 

Stabilizing Bath: (The tank soltuion and the replenisher had the same formulation)

[0193] The changes of photographic characteristics of magenta during running (ΔD_{G min} ΔS_G, and ΔD_{G max} ) were obtained in the same manner as described in Example 1. The results obatined are shown in Table 7.

[0194] It is apparent form Table 7 that the processing method according to the present invention brings about marked improvements on variation of photographic characteristics of magenta (ΔD_{G min} , ΔS_G, and ΔD_{G max} ). This effect is particularly pronounced when the color developer contains substantially no benzyl alcohol'and/or a bromine ion as can be seen from the results of Run Nos. 8, 9, and 10.

EXAMPLE 4

[0195] A multi-layer color paper having the following layer structure was prepared by coating these layers in the order listed on a paper support having a polyethylene laminate on both sides thereof. The polyethylene layer on the side to be coated with a 1 st layer contained a white pigment (Ti0₂) and a bluing dye.

[0196] The method of preparing the coating compositions was as follows, taking the composition for the first layer for instance.

Preparation of Coating Composition:

[0197] To a mixture of 10.2 g of yellow coupler (ExY-1), 9.1 g of yellow coupler (ExY-2), and 4.4 g of dye image stabilizer (Cpd-1) were added 27.2 m t of ethyl acetate and 7.7 m ℓ (8.0 g) of high-boiling organic solvent (Solv-1) to form a solution. The solution was emulsified and dispersed in 185 m of a 10% gelatin aqueous solution containing 8 mℓ of a 10% sodium dodecylbenzenesulfonate aqueous solution. The resulting dispersion was mixed with emulsions EM1 and EM2, and the gelatin concentration was adjusted so as to have the composition for the first layer.

[0198] Each of the 1st to 7th layers further contained a sodium salt of 1-oxy-3,5-dichloro-s-triazine as a gelatin hardening agent and Cpd-2 as a thickener.

Layer Structure:

lst Layer (Blue-Sensitive Layer):

[0199] 

2nd Layer (Color Stain Preventing Layer):

3rd Layer (Green-Sensitive Laver):

[0200] 4th Laver (Ultraviolet Absorbing Layer):

[0201] 5th Layer (Red-Sensitive Layer):

6th Layer (Ultraviolet Absorbing Layer):

[0202] 

7th Layer (Protective Laver):

[0203] In addition, Cpd-13 and Cpd-14 were used as anti-irradiation dyes. Each layer furthermore contained Alkanol XC (a trade name of Du Pont), a sodium alkylbenzenesulfonate, a succinic ester, and Magefacx F-120 (a trade name of Dai-Nippon Ink & Chemicals, Inc.) as dispersing agent or coating aid, and Cpd-15 and Cpd-16 as stabilizer for silver halide.

[0204] Data of the emulsions used in the sample preparation are shown in Table 8.

[0205] The compounds used in the sample preparation are as follows.

Solv-1: Dibutyl phthalate

Solv-2: Tricresyl phosphate

Soiv-3: Trioctyl phosphate

Solv-4: Trinonyl phosphate

[0206] The resulting sample was continuously processed under conditions shown in Table 9 below using processing solutions having formulations described below until the total quantity of the color developer replenisher reached twice the volume of the development tank.

Color Developer:



Blix Bath:

Washing Water: (The tank solution and the replenisher had the same formulation)

[0207] Deionized water having a calcium or magnesium content of not more than 3 ppm was used.

[0208] Each of the samples was exposed to light through an optical wedge and the processed either before and after the above-described continuous running to evaluate changes in magenta minimum density (ΔD_min) and magenta gradation (A-y) with the progress of running. The gradation is a difference of density between the density of 0.5 and the density at the logE point higher by 0.3 thatn the logE providing the density of 0.5. The results obtained are shown in Table 10 below.

[0209] As is apparent from Table 10, in the runs out of the scope of this invention, the photographic characteristics are seriously deteriorated according as the replenishment rate decreases (Run Nos. 6 to 12). According to the construction of the present invention, satisfactory photographic characteristics can be obtained even when the replenishment rate is less than 200 mL/m² (Run Nos. 13 to 18 and 22 to 28).

EXAMPLE 5

[0210] The same color paper as prepared in Example 1 was continuously processed under conditions shown in Table 11 using processing solutions whose formulation are described below until the total quantity of the color developer replenisher reached three times the developer tank.

Color Developer:

[0211] 

[0212] Blix Bath: (The tank solution and the replenisher had the same formulation)

[0213] Rinsing Solution: (The tank solution and the replenisher had the same formulation)

[0214] The sample was exposed to light through an optical wedge and processed either before and after the abovedescribed continuous processing. The changes of minimum density and gradation (gamma) with the progress of running were obtained, and the results are shown in Table 12.

[0215] The results of Table 12 prove that satisfactory results can be obtained by following the construction of the present invention (Run Nos. 8 to 18).

[0216] 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 method for continuously processing an imagewise exposed silver halide color photographic material with a color developer containing at least on6 aromatic primary amine color developing agent, in which said color developer contains at least one compound selected from the group consisting of a compound represented by formula (I):

wherein R¹, R², and R³ each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; R⁴ represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrazino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted amino group; or R³ and R^4. are taken together to form a heterocyclic group; X¹ represents a divalent group; and n represents 0 or 1, provided that when n is 0, R4 represents an alkyl group, an aryl group, or a heterocyclic group, and a compound represented by formula (II):

wherein R⁵ represents a substituted alkylene group; and R⁶, R⁷, R⁸, and R⁹, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and said color developer is replenished at a replenishment rate of from 20 to 120 m per m² of the photographic material.

2. A method as claimed in claim 1, wherein said compound represented by formula (I) is present in an amount of from 0.01 to 50 g per liter of the color developer.

3. A method as claimed in claim 1, wherein said compound represented by formula (II) is present in an amount of from 0.1 g to 20 g per liter of the color developer.

. 4. A method as claimed in claim 1, wherein said photographic material contains at least one magenta coupler represented by formula (III):

wherein R₁₀ represents a hydrogen atom or a substituent; X represents a hydrogen atom or a group releasable on coupling reaction with an oxidation product of an aromatic primary amine developing agent; Z_a, Z_b, and Z_c each represents a methine group, a substituted methine group, = N- or -NH-; one of the Z_a-Z_b bond and Z_b-Z_c bond is a double bond, with the other being a single bond; when the Zb-Zc bond is a carbon-carbon double bond, it may be a part of an aromatic ring; the formula (III) includes a dimer or a higher polymer formed at R₁₀ or X or at Z_a, Z_b or Z_c representing a substituted methine group.

A method as claimed in claim 1, wherein said color developer contains substantially no bromine or iodine ion.

6. A method as claimed in claim 1, wherein said color developer contains substantially no sulfite ion.

7. A method as claimed in claim 1, wherein said color developer contains substantially no hydroxylamine.

8. A method as claimed in claim 1, wherein said color developer is replenished at a replenishment rate of from 30 to 100 mℓ/m².