Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group
  • G03C7/30547—Dyes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image
  • G03C7/3335—Coloured coupling substances, e.g. for the correction of the coloured image containing an azo chromophore

Definitions

• This invention relates to a color photographic material having improved color reproducibility and more particularly to a silver halide color photographic material containing a colored coupler for color correction, which can release a water-soluble pyridone azo dye.
• Silver halide emulsions selectively sensitive to blue light, green light and red light, respectively, are used in combination with yellow, magenta, and cyan dye-forming couplers which are complementary color to the light.
• the thus-formed dye images do not have always ideal spectral absorption characteristics and often absorb light beyond the primary wavelength range, because absorption is spread, the absorption curve is extended or there is secondary absorption.
• a cyan dye image should absorb only red light, but generally absorbs some undesirable green light and blue light.
• a magenta dye image should absorb only green light, but absorbs some undesirable blue light and red light.
• the color correction effect of the colored couplers can be achieved when couplers containing a dye structure give developed color images by coupling with oxidized aromatic primary amine developing agents and at the same time the original dye structure is decomposed or flows into developing solutions whereby its absorption is lost (decolorization).
• decolorizable dye structures there have been proposed various structures such as azo dyes, azomethine dyes, benzylidene dyes, oxonol dyes, merocyanine dyes, cyanine dyes, styryl dyes, hemiox- onol dyes, anthraquinone dyes and xanthene dyes.
• yellow colored couplers e.g., yellow colored cyan couplers
• Decolorizable dye structures are limited to arylene azo dyes and styryl dyes.
• the characteristics required for the yellow colored couplers are that the molecular extinction coefficient is high; the spectral absorption characteristics are close to the undesired absorption of the dye images of couplers used in combination in the blue light region; and the yellow dye images have high fastness to heat and light.
• the above-described yellow colored couplers are not always fully satisfactory with respect to their performance. For example, they have the disadvantages that molecular extinction coefficient is low, the hue is orange to reddish, or the fastness of the yellow dye images is inferior.
• a first object of the present invention is to provide a silver halide color photographic material containing a colored coupler having excellent spectral absorption characteristics.
• a second object of the present invention is to provide a silver halide color photographic material having a high molecular extinction coefficient.
• a third object of the present invention is to provide a silver halide color photographic material containing a colored coupler which gives a dye image having high fastness.
• a fourth object of the present invention is to provide a silver halide color photographic material having improved color reproducibility containing a novel colored coupler.
• a silver halide color photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer, said photographic material comprising at least one colored coupler capable of releasing a water-soluble compound comprising a 6 hydroxy-2-pyridone-5-azo group by a coupling reaction with an oxidized aromatic primary amine developing agent.
• the colored couplers according to the present invention are illustrated in greater detail.
• the colored couplers of the present invention are represented by formula (I):
• Cp represents a group (a coupler moiety) where the bond between Cp and -(T) l is cleaved by the coupling reaction of the coupler with an oxidized aromatic primary amine developing agent;
• T represents a timing group; 1 is 0 or 1;
• X represents a divalent linking group which is bonded to (T) z through N, 0 or S;
• Y represents an arylene group or a divalent heterocyclic group;
• R 1 and R 2 which may be the same or different each represents a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, a carbonamido group, a sulfonamido group or an alkylsulfonyl group; and R 3 represents a hydrogen
• Coupler moiety represented by Cp can be used as the coupler moiety represented by Cp, including yellow coupler moieties (e.g., open chain ketomethylene type couplers moieties), magenta coupler moieties (e.g., 5-pyrazolone type, pyrazoloimidazole type and pyrazolotriazole type coupler moieties), cyan coupler moieties (e.g., phenol type and naphthol type coupler moieties) and non-color forming coupler moieties (e.g., indanone type and acetophenone type coupler moieties).
• Heterocyclic type coupler moieties described in U.S. Patent 4,315,070, 4,183,752, 3,961,959 or 4,171,223 can be used.
• Cp include coupler moieties represented by formulas (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9), and (Cp-10).
• coupler moieties are preferred, because they have a high coupling rate.
• the free bonds at the coupling positions represent the bonding positions of the groups which are eliminated by coupling.
• the total number of carbon atoms in the group is 8 to 40, preferably 10 to 30. In other cases, the total number of carbon atoms is preferably not more than 15.
• the couplers are bis type, telomer type or polymer type, any one of the above substituent groups is a bivalent group bonded to a repeating unit. In this case, the total numbers of carbon atoms may be beyond the above range.
• R 41 represents an aliphatic group, an aromatic group or a heterocyclic group
• R 42 represents an aromatic group or a heterocyclic group
• R 43 , R 44 , and R 4 s which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
• R 51 has the same meaning as R 41 ;
• R 52 and R 53 each has the same meaning as R 42 ;
• R 54 represents R 41 , N ⁇ C-;
• Rss has the same meaning as R 41 ;
• R 56 and R 57 each repersents R 43 , R 41 S-, R 43 0-, R 58 has the same meaning as R 41 ;
• R 59 represents R 41 , R 41 O-, R 41 S-, a halogen atom or d is 0 or an integer of from 1 to 3 and when d is 2 or 3, plural R 59 groups may be the same or different, or each R 59 is a divalent group and these divalent groups may be linked to form a ring structure.
• Typical examples of the divalent groups which form a ring structure include the following groups.
• R 60 has the same meaning as R 4 . 1 ;
• R 61 has the same meaning as R 41 ;
• Rs 2 represents R 41 , R 41 CONH-, R 41 OCONH-, R 41 SO 2 NH-, R 43 O-, R 41 S-, a halogen atom or
• R 63 represents R 41 , R 41 SO 2 -, R 43 0CO-, R 43 O-SO 2 -, a halogen atom, a nitro group, a cyano group or R 43 CO-; and
• e is 0 or an integer of 1 to 4.
• groups are defined as follows, unless otherwise defined.
• the aliphatic group is a saturated or unsaturated linear or cyclic straight-chain or branched chain, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.
• Typical examples thereof include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, i-butyl group, t-amyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, 1,1,3,3-tetramethylbutyl group, decyl group, dodecyl group, hexadecyl group and octadecyl group.
• the aromatic group is a substituted or unsubstituted phenyl or naphthyl group having 6 to 20 carbon atoms.
• the heterocyclic group is preferably a 3-membered to 8-membered a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms wherein the hetero-atom is selected from a nitrogen, oxygen and sulfur atom.
• heterocyclic group examples include a 2-pyridyl group, 2-thienyl group, 2-furyl group, 1-imidazolyl group, 1-indolyl group, phthalimido group, 1,3,4-thiadiazole-2-yl group, 2-quinolyl group, 2,4-dioxo-1,3-imidazolidine-5-yl group, 2,4-dioxo-1,3-imidazolidine-3-yl group, succinimido group, 1,2,4-triazole-2-yl group and 1-pyrazolyl group.
• the above-described aliphatic hydrocarbon group, aromatic group and heterocyclic group may optionally have one or more substituent groups.
• substituent groups include a halogen atom, R 47 O-, R 47 OSO 2 -, a cyano group and a nitro group, wherein R 46 represents an aliphatic group, an aromatic group or a heterocyclic group and R 47 , R 48 and R 49 each represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom.
• the aliphatic group, the aromatic group and the heterocyclic group have the same meanings as those described above.
• R 51 to R 63 and d and e are as follows.
• R 51 is an aliphatic group or an aromatic group.
• R 52 , R 53 and R 55 are each an aromatic group.
• R 54 is preferably R 41 CONH- or R 56 and R 57 are each preferably an aliphatic group, R 41 O-or R 41 S-; and R 58 is preferably an aliphatic group or an aromatic group.
• R 59 is preferably a chlorine atom, an aliphatic group or 41 CONH-; d is preferably 1 or 2; and R 60 is preferably an aromatic group.
• R 59 is preferably R 41 CONH-; d is preferably 1; and R 61 is preferably an aliphatic group or an aromatic group.
• e is preferably 0 or 1;
• R 62 is preferably R 41 OCONH-, R 41 CONH-or R 41 SO 2 NH- and these groups are preferably attached to the 5-position of the naphthol ring.
• R 63 is preferably R 41 CONH-, R 41 SO 2 NH-, R 41 SO 2 -, a nitro group or a cyano group.
• R 63 is preferably R 43 OCO- or a R 43 CO-.
• R 51 to R 63 are as follows.
• R 51 examples include a t-butyl group, 4-methoxyphenyl group, phenyl group, 3- ⁇ 2-(2,4-di-t-amyl- phenoxy)butaneamido ⁇ phenyl group and methyl group.
• R 52 and R 53 include 2-chloro-5-dodecyloxycarbonylphenyl group, 2-chloro-5-hexadecylsulfonamidophenyl group, 2-chloro-5-tetradecaneamidophenyl group, 2-chloro-5- ⁇ 4-(2,4-di-t-amylphenoxy)butaneamido ⁇ phenyl group, 2-chloro-5- ⁇ 2-(2,4-di-t-amylphenoxy)butaneamido ⁇ phenyl group, 2-methoxyphenyl group, 2-methoxy-5-tetradecylox- ycarbonylphenyl group, 2-chloro-5-(1-ethoxycarbonylethoxycarbonyl)phenyl group, 2-pyridyl group, 2-chloro-5-octyloxycarbonylphenyl group, 2,4-dichlorophenyl group, 2-chloro-5-(1-d
• R 54 examples include a 3- ⁇ 2-(2,4-di-t-amy)phenoxy)butaneamido ⁇ -benzamidogroup, 3- ⁇ 4-(2,4-di-t-amylphenoxy)butaneamido ⁇ benzamido group, 2-chloro-5-tetradecaneamidoanilino group, 5-(2,4-di-t-amyl- phenoxyacetamido)benzamido group, 2-chloro-5-dodecenylsuccinimidoanilino group, 2-chloro-5- ⁇ 2-(3-t-butyl-4-hydroxyphenoxy)tetradecaneamido ⁇ anilino group, 2,2-dimethylpropanamido group, 2-(3-pentadecyl- phenoxy)butaneamido group, pyrrolidino group and N,N-dibutylamino group.
• R 55 examples include a 2,4,6-trichlorophenyl group, 2- chlorophenyl group, 2,5-dichlorophenyl group, 2,3-dichlorophenyl group, 2,6-dichloro-4-methoxyphenyl group, 4- ⁇ 2-(2,4-di-t-amylphenoxy)butaneamido ⁇ phenyl group and 2,6-dichloro-4- methanesulfonylphenyl group.
• R 56 examples include a methyl group, ethyl group, isopropyl group, methoxy group, ethoxy group, methylthio group, ethylthio group, 3-phenylureido group, and 3-(2,4-di-t-amylphenoxy)propyl group.
• R 57 examples include a 3-(2,4-di-t-amylphenoxy)propyl group, 3-[4- ⁇ 2-[4-(4-hydroxyphenylsulfonyl)phenoxy]tetradecaneamido ⁇ phenyl]propyl group, methoxy group, methylthio group, ethylthio group, methyl group, 1-methyl 2- ⁇ 2-octyloxy-5-[2-octyloxy-5-(1,1,3,3-tetramethylbutyl)-phenylsulfonamido]phenylsulfonamido ⁇ ethyl group, 3- ⁇ 4-(4-dodecyloxyphenylsulfonamido)phenyllpropyl group, 1,1-dimethyl-2- ⁇ 2-octyloxy-5-(1,1,3,3-tetramethylbutyl)phenylsulfonamido ⁇ ethylgroup and dodecyl- thio group
• R 58 examples include a 2-chlorophenyl group, pentafluorophenyl group, heptafluoropropyl group, 1-(2,4-di-t-amylphenoxy)propyl group, 3-(2,4-di-t-amylphenoxy)propyl group, 2,4-di-t-amylphenoxymethyl group and furyl group.
• R 59 examples include a chlorine atom, a methyl group, ethyl group, propyl group, butyl group, isopropyl group, 2-(2,4-di-t-amylphenoxy)-butaneamido group, 2-(2,4-di-t-amyl- phenoxy)-hexaneamido group, 2-(2,4-di-t- octylphenoxy)octaneamido group, 2-(2-chlorophenoxy) tetradecaneamido group, 2-(4-(4-hydroxyphenylsulfonyl) phenoxy ⁇ tetradecaneamido group and 2- ⁇ 2-(2,4-dit-amylphenoxyacetamido)phenoxylbutaneamido group.
• R 60 examples include a 4-cyanophenyl group, 2-cyanophenyl group, 4-butylsulfonylphenyl group, 4-propylsulfonylphenyl group, 4-chloro-3-cyanophenyl group, 4-ethoxycarbonylphenyl group and 3,4-dichlorophenyl group.
• R 61 examples include a dodecyl group, hexadecyl group, cyclohexyl group, 3-(2,4-di-t-amylphenoxy)propyl group, 4-(2,4-di-t-amylphenoxy)-butyl group, 3-dodecyloxypropyl group, t-butyl group, 2-methoxy-5-dodecyloxycarbonylphenyl group and 1-naphthyl group.
• R s2 examples include an isobutyloxycarbonylamino group, ethoxycarbonylamino group, phenylsulfonylamino group, methanesulfonamido group, benzamido group, trifluoroacetamido group, 3-phenylureido group, butoxycarbonylamino group and acetamido group.
• R 63 examples include a 2,4-di-t-amylphenoxyacetamido group, 2-(2,4-di-t-amylphenoxy)butaneamido group, hexadecylsulfonamido group, N-methy-N-octadecylsulfamoyl group, N,N-dioctylsulfamoyl group, 4-t-octylbenzoyl group, dodecyloxycarbonyl group, chlorine atom, nitro group, cyano group, N- ⁇ 4-(2,4-di-t-amylphenoxy)butyl ⁇ carbamoyl group, N-3-(2,4-di-t-amylphenoxy)propylsulfamoyl group, methanesulfonyl group and hexadecylsulfonyl group.
• cyan coupler residues represented by formulas (Cp-7) and (Cp-8) are preferred, with naphthol type cyan couplers represented by formula (Cp-8) being particularly preferred.
• the timing group represented by T is a group which is cleaved from X after the cleavage of the bond between T and Cp by the coupling reaction of the coupler of formula (I) with an oxidized aromatic primary amine developing agent.
• the timing group is used for various purposes of controlling coupling reactivity, stabilization of the couplers, and controlling the releasing timing of the X-containing residue. Examples of the timing group include the following bonding groups.
• Examples of the groups include those represented by the following general formula (T-1) described in U.S. Patent 4,146,396, JP-A-60-249148 and JP-A-60-249149.
• T-1 represents the position where T is bonded to Cp in formula (I) and ** represents the position where T is bonded to X in formula (I).
• W represents an oxygen or sulfur atom or R 11 and R 12 each represents a hydrogen atom or a substituent group; R 18 represents a substituent group; and t is 1 or 2.
• t is 2, the two groups may be the same or different.
• R 11 and R 12 are each a substituent group
• examples of R 11 , R 12 and R 18 include R 15 , R 15 CO-, R 15 SO 2 -, wherein R 15 represents an aliphatic group, an aromatic group or a heterocyclic group and R 16 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
• R 11 , R 12 and R 13 may be a divalent group and these bonding groups may be linked to form a ring structure. Such ring structures are included within the scope of the present invention.
• Examples of the groups represented by formula (T-1) include the following groups, but the present invention is not to be construed as being limited thereto.
• Timing groups represented by the following general formula (T-2) described in U.S. Patent 4,248,292. *-Nu-Link-E-** (T-2)
• Nu represents a nucleophilic group (examples of nucleophilic species being an oxygen and sulfur atoms); E represent an electrophilic group which is a group which cause the cleavage of the bond marked ** by nucleophilic attack by Nu; and Link is a linking group through which Nu and E are sterically positioned such that an intramolecular nucleophilic substitution reaction takes place.
• Examples of the groups represented by formula (T-2) include the following groups, but the present invention is not to be construed as being limited thereto.
• Examples of the groups include those represented by the following general formula (T-3) described in U.S. Patents 4,409,323 and 4,421,845, JP-A-57-188035, JP-A-58-98728, JP-A-58-209736, JP-A-58-209737 and JP-A-58-209738.
• * and **, W, R 11 , R 12 and t are as defined in formula (T-1).
• R 11 and R 12 may be linked to form a member of a benzene ring or a heterocyclic ring.
• R 11 or R 12 may be combined with W to form a benzene ring or a heterocyclic ring.
• Z 1 and Z 2 are independently a carbon atom or a nitrogen atom; x and y are each 0 or 1. When Z 1 is carbon atom, x is 1, and when Z 1 is nitrogen atom, x is 0. The relationship between Z 2 and y is the same as that between Z 1 and x. t is 1 or 2. When t is 2, the two groups may be the same or different.
• Examples of the groups represented by the formula (T-3) include the following groups, but the present invention is not to be construed as being limited thereto.
• Examples of the groups include bonding groups described in West German Patent (Laid Open) No. 2,626,315 which are groups represented by the following formulas (T-4) and (T-5).
• Examples of the groups include bonding groups described in U.S. Patent 4,546,073, which are groups represented by the following formula (T-6). wherein * and ** and W are as defined and R 16 has the same meaning as R 18 in formula (T-1). Examples of the groups represented by formula (T-6) include the following groups, but the present invention is not to be construed as being limited thereto.
• Examples of the groups include those described in JP-A-57-56837, JP-A-60-214358, JP-A-60-218645, JP-A-60-229030, JP-A-61-156127 and JP-A-63-37346. More specifically, examples thereof include the following groups, but the present invention is not to be cosntrued as being limited thereto.
• timing groups represented by formulas (T-1) to (T-3) are preferred in the present invention.
• l is an integer of 0 or 1.
• t is 0, that is, Cp and X are directly bonded to each other.
• X in formula (I) is a divalent bonding group which is bonded to (T) l through N, 0 or S. More preferably, X is -O-, -S-, -OSO 2 -, -OSO 2 NH- or a divalent group which is bonded to (T) t through N, such as a divalent heterocyclic group (e.g., a group derived from pyrrolidine, piperidine, morpholine, piperazine, pyrrole, pyrazole, imidazole, 1,2,4-triazole, benzotriazole, succinimide, phthalimide, oxazolidine-2,4-dione, imidazolidine-2,4-dione, or 1,2,4-triazolidine-3,5-dione) or a bonding group which is a composite group derived from these groups and an alkylene group (e.g., methylene, ethylene, trimethylene), a cycloalky
• X is a group represented by formula (II)
• * represents the position where X 1 is bonded to (T) l ; ** represents the position where X 2 is bonded to Y;
• X 1 represents -0- or -S-;
• L represents an alkylene group;
• X represents a single bond, -0-, -S-, -CO-, -S0 2 -, -S0 2 NH-, -NHS0 2 -, -S0 2 0-, -OS0 2 -, -OS0 2 NH or -NHS0 2 0-; and
• m is 0 or an integer of 1 to 3.
• the total number of carbon atom s(hereinafter referred to as the C-number) of X is preferably 0 to 12, more preferably 0 to 8.
• Y in formula (I) is an arylene group or a divalent heterocyclic group.
• the arylene group may be a condensed ring, and the arylene group may have one or more substituent groups (e.g., halogen, hydroxyl, nitro, cyano, alkyl, cycloalkyl, aryl, carbonamido, sulfonamido, alkoxy, aryloxy, acyl, sulfonyl, carboxyl, sulfo, carbamoyl, sulfamoyl).
• the C-number is preferably 6 to 15, more preferably 6 to 10.
• the heterocyclic group is a 3-membered to 8-membered (preferably 5-membered to 7-membered) monocyclic or condensed ring heterocyclic group containing at least one hetero-atom selected from the group consisting of N, 0, S, P, Se and Te as a member of the heterocyclic ring (e.g., a group derived from pyridine, thiophene, furan, pyrrole, pyrazole, imidazole, thiazole, oxazole, benzothiazole, benzoxazole, benzofuran, benzothiophene, 1,3,4-thiadiazole, indole, or quinoline).
• the heterocyclic group may have one or more substituent groups (examples of the substituent groups include those already described above in the definition of the substituent groups for the arylene group of Y).
• the C-number is preferably 2 to 15, more preferably 2 to 10.
• R 2 or R 3 in formula (I) is an alkyl group
• the alkyl group includes both straight-chain and branched chain alkyl groups which may have unsaturated bonds and one or more substituent groups (e.g., halogen, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamido, sulfonamido, carbamoyl, sulfamoyl, or sulfonyl).
• substituent groups e.g., halogen, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamido, sulfonamido, carbamoyl, sulfamoyl, or s
• R i , R 2 or R 3 is a cycloalkyl group
• the cycloalkyl group is a 3-membered to 8-membered cycloalkyl group which may have crosslinking groups, unsaturated bonds or substituent groups (examples of the substituent groups include those already described above in the definition of the substituent groups for the alkyl group of R 1 , R 2 or Rs).
• R 1 , R 2 or R 3 is an aryl group
• the aryl group may be a condensed ring and may have substituent groups (examples of the substituent groups include alkyl, cycloalkyl and those already described above in the definition of the substituent groups for the alkyl group of R 1 , R 2 or R 3 ).
• the heterocyclic group is a 3-membered to 8-membered (preferably 5-membered to 7-membered) monocyclic or condensed ring heterocyclic group containing at least one hetero-atom selected from the group consisting of N, S, 0, P, Se and Te as a member of the heterocyclic ring.
• the heterocyclic group include imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl and quinolinyl.
• the heterocyclic group may have one or more substituent groups (examples of the substituent groups are the same as those for the aryl group of R i , R 2 or R 3 ).
• the carboxyl group includes a carboxylate group; the sulfo group includes a sulfonato group; the phosphino group includes a phosphinato group; and the phosphono group includes a phosphonato group.
• Those groups may include any counter ions, including Li*, Na , K or ammonium.
• R 1 is a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms (e.g., methyl, t-butyl, sulfomethyl, 2-sulfoethyl, carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl, benzyl, ethyl, isopropyl) or an aryl group having 6 to 12 carbon atoms (e.g., phenyl, 4-methoxyphenyl, 4-sulfophenyl) with a hydrogen atom, a methyl group or a carboxyl group being particularly preferred.
• an alkyl group having 1 to 10 carbon atoms e.g., methyl, t-butyl, sulfomethyl, 2-sulfoethyl, carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl, benzyl, ethyl, isopropyl
• R 2 is a cyano group, carboxyl group, a carbamoyl group having 1 to 10 carbon atoms, a sulfamoyl group having 0 to 10 carbon atoms, a sulfo group, an alkyl group having 1 to 10 carbon atoms (e.g., methyl, sulfomethyl), a sulfonyl group having 1 to 10 carbonatoms (e.g., methylsulfonyl, phenylsulfonyl), a carbonamido group having 1 to 10 carbon atoms (e.g., acetamido, benzamido) or a sulfonamido group having 1 to 10 carbon atoms (e.g., methanesulfonamido, toluenesulfonamido) with a cyano group, carbamoyl group or carboxyl group being particularly preferred.
• a cyano group e.g.
• R 3 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (e.g., methyl, sulfomethyl, carboxyethyl, 2-sulfoethyl, 2-carboxyethyl, ethyl, n-butyl, benzyl, 4-sulfobenzyl) or an aryl group having 6 to 15 carbon atoms (e.g., phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 4-methoxyphenyl, 2,5-dicarboxyphenyl, 3,5-dicarboxyphenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 2,5- disulfophenyl). More preferably, R 3 is an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 10 carbon atoms.
• Examples of Cp, X, Y and in formula (I) include the following groups (examples of T have been already described above), but the present invention is not construed as being limited thereto.
• Examples of the colored couplers of the present invention include the following compounds, but the present invention is not to be construed as being limited thereto.
• the water soluble compound (dye) comprising a 6-hydroxy-2-pyridone-5-azo group, which is released from the coupler by development processing should be dissolved out from the photographic material.
• the compound preferably is soluble in a developing solution of pH 9 to 12 in an amount of at least 1g/l, more preferably 3g/R.
• the colored couplers of the present invention can be generally synthesized by the diazo coupling reaction of a 6-hydroxy-2-pyridone compound with an aromatic diazonium salt or heterocyclic diazonium salt having a coupler structure.
• the former 6-hydroxy-2-pyridone compounds can be synthesized by methods described in Klinsberg, Heterocyclic Compound - Pyridine and Its Derivatives , Part 3 (Interscience 1962); J. Am. Chem. Soc. , Vol. 65. page 449 (1943);J. Chem. Tech. Biotechnol. , Vol. 36, page 410 (1986); Tetrahedron , Vol. 22, page 445 (1966); JP-B-61-52827 (the term "JP-B” as used herein means an "examined Japanese patent publication”); West German Patents 2,162,612, 2,349,709 and 2,902,486; and U.S. Patent 3,763,170.
• the latter diazonium salts can be synthesized according to the methods described in U.S. Patents 4,004,929 and 4,138,258, JP-A-61-72244 and JP-A-61-273543.
• the diazo coupling reaction of the 6-hydroxy-2-pyridone compounds with the diazonium salts can be carried out in a solvent such as methanol, ethanol, methyl cellosolve, acetic acid, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dioxane, water or the like or a mixture thereof.
• reaction temperature is generally from -78 to +60° C, preferably from -20 to + 30 C.
• the resulting crude crystal was purified from hot methanol in the same manner as in Synthesis Example 1 to give 14.8 g of the desired coupler (3) with a melting point of 246 to 251 ° C (decomposition).
• the structure of the compound was confirmed by 1 HNMR spectrum, mass spectrum and elemental analysis.
• the compound exhibited a maximum absorption wavelength in methanol at 457.6 nm and had a molecular extinction coefficient of 42700.
• the compound was found to have good spectral absorption characteristics as a yellow colored coupler.
• the coupler (22) had a melting point of 154-6° C. The structure thereof was confirmed by 1 HNMR spectrum, mass spectrum and elemental analysis. The compound exhibited a maximum absorption wavelength in methanol at 458.2 nm and had a molecular extinction coefficient of 42800. The compound was found to have good spectral absorption characteristics as a yellow colored coupler.
• the total amount of the coupler of formula (I) according to the present invention, which is added to the photographic material is preferably 1x10 -6 to 3x10 -3 mol/m 2 , more preferably 1x10 -5 to 1 x 10- 3 mol/m 2 . It is preferred that the coupler of the present invention is added to light sensitive silver halide emulsion layers. More preferably, the same layer contains the colored coupler of the present invention together with an uncolored coupler.
• couplers of formula (I) according to the present invention can be added in the same manner as in the addition of conventional couplers described hereinafter.
• the colored couplers of the present invention are used in combination with cyan couplers.
• the cyan couplers are phenol type couplers and naphthol type couplers.
• Preferred examples of the cyan couplers are those described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Patent Application (Laid-Open) No. 3,329,729, European Patents 121,365A and 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212 and 4,296,199 and JP-A-61-42658.
• the colored couplers of the present invention are used in combination with naphthol cyan couplers. It is particularly preferred that the colored couplers of the present invention are used together with naphthol couplers represented by the following formula (C).
• R 1 represents -CONR 4 R 5 , -SO 2 NR 4 R 5 , NHCOR 4 , -NHCOOR 6 , -NHS0 2 R 6 , -NHCONR 4 R 5 or -NHSO 2 NR 4 R 5 ;
• R 2 represents a group attached to the naphthalene ring; l is 0 or an integer of 1 to 3;
• R 3 represents a substituent group;
• X represents a hydrogen atom or a group which is eliminated by the coupling reaction with an oxidized aromatic primary amine developing agent;
• R4 and Rs which may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; and Rs is an alkyl group, an aryl group or a heterocyclic group.
• R 2 groups When t is an integer of two or more, plural R 2 groups may be the same or different, or may be linked to form a ring.
• R 2 and R 3 or R 3 and X may be combined together to form a ring. They may be bonded to each other through a divalent or polyvalent group at a position of Ri, R 2 , R 3 or X to form a dimer or a polymer higher than dimer.
• R 1 is -CONR 4 R 5 , -SO 2 NR 4 R 5 , -NHCOR 4 , -NHCOOR 6 , -NHS0 2 R 6 , -NHCONR 4 Rs or -NHSO 2 NR 4 R 5 ;
• R 4 , Rs and R 6 are each an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 2 to 30 carbon atoms and R 4 . and Rs may be a hydrogen atom.
• R 2 is a group (including an atom; the same applies hereinbelow) which can be attached to the naphthalene ring.
• R 2 include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amino group, a sulfo group, a cyano group, an alkyl group, an aryl group, a heterocyclic group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, an acyl group, an acyloxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoylamino group, an alkoxycarbonylamino group, a nitro
• R 3 is a substituent group and preferably a group represented by the following formula (C-1)
• Y is m is 0 or 1; and R 7 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, -COR s , -OR 1 o, -CO 2 R 10 , -SO 2 OR 10 or -SO 2 R 10 .
• R 8 , Rs and R 10 have the same meaning as R 4 , R 5 and R ⁇ , respectively.
• R i , R4 and R 5 of or in R 7 , R 8 and R g of may be combined together to form a nitrogen-containing heterocyclic ring (e.g., a pyrrolidine ring, piperidine ring, morpholine ring).
• a nitrogen-containing heterocyclic ring e.g., a pyrrolidine ring, piperidine ring, morpholine ring.
• X is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized aromatic primary amine developing agents (a "coupling-off" group or atom).
• the coupling-off group include halogen atoms, thiocynato group and a heterocyclic group having 1 to 30 carbon atoms which is attached to the coupling active site through a nitrogen atom (e.g., a succinimido group, phthalimido group, pyrazolyl group, hydantoinyl group, or 2-benztriazolyl group).
• R 11 has the same meaning as R 6 .
• the above-described alkyl group may be a straight-chain, branched chain or cyclic alkyl group and may have unsaturated bonds or one or more substituent groups (examples of the substituent groups include a halogen atom, a hydroxyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyloxy group and an acyl group).
• substituent groups include a halogen atom, a hydroxyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyloxy group and an acyl group).
• alkyl group examples include methyl, isopropyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, n-dodecyl, n-hexadecyl, 2-methoxyethyl, benzyl, trifluoromethyl, 3-dodecyloxypropyl and 3-(2,4-di-t-pentylphenoxy)propyl.
• the aryl group may be a condensed ring (e.g., naphthyl group) and may have one or more substituent groups (examples of the substituent groups include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group and an arylsulfonyl group).
• substituent groups include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamido group, a carbamoy
• aryl group examples include phenyl, tolyl, pentafluorophenyl, 2-chlorophenyl, 4-hydroxyphenyl, 4-cyanophenyl, 2-tetradecyloxyphenyl, 2-chloro-5-dodecyloxyphenyl and 4-t-butylphenyl.
• the heterocyclic group is a 3-membered to 8-membered monocyclic or condensed ring-form heterocyclic group containing at least one hetero-atom selected from the group consisting of 0, N, S, P, Se and Te as a member of the heterocyclic ring and may have one or more substituent groups (examples of the substituent groups include a halogen atom, a carboxyl group, a hydroxyl group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group and an arylsulfonyl group).
• heterocyclic group examples include 2-pyridyl, 4-pyridyl, 2-furyl, 2- thienyl, benztriazole-1-yl, 5-phenyltetrazole-1-yl, 5-methylthio-1,3,4-thiadiazole-2-yl and 5-methyl-1,3,4-oxadiazole-1-yl.
• Preferred substituent groups of the coupler (C) of the present invention are as follows.
• R 1 is -CONR 4 R s or -SO 2 NR 4 R 5 .
• Examples thereof include carbamoyl, N-n-butylcarbamoyl, N-n-dodecylcarbamoyl, N-(3-n-dodecyloxypropyl)carbamoyl, N-cyclohexylcarbamoyl, N-[3-(2,4-di-t-pentyl- phenoxy)propyl]carbamoyl, N-hexadecylcarbamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl, N-(3-dodecyloxy-2-methylpropyl)carbamoyl, N-[3-(4-t-octylphenoxy)propyl]-carbamoyl, N-hexadecyl-
• R 2 is a halogen atom, an alkyl group (e.g., methyl, isopropyl, t-butyl, cyclopentyl), a carbonamido group (e.g., acetamido, pivalinamido, trifluoroacetamido, benzamido), a sulfonamido (e.g., methanesulfonamido, toluenesulfonamido) or a cyano group.
• an alkyl group e.g., methyl, isopropyl, t-butyl, cyclopentyl
• a carbonamido group e.g., acetamido, pivalinamido, trifluoroacetamido, benzamido
• a sulfonamido e.g., methanesulfonamido, toluenesulfonamido
• X is a hydrogen atom, a halogen atom, -OR 11 [e.g., an alkoxy group such as ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-(2-hydroxyethoxy)ethoxy, 2-methylsulfonylethoxy, ethoxycarbonyl- methoxy, carboxymethoxy, 3-carboxypropoxy, N-(2-methoxyethyl)carbamoylmethoxy, 1-carboxytridecyloxy, 2-methanesulfonamidoethoxy, 2-(carboxymethylthio)ethoxy or 2-(1-carboxytridecylthio)ethoxy or an aryloxy group such as 4-cyanophenoxy, 4-carboxyphenoxy, 4-methoxyphenoxy, 4-t-octylphenoxy, 4-nitrophenoxy, 4-(3-carboxypropaneamido)phenoxy or 4-acetamidophenoxy]
• the couplers of formula (C) may be in the form of a dimer or a higher polymer by combining two or more of them together through a divalent or higher valent group at a position of Ri, R 2 , R 3 or X.
• the number of carbon atoms of each substituent group may be beyond the range described above.
• couplers of formula (C) are in the form of a higher polymer
• typical examples thereof include homopolymers or copolymers of addition polymerizable ethylenically unsaturated compounds having a cyan dye-forming coupler residue (cyan color forming monomers).
• Couplers represented by the following formula (C-2) are preferred.
• G is a repeating monomer unit derived from a color forming monomer and a linking group represented by the following formula (C-3);
• H j is a repeating unit derived from a non-color forming monomer;
• i is a positive integer;
• j is 0 or a positive integer;
• gi and hj are the weight fractions of G i and Hj, respectively.
• G i or H i is composed of two or more repeating units.
• R is a hydrogen atom, a chlorine atom or an alkyl group having 1 to 4 carbon atoms;
• A is -CONH-, -COO- or a substituted or unsubstituted phenylene group;
• B is a divalent group having carbon atoms at both terminals such as a a substituted or unsubstituted alkylene, phenylene or oxydial- kylene group;
• L is -CONH-, -NHCONH-, -NHCOO-, -NHCO-, -OCONH-, -NH-, -COO-, -OCO-, -CO-, -0-, SO z -, -NHSO 2 - or -S0 2 NH-;
• a, b, c are each 0 or 1; and
• Q is a moiety of a cyan coupler formed by removing one hydrogen atom from Ri, R 2 , R 3 or X in the compound
• non-color forming ethylenic monomer represented by H j that are incapable of coupling with an oxidized aromatic primary amine developing agent
• acrylic acid a-chloroacrylic acid, o-alkylacrylic acids (e.g., methacrylic acid), amides and esters derived from these acrylic acids (e.g., acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and j8-hydroxyethyl methacrylate), vinyl esters
• Acrylic esters, methacrylic esters and maleic esters are particularly preferred. These non-color forming ethylenic monomers may be used as a mixture of two or more of them. For example, a combination of methyl acrylate and butyl acrylate, a combination of butyl acrylate and styrene, a combination of butyl methacrylate and methacrylic acid or a combination of methyl acrylate and diacetone acrylamide can be used.
• Ethylenically unsaturated monomers to be copolymerized with the vinyl monomers corresponding to the formula (C) can be chosen so that the forms such as solid, liquid or micelle forms of the resulting copolymers, the physical properties and/or chemical properties (e.g., solubility in water or organic solvents) thereof, the compatibility thereof with binders such as gelatin in photographic colloid compositions, flexibility, thermal stability, the coupling reactivity thereof with the oxidants of developing agents and non- diffusibility in photographic colloid are favorably affected, as is known in the field of polymer couplers.
• These copolymers may be any of a random copolymer and a specific sequence-copolymer (e.g., a block copolymer, an alternating copolymer).
• the number-average molecular weight of the cyan polymer couplers used in the present invention is usually on the order of from several thousands to millions, but oligomer type polymers having a number-average molecular weight of 5000 or less can be used.
• the cyan polymer couplers used in the present invention may be any of lipophilic polymers soluble in organic solvents (e.g., ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone, dibutyl phthalate, tricresyl phosphate), hydrophilic polymers miscible with hydrophilic colloid such as an aqueous gelatin solution and polymers having a structure capable of forming a micelle in hydrophilic colloid.
• organic solvents e.g., ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone, dibutyl phthalate, tricresyl phosphate
• hydrophilic polymers miscible with hydrophilic colloid such as an aqueous gelatin solution and polymers having a structure capable of forming a micelle in hydrophilic colloid.
• lipophilic non-color forming ethylenic monomers e.g., acrylic esters, methacrylic esters, maleic esters, a vinylbenzene
• lipophilic non-color forming ethylenic monomers e.g., acrylic esters, methacrylic esters, maleic esters, a vinylbenzene
• acrylic esters, methacrylic esters, maleic esters, a vinylbenzene are mainly used as copolymerizable components to obtain the lipophilic polymer couplers soluble in organic solvents.
• the lipophilic polymer couplers obtained by polymerizing the vinyl monomers giving the coupler units of formula (3-C) may be prepared by emulsifying and dispersing the solutions of the couplers in organic solvents in the form of a latex in an aqueous gelatin solution or by direct emulsion polymerization.
• a method for emulsifying and dispersing the lipophilic polymer couplers in the form of latex in an aqueous gelatin solution is described in U.S. Patent 3,451,820.
• Emulsion polymerization can be carried out by methods described in U.S. Patents 4,080,211 and 3,370,952.
• hydrophilic non-color forming ethylenic monomers such as N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide, 3-sulfonatopropyl acrylate, sodium styrenesulfonate, potassium styrene-sulfinate, acrylamide, methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone and N-vinylpyridine are used as copolymerizable components to obtain hydrophilic polymer couplers soluble in neutral or alkaline water.
• hydrophilic non-color forming ethylenic monomers such as N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide, 3-sulfonatopropyl acrylate, sodium styrenesulfonate, potassium styrene-sulfinate, acrylamide, methacrylamide, acrylic acid, methacrylic acid, N-viny
• the hydrophilic polymer couplers can be added to coating solutions in the form of an aqueous solution.
• the couplers may be dissolved in a mixed solvent of water and a water-miscible organic solvent such as a lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexanone, ethyl lactate, dimethylformamide or dimethylacetamide and then added. Further, the couplers may be dissolved in an aqueous alkaline solution or an alkaline water-containing organic solvent and then added. A small amount of a surfactant may be added.
• each substituent group in the formula (C) and the cyan couplers of the formula (C) include the following groups and compounds, but the present invention is not to be construed as being limited thereto.
• A represents a cyclohexyl group; represents a cyclopentyl group; and -C 8 H 1 7( t ) represents
• the photographic material of the present invention has a support having thereon at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer.
• a support having thereon at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer.
• a typical example is a silver halide photographic material having at least one sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity, but different light sensitivity, the sensitive layer being a unit sensitive layer having color sensitivity to any one of blue light, green light and red light.
• the unit sensitive layers are generally arranged in the order of a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer from the support.
• the arrangement may be in the reverse order to that described above according to purpose. Further, the arrangement may be such that a different light-sensitive layer is inserted into the same color sensitive layers.
• Non-sensitive layers such as various interlayers may be provided between silver halide sensitive layers, or on the uppermost layer or lowermost layer thereof.
• the interlayers may contain couplers, or DIR compounds described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037 and JP-A-61-20038.
• the interlayers may also contain color mixing inhibitors as used conventionally.
• a plurality of silver halide emulsion layers which constitute each unit sensitive layer preferably include a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent 1,121,470 and U.K. Patent 923,045. It is preferred that the layers are disposed such that light sensitivity is lower toward the support.
• a non-sensitive layer may be provided between silver halide emulsion layers.
• the low-sensitivity emulsion layer may be provided on the farther side from the support and the high-sensitivity emulsion layer may be provided on the side nearer to the support as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543.
• the layer may be arranged in order of low-sensitivity blue-sensitive layer (BL)-/high-sensitivity blue-sensitive layer (BH)/high-sensitivity green-sensitive layer (GH)/low-sensitivity green-sensitive layer (GL)/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL) from the outermost layer, or in order of BH/BUGUGH/RH/RL, or in order of BH/BUGH/GURURH.
• BL low-sensitivity blue-sensitive layer
• BH high-sensitivity blue-sensitive layer
• GH high-sensitivity green-sensitive layer
• GL low-sensitivity red-sensitive layer
• RL high-sensitivity red-sensitive layer
• the arrangement may be made in order of blue-sensitive layer/GH/RH/GURL from the outermost layer as described in JP-B-55-34932. Further, the arrangement may be made in order of blue-sensitive layer/GURUGH/RH from the outermost layer as described in JP-A-56-25738 and JP-A-62-63936.
• the layer structure contains three layers having different light sensitivity in such an arrangement that the upper layer is a silver halide emulsion layer having the highest light sensitivity, the medium layer is a silver halide emulsion layer having a light sensitivity lower than that of the upper layer and the lower layer is a silver halide emulsion layer having a light sensitivity lower than that of the medium layer so that light sensitivity becomes lower toward the support in order as described in JP-B-49-15495.
• the arrangement may be made in order of medium-sensitive emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer from the outermost layer.
• the arrangement may be made in order of high-sensitivity emulsion layer/low sensitivity emulsion layer/medium-sensitivity emulsion layer or in order of low sensitivity emulsion layer/medium-sensitivity emulsion layer/high-sensitivity emulsion layer.
• the layer structure is composed of four or more layers, the above-described various arrangements can be made.
• the preferred silver halide contained in the photographic emulsions of the photographic materials of the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide, each having a silver iodide content of not higher than about 30 mol%. Particularly preferred is silver iodobromide or silver iodochlorobromide, each having a silver iodide content of about 2 mol% to about 25 mol%.
• Silver halide grains in the photographic emulsions may have a regular crystal form such as cube, octahedron or tetradecahedron, an irregular crystal form such as a sphere or tabular form, a crystal having a defect such as a twinning plane or a composite form thereof.
• the size of silver halide grains may be in the range of from fine grains having a grain size of not larger than about 0.2 l lm to large-size grains having a grain size of about 10 ⁇ rn in terms of the diameter of projected area. Any of a polydisperse emulsion and monodisperse emulsion may be used.
• the silver halide photographic emulsions of the present invention can be prepared according to the methods described in Research Disclosure (RD) No. 17643 (December 1978) pp 22-23 I. Emulsion Preparation and Types ; ibid. No. 18716 (November 1979), p. 648; ibid. No. 307105 (November 1989), pp 863-865; P. Glafkides, Chimie et Phisique Photographique (Paul Montel 1967), G.F. Duffin, Photographic Emulsion Chemistry (Focal Press 1966) and V.L. Zelikman et al, Making and Coating Photographic Emulsion (Focal Press 1964).
• Tabular grains having an aspect ratio of not lower than about 3 can be used in the present invention.
• the tabular grains can be easily prepared by the methods described in Gutoff, Photographic Science and Engineering , Vol. 14, pp 248-257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and U.K. Patent 2,112,157.
• Grains having a uniform crystal structure or a crystal structure different in halogen composition between the interior thereof and the surface thereof can be used.
• Grains having a laminar crystal structure may be used.
• Silver halide having a different composition may be joined to the grains by epitaxial growth.
• a compound such as silver rhodanide or lead oxide other than silver halide may be joined to the grains.
• a mixture of grains having various crystal forms may be used.
• the internal latent image type emulsion may be a core/shell type internal latent image type emulsion described in JP-A-63-264740.
• a method for preparing the core/shell type internal latent image type emulsion is described in JP-A-59-133542.
• the thickness of the shell of the emulsion varies depending on processing conditions, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.
• Silver halide emulsions are usually subjected to physical ripening, chemical ripening and spectral sensitization and then used. Additives used for these stages are described in Research Disclosure No. 17643, ibid. No. 18716 and ibid. No. 30716 and listed in a Table below.
• two or more emulsions differing in at least one of grain size, grain size distribution, halogen composition, grain form and sensitivity of the sensitive silver halide emulsion can be mixed in the same layer.
• Silver halide grains wherein the surfaces of grains are fogged as described in U.S. Patent 4,082,553, silver halide grains wherein the interiors of grains are fogged as described in U.S. Patent 4,626,498 and JP-A-59-214852 and colloidal silver can be preferably used in light-sensitive silver halide emulsion layers and/or substantially non-light-sensitive hydrophilic colloid layers.
• the term "silver halide grains wherein the interiors or surfaces of grains are fogged" as used herein refers to silver halide grains which can be developed uniformly (non-imagewise) irrespective of the unexposed area or exposed area of the photographic material. Methods for preparing silver halide grains wherein the interiors or surfaces of the grains are fogged are described in U.S. Patent 4,626,498 and JP-A-214852.
• the silver halide which forms the internal nucleus of the core/shell type silver halide grains wherein the interiors of the grains are fogged may be grains having the same halogen composition or different halogen compositions. Any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used as silver halide wherein the interiors or surfaces of the grains are fogged. Though there is no particular limitation with regard to the grain size of these fogged silver halide grains, mean grain size is preferably 0.01 to 0.75 um, particularly preferably 0.05 to 0.6 u.m. There is no particular limitation with regard to the shape of grains.
• Grains may have a regular crystal form, and the emulsion may be polydisperse emulsion, but a monodisperse emulsion is preferred in which at least 95% (in terms of weight or the number of grains) of silver halide grains is composed of grains having a grain size within the mean grain size ⁇ 40%.
• non-light-sensitive finely divided silver halide grains are used in the present invention.
• non-sensitive finely divided silver halide grains refers to finely divided silver halide grains which are not light-sensitive during imagewise exposure for obtaining a dye image and are substantially not developed in the processing stage. Grains which are previously not fogged are preferable.
• Finely divided silver halide grains have a silver bromide content of 0 to 100 mol% and may optionally contain silver chloride and/or silver iodide. Grains containing 0.5 to 10 mol% of silver iodide are preferred.
• Finely divided silver halide grains have a mean grain size (the mean value of diameters of the circles having areas corresponding to projected areas) of preferably 0.01 to 0.5 urn, more preferably 0.02 to 0.2 ⁇ m.
• Finely divided silver halide grains can be prepared in the same manner as in the preparation of usual light-sensitive silver halides. In the preparation of finely divided silver halide grains, it is not necessary that the surfaces of silver halide grains be optically sensitized or spectrally-sensitized. However, it is preferred that a conventional stabilizer such as triazole, azaindene, benzthiazolium, a mercapto compound or a zinc compound be added before the finely divided silver halide grains are added to coating solutions. Colloidal silver is preferably incorporated in layers containing the finely divided silver halide grains.
• the coating weights of coating solutions to be coated on the photographic materials of the present invention are preferably not more than 6.0 g/m 2 , more preferably not more than 4.5 g/m 2 in terms of silver.
• the photographic materials of the present invention contain fogging agents, development accelerators and solvents for silver halide or compounds releasing their precursors as described in JP-A-1-106052, irrespective of the amount of developed silver formed by development.
• dyes dispersed by the methods described in W088/04794 and Published PCT Application No. 502912/1989 (in Japan) or dyes described in EP317,308A, U.S. Patent 4,420,555 and JP-A-1-259358 are incorporated in the photographic materials of the present invention.
• color couplers can be used in the present invention. Examples thereof are described in patent specifications cited in the above-described Research Disclosure No. 17643, VII-C to G and ibid. No. 307105, VII-C to G.
• yellow couplers include those described in U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752 and 4,248,961, JP-B-58-10739, U.K. Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968, 4,314,023 and 4,511,649 and European Patent 249,473A.
• magenta couplers are preferred as magenta couplers. Particularly preferred are magenta couplers described in U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Patents 4,500,630, 4,540,654 and 4,556,630 and W088/04795.
• preferred cyan couplers include those described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Patent Application (Laid-Open) No. 3,329,729, European Patents 121,365A and 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,254,212 and 4,296,199 and JP-A-61-42658.
• couplers capable of releasing a compound residue having a water-soluble 6-hydroxy-2-pyridone-5-azo group there are preferred compounds described in Research Disclosure No. 17643, item VII-G, ibid. No. 307105, item VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258 and U.K. Patent 1,146,368, as colored couplers for correcting the unnecessary absorption of developed dyes. It is also preferred to use couplers for correcting the unnecessary absorption of developed dyes by fluorescent dyes released during coupling as described in U.S. Patent 4,774,181 or couplers having, as an elimination group, a dye precursor group capable of reacting with developing agents to form a dye as described in U.S. Patent 4,777,120.
• couplers which release imagewise nucleating agents or development accelerators during development there are preferred those described in U.K. Patents 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840.
• Compounds which release fogging agent, development accelerator and solvents for silver halide by a redox reaction with oxidized developing agents as described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-45687 are also preferred.
• Couplers used in the present invention can be introduced into photographic materials by various known dispersion methods.
• Examples of the high-boiling organic solvents which have a boiling point of not lower than 175°C at normal pressure used in the oil-in-water dispersion method include phthalic esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate), phosphoric or phosphonic esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate,
• Organic solvents having a boiling point of not lower than about 30 C, preferably not lower than about 50 C, but not higher than about 160 C can be used as co-solvents.
• the co-solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.
• antiseptic and antifungal agents such as 1,2-benzoisothiazoline-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941 and phenethyl alcohol are added to the color photographic materials of the present invention.
• antiseptic and antifungal agents such as 1,2-benzoisothiazoline-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941 and phenethyl alcohol are added to the color photographic materials of the present invention.
• the present invention can be applied to various color photographic materials.
• Typical examples of the color photographic materials according to the present invention include general-purpose and movie color negative films, reversal color films for slide or TV, color paper, color positive films and reversal color paper.
• Examples of supports which can be used in the present invention include those described in the above-described RD No. 17643 (page 28), RD No. 18716 (right column of page 647 to left column of page 648) and RD No. 307105 (page 879).
• the total of the layer thicknesses of the entire hydrophilic colloid layers on the emulsion layer side thereof is preferably not more than 28 u.m, more preferably not more than 23 ⁇ m, still more preferably not more than 18 u.m, particularly preferably not more than 16 ⁇ m.
• the layer-swelling rate T 1/2 is preferably not longer than 30 seconds, more preferably not longer than 20 seconds.
• the layer thickness refers to a layer thickness obtained by measuring the thickness of a layer at 25 C and 55% RH under air conditioning (2 days).
• the layer-swelling rate T 1/2 can be measured by known method in the field of photography, for example, by using a swellometer described in A. Green et al., Photogr. Sci.
• T 1/2 is defined as the time taken until layer thickness reaches 1/2 of saturated layer thickness when processing is conducted with a color developing solution at 30° C for 3 min 15 sec and 90% of the attainable maximum swollen layer thickness is referred to as saturated layer thickness.
• the layer-swelling rate T 1/2 can be controlled by adding a hardening agent to gelatin as a binder or by changing conditions with time after coating.
• a swelling ratio of 150 to 400% is preferred.
• the swelling ratio can be calculated from the maximum swollen layer thickness under the above conditions by using the formula (maximum swollen layer thickness - layer thickness)/layer thickness.
• the photographic material of the present invention be provided with hydrophilic layer (referred to as a backing layers having a total dry thickness of 2 to 20 ⁇ m on the opposite side to the emulsion layer side. It is preferred that the backing layer contain a light absorber, filter dye, ultraviolet light absorber, antistatic agent, hardening agent, binder, plasticizer, lubricant, coating aid, and surfactant.
• the swelling ratio of the backing layer is preferably 150 to 500%
• the color photographic materials of the present invention can be developed according to conventional methods described in RD No. 17643 (pp 28-29), RD No. 18716 (left column to right column of page 651) and RD No. 307105 (pp 880-881).
• Color developing solutions which can be used in the processing of the photographic materials of the present invention are preferably aqueous alkaline solutions mainly composed of aromatic primary amine color developing agents. Aminophenol compounds are useful as the color developing agents and p-phenylenediamine compounds are preferred as the color developing agents.
• Typical examples thereof include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-S-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-0-methoxyethylaniline and salts thereof such as sulfate, hydrochloride and p-toluenesulfonate.
• 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate is particularly preferred. These compounds may be used either alone or in combination of two or more of them according to purpose.
• the color developing solutions contain pH buffering agents such as alkali metal carbonates, borates and phosphates, developed restrainers such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles and mercapto compounds and anti-fogging agents.
• pH buffering agents such as alkali metal carbonates, borates and phosphates
• developed restrainers such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles and mercapto compounds and anti-fogging agents.
• the color developing solutions may optionally contain preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazine such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids; organic solvents such as ethylene glycol and diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines; color forming couplers, competitive couplers; auxiliary developing agents such as 1-phenyl- 3-pyrazolidone; tackifiers; and chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyeth
• Black-and-white developing solutions may contain conventional developing agents such as dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone) and aminophenols (e.g., N-methyl-p-aminophenol). These developing agents may be used either alone or in combination of two or more of them.
• dihydroxybenzenes e.g., hydroquinone
• 3-pyrazolidones e.g., 1-phenyl-3-pyrazolidone
• aminophenols e.g., N-methyl-p-aminophenol
• the pH of the color developing solutions and the black-and-white developing solutions is generally in the range of 9 to 12.
• the replenishment rate of these developing solutions varies depending on the types of the color photographic materials, but is usually not more than 3 1 per m 2 of the photographic material.
• the replenishment rate can be reduced to 500 ml or less when the concentration of bromide ion in the replenisher is reduced.
• the contact area of the photographic processing solution with air in the processing tank is represented by opening ratio defined below.
• the opening ratio is preferably not higher than 0.1, more preferably 0.001 to 0.05.
• Methods for reducing the opening ratio include a method wherein a cover such as a floating lid is provided on the surface of the photographic processing solution in the processing tank; a method wherein a movable lid is used as described in JP-A-1-82033; and a slit development method described in JP-A-63-216050. It is preferred the opening ratio be reduced not only for color development and black and white development stages, but also all of the subsequent stages such as bleaching, bleaching- fixing, fixing, rinsing and stabilization stages.
• the replenishment rate can be reduced by inhibiting the accumulation of bromide ion in the developing solution.
• Color development is usually 2 to 5 minutes. However, when a higher temperature and a higher pH are used and the color developing agents are used at a higher concentration, processing time can be shortened.
• the photographic emulsion layer is generally bleached.
• Bleaching may be carried out simultaneously with fixing (bleaching-fixing treatment) or separately carried out.
• a bleaching-fixing treatment may be conducted to expedite processing. Processing may be conducted with a bleaching-fixing bath composed of two consecutive baths. Fixing may be conducted before the bleaching-fixing treatment.
• bleaching may be conducted according to purpose. Examples of bleaching agents include compounds of polyvalent metals such as iron(III), peracids, quinones and nitro compounds.
• Typical examples of the bleaching agents include organic complex salts of iron(III) such as complex salts of aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid), citric acid, tartaric acid, and malic acid.
• aminopolycarboxylic acids e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid
• citric acid tartaric acid
• malic acid e.g., citric acid, tartaric acid, and malic acid
• iron(III) complex salts of aminopolycarboxylic acids such as (ethylenediaminetetraacetonato)-iron(lll) complex and (1,3-diaminopropanetetraacetonato)iron(III) complex are preferred for rapid processing and prevention of environmental pollution.
• iron(III) complex salts of aminopolycarboxylic acids are useful for bleaching solutions and bleaching-fixing solutions.
• the pH of the bleaching solutions containing the iron(III) complex salts of aminopolycarboxylic acids and the bleaching-fixing solutions containing the iron(III) complex salts is generally in the range of 4.0 to 8. A lower pH may be used to expedite processing.
• the bleaching solution, the bleaching-fixing solution and the pre-bath thereof may contain bleaching accelerators.
• the bleaching accelerators include compounds having a mercapto group or disulfide group described in U.S. Patent 3,893,858, West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426 and Research Disclosure No.
• the compounds having a mercapto group or disulfide group are preferred for their high accelerating effect.
• Patent 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are preferred. Further, the compounds described in U.S. Patent 4,552,834 are preferred. These bleaching accelerators may be incorporated in the photographic materials. These bleaching accelerators are particularly effective in conducting bleaching-fixing of the color photographic materials for photographing.
• the bleaching solution and the bleaching-fixing solution contain organic acids to prevent stain from being caused by bleaching.
• organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5.
• organic acids examples include acetic acid and propionic acid.
• fixing agents used in the fixing solution and the bleaching-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of an iodide.
• the thiosulfates are widely used as the fixing agents. Particularly, ammonium thiosulfate is most widely used.
• a combination of a thiosulfate with a thiocyanate, a thioether compound or a thiourea is also preferred.
• Sulfites, bisulfites, carbonyl bisulfite adducts and sulfinic acid compounds described in European Patent 294769A are preferred as preservatives for the fixing solution and the bleaching-fixing solution. It is also preferred that aminopolycarboxylic acids or organic phosphonic acids are added to the fixing solution or the bleaching-fixing solution to stabilize the solution.
• compounds having a pKa of 6.0 to 9.0 preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole, in an amount of 0.1 to 10 mol/1 are added to the fixing solution or the bleaching-fixing solution to adjust the pH.
• Desilvering time is preferably 1 to 3 min, more preferably 1 to 2 min.
• Processing temperature is 25 to 50 C, preferably 35 to 45 C. When desilvering is carried out at a temperature within the preferred range, the desilvering rate is increased and stain is effectively prevented from being formed after processing.
• agitation in the desilvering stage be intensified as much as possible.
• Methods for intensifying agitation include a method wherein a jet of the processing solution collides with the surfaces of the emulsions of photographic materials as described in JP-A-62-183460; a method wherein stirring is improved by a rotating means as described in JP-A-62-183461; a method wherein a wiper blade provided in the solution is brought into contact with the surfaces of the emulsions, the photographic material is transferred to thereby form a turbulent flow, whereby a stirring effect is improved; and a method wherein the whole amount of the processing solution circulated is increased.
• Such means for improving agitation are effectively applicable to any of the bleaching solution, the bleaching-fixing solution and the fixing solution. It is believed that an improvement agitation accelerates the feed of the bleaching solution and the fixing solution into the emulsion layers and as a result, the desilvering rate is enhanced.
• the above-described means for improving agitation is more effective when the bleaching accelerators are used. The accelerating effect can be greatly increased and the problem of inhibiting fixation caused by the bleaching accelerators can be solved.
• automatic processors for use in the processing of the photographic materials of the present invention be provided with photographic material conveying means described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259.
• the conveying means can greatly reduce the amount of the processing solution brought over from the previous bath to the subsequent bath so that preservation of the performance of the processing solution is very high. This is particularly effective in shortening the processing time in each stage or reducing the replenishment rate of the processing solution.
• the silver halide color photographic materials of the present invention are subjected to washing and/or stabilization after desilvering.
• the amount of rinsing water in the washing stage varies widely depending on the characteristics (e.g., depending on materials used such as couplers) of the photographic materials, their use, the temperature of rinsing water, the number of rinsing tanks (the number of stages), replenishing system (countercurrent, direct flow) and other conditions.
• the relationship between the amount of water and the number of rinsing tanks in the multi-stage countercurrent system can be determined by the method described in Journal of the Society of Motion Picture and Television Engineers , Vol. 64, p. 248-253 ( May 1955).
• the amount of rinsing water can be greatly reduced.
• the residence time of water in the tanks is prolonged and as a result, bacteria are grown and the resulting suspended matter is deposited on the photographic material.
• a method for reducing calcium ion and magnesium ion concentrations described in JP-A-62-288838 can be effectively used for the color photographic materials of the present invention to solve this problem.
• isothiazolone compounds thiabendazole compounds, chlorine-containing germicides such as sodium chlorinated isocyanurate and benztriazole described in JP-A-57-8542 and germicides described in Chemistry of Germicidal Antifungal Agent , (1986) written by Hiroshi Horiguchi (Sankyo Shuppan), Sterilization, Disinfection , Antifungal Technique , edited by Sanitary Technique Society and Antibacterial and Antifungal Cyciopedie , (1986) edited by Nippon Antibacterial Antifungal Society, can be used.
• the pH of rinsing water in the treatment of the photographic materials of the present invention is in the range of 4 to 9, preferably 5 to 8.
• the temperature of rinsing water and washing time vary depending on the characteristics of the photographic materials and use, but the temperature and time of washing are generally 15 to 45 C for 20 seconds to 10 minutes, preferably 25 to 40 C for 30 seconds to 5 minutes.
• the photographic materials of the present invention may be processed directly with stabilizing solutions in place of rinsing water. Such stabilizing treatment can be carried out by conventional methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345.
• a stabilizing treatment subsequent to rinsing may be conducted.
• the stabilizing treatment may be used as the final bath for the color photographic materials for photographing.
• An example thereof include a stabilizing bath containing a dye stabilizer and a surfactant.
• the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N- methylol compounds, hexamethylenetetramine and aldehyd-sulfite adducts.
• the stabilizing bath may contain various chelating agents and antifungal agents.
• Overflow solution from the replenishment of rinsing water and/or stabilizing can be reused in other stages such as desilvering stage.
• the color developing agents may be incorporated in the silver halide color photographic materials of the present invention for the purpose of simplifying and expediting processing. It is preferred that precursors for the color developing agents are used for the incorporation thereof in the photographic materials. Examples of the precursors include indoaniline compounds described in U.S. Patent 3,342,597; Schiff base compounds described in U.S. Patent 3,342,599 Research Disclosure No. 14850 and ibid. , No. 15159; aldol compounds described in Research Disclosure No. 13924; metal complex salts described in U.S. Patent 3,719,492; and urethane compounds described in JP-A-53-135628.
• 1-phenyl-3-pyrazolidones may be incorporated in the silver halide color photographic materials of the present invention for the purpose of accelerating color development.
• Typical examples of the compounds include those described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
• various processing solutions are used at a temperature of 10 to 50 C.
• a temperature of 33 to 38 * C is used.
• a higher temperature can be used to accelerate processing and to shorten processing time, while a lower temperature is used to improve image quality and to improve the stability of the processing solutions.
• the silver halide photographic materials of the present invention include heat developable photosensitive materials described in U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056 and European Patent 210,660A2.
• a sample 102 was prepared in the same way as in the preparation of the sample 101 except that comparative colored coupler R-1 in an amount of 0.08 g/m 2 was added to the emulsion layer.
• Each of samples 103 to 107 was prepared in the same way as in the preparation of the sample 102 except that an equimolar amount of each of couplers indicated in Table 1 was used in place of the coupler R-1.
• a sample 108 was prepared in the same way as in the preparation of the sample 104 except that tricresyl phosphate was omitted from the emulsion layer.
• Each of samples 109 to 111 was prepared in the same way as in the preparation of the sample 108 except that an equimolar of each of a coupler component composed of C-7/C-30 (molar ratio: 3/1), a coupler component composed of C-7/C-10 (molar ratio: 2/1) and a coupler component composed of C-10 was used in place of the coupler C-30.
• Each of samples 112 to 113 was prepared in the same way as in the preparation of the sample 111 except that an equimolar amount of each of colored coupler 13 and 28 was used in place of colored coupler used for the sample 111.
• Each processing solution used in each stage had the following composition.
• the surface of a cellulose triacetate film support having an undercoat layer applied thereto was multi- coated with the following layers having the following compositions to prepare a multi-layer color photographic material as a sample 201.
• the values for each component are coating weights in terms of g/m 2.
• the amount of silver halide is the coating weight in terms of silver.
• the amounts of sensitizing dyes are represented by moles per mol of silver halide in the same layer.
• a hardening agent H-1 for gelatin and surfactant were added to each layer.
• a sample 202 was prepared in the same way as in the preparation of the sample 201 except that an equimolar amount of the coupler (3) of the present invention was used in place of colored coupler EX-3 used in each of the fourth and fifth layers of the sample 201.
• a sample 203 was prepared in the same way as in the preparation of the sample 201 except that an equimolar amount of cyan coupler C-7 (preferably used in the present invention) was used in place of EX-2 used in each of the third, fourth and fifth layers of the sample 201 and an equimolar amount of cyan coupler C-34 was used in place of EX-4 used in the fifth layer of the sample 201.
• an equimolar amount of cyan coupler C-7 (preferably used in the present invention) was used in place of EX-2 used in each of the third, fourth and fifth layers of the sample 201 and an equimolar amount of cyan coupler C-34 was used in place of EX-4 used in the fifth layer of the sample 201.
• Each of samples 204 to 208 was prepared in the same way as in the preparation of the sample 203 except that an equimolar amount of each of the couplers (1), (2), (3), (4) and (24) of the present invention was used in place of colored coupler EX-3 used in each of the fourth and fifth layers of the sample 203.
• Relative sensitivity was a relative value which was determined by the logarithm of the reciprocal of exposure amount giving a cyan density of (Fog + 0.2) when the sensitivity of the sample 201 was referred to as 0.
• Color turbidity was the value obtained by subtracting the fogged yellow density from the yellow density at a density giving a cyan density of (Fog + 1.5).
• Cyan density at a point of an initial density of 1.00 was referred to as a density after forced deterioration.
• Color development was carried out at 38 C under the following conditions by using an automatic processor.
• rinse (1) and (2) were a countercurrent rinse system from (2) to (1).
• Each processing solution had the following composition.
• the replenishment rate of each processing solution was such that the replenishment rate of color developing solution was 1200 ml per m 2 of the color photographic material and that of each of other processing solutions including rinse was 800 ml.
• the amount of the processing solution came over from the previous-bath to the rinse stage was 50 ml per m 2 of the color photographic material.
• Tap water containing calcium ion (32 mg/l) and magnesium ion (7.3 mg/l) was passed through a column packed with an H type strongly acidic cation exchange resin and an OH type strongly basic anion exchange resin to reduce calcium ion to 1.2 mg/l and magnesium ion to 0.4 mg/l.
• Sodium isocyanurate dichloride in amount of 20 mg/l was then added to the treated water.
• Drying temperature was 50 C.
• each of samples 301 to 303 was prepared in the same way as in the preparation of the sample 201 except that each of the couplers (24), (26) and (28) of the present invention in an amount of 0.008 g/m 2 was added to the three layers of the seventh, eighth and ninth layers of the sample 201.
• a cellulose triacetate film support having an undercoat applied thereto was coated with the following layers having the following compositions to prepare a multi-layer color photographic material as a sample 401.
• Second Layer Low-sensitivity Red-sensitive Emulsion Layer
• Twelfth Layer Low-sensitivity Blue-sensitive Emulsion Layer
• stabilizer Cpd-3 (0.07 g/m 2 ) for emulsions and surfactants W-1 (0.006 g/m 2 ), W-2 (0.33 g/m 2 ) and W-3 (0.10 g/m 2 ) as coating aid or emulsifying dispersant were added to each layer.
• 1,2-benzisothiazoline-3-one, 2-phenoxyethanol and phenethyl alcohol were added to improve mildewproofness and antifungal properties.
• a sample 402 was prepared in the same way as in the preparation of the sample 401 except that comparative colored coupler R-1 in an amount of 0.020 g/m 2 , 0.025 g/m 2 and 0.050 g/m 2 was added to the first layer, the second layer and the fourth layer of the sample 401, respectively.
• Each of samples 403 to 408 was prepared in the same way as in the preparation of the sample 402 except that an equal weight of each of colored couplers indicated in Table 4 was used in place of colored coupler R-1.
• Example 2 Relative sensitivity and color turbidity were determined in the same manner as in Example 2.

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