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
  • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
  • G03C7/3005—Combinations of couplers and photographic additives
  • G03C7/3008—Combinations of couplers having the coupling site in rings of cyclic compounds and photographic additives
  • G03C7/301—Combinations of couplers having the coupling site in pyrazoloazole rings and photographic additives
• • 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
  • G03C7/36—Couplers containing compounds with active methylene groups
  • G03C7/38—Couplers containing compounds with active methylene groups in rings
  • G03C7/381—Heterocyclic compounds
  • G03C7/382—Heterocyclic compounds with two heterocyclic rings
  • G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms
  • G03C7/3835—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms four nitrogen atoms
• • 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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/39212—Carbocyclic
  • G03C7/39216—Carbocyclic with OH groups

Definitions

• the present invention relates to a silver halide color photographic material, and more particularly, to a silver halide color photographic material that forms a dye image which is stable against heat or light and in which no stain is likely to occur.
• the oxidized product of an aromatic primary amine color developing agent enters into coupling reaction with a color former to form a color image composed of, for example, indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine or other dyes similar thereto.
• color reproduction is usually achieved by the substractive process using a silver halide color photographic material wherein blue-, green- and red-sensitive silver halide emulsion layers contain color formers, or couplers that will develop colors which are the respective complements of blue, green and red, namely, yellow, magenta and cyan colors.
• An illustrative coupler used to form a yellow color image is acylacetanilide compound.
• exemplary magenta image forming couplers include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole and indazolone compounds.
• couplers commonly used for cyan image formation are included phenolic and naphtholic compounds.
• the dye images formed by the coupling reaction with such color formers and the oxidation product of aromatic primary amine color developing agent are required to undergo no discoloration or fading even if they are exposed to light or stored under hot and humid atmosphere for a prolonged period. It is also required that the background of a silver halide color photographic material (to be hereunder referred to simply as a color photographic material) or the areas where no color has formed should not undergo any yellow staining (hereunder Y staining) as a result of exposure to light or moist heat.
• Magenta couplers are much more sensitive than yellow and cyan couplers to Y staining in the background caused by heat or moist heat as well as to the fading of the image areas resulting from prolonged exposure to light, and this has often caused serious problems in conventional color photography.
• Couplers extensively used for magenta dye formation are 5-pyrazolones. Dyes produced from such compounds generally have primary absorption at about 550 nm but they also have secondary absorption at about 430 nm. In order to minimize such secondary absorption, various efforts have been made. For example, magenta couplers having an anilino group at 3-position of 5-pyrazolones have relatively small degree of secondary absorption and are particularly useful for obtaining color images in print format. Details of this technique are found in U.S. Patent No. 2,343,703 and British Patent No. 1,059,994. However, such substituted magenta couplers are very poor in image keeping quality, especially in the fastness of color image to light. In addition, the background is highly sensitive to Y staining.
• magenta couplers that have been proposed as means capable of reducing the secondary absorption at about 430 nm include pyrazolobenzimidazoles (British Patent No. 1,047,612), indazolones (U.S. Patent No. 3,770,447), lH-pyrazolo-[5,1-c]-1,2,4-triazole type couplers (U.S. Patent No. 3,725,067 and British Patent Nos. 1,252,418 and 1,334,515), 1H-pyrazolo-[1,5-b]-1,2,4-triazole type couplers (Research Disclosure No.
• the azomethine dye formed from these couplers has a very small degree of fastness of light.
• such dye is highly likely to discolor upon exposure to light and has yet to be used commercially in color photographic materials, especially in color prints which are subject to considerable degradation resulting from the discoloration of dyes.
• Unexamined Published Japanese Patent Application No. 125732/1984 proposes a technique for improving the light fastness of the magenta dye image from the 1H-pyrazolo-[5,1 - c]-1,2,4-triazole type magenta coupler by using it in combination with a phenolic compound or a phenyl ether compound.
• this technique is not completely satisfactory in preventing the magenta dye image from fading upon exposure to light, and is practically incapable of preventing the light discoloration of such dye image.
• One object, therefore, of the present invention is to provide a color photographic material that is capable of faithfyl color reproduction and which exhibits a highly improved light fastness in magenta dye image.
• Another object of the invention is to provide a color photographic material producing a magenta dye image that experiences a minimal degree of discoloration upon exposure to light.
• a further object of the invention is to provide a color photographic material that is protected against the occurrence of Y stain in the background resulting from exposure to light or moist heat.
• a silver halide color photographic material containing a magenta color image-forming coupler represented by the following formula (I) and a compound represented by the following formula (II): wherein Z represents the group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic ring, provided that the ring to be formed by said Z may have a substituent;
• the substituent represented by R includes, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkinyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, a spiro-compound residue, a bridged hydrocarbon compound residue, an alkoxy group, an aryloxy group, a heterocyclicoxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an acylamino group, a sulfonamide group, an imido group, a ureido group, a
• the halogen atom includes, for example, chlorine and bromine atoms, the chlorine atom being particularly preferable.
• the alkyl group represented by R is preferably one having 1 to 32 carbon atoms
• the alkenyl group and the alkinyl group are preferably those having 2 to 32 carbon atoms
• the cycloalkyl group and the cycloalkenyl group are preferably those having 3 to 12, particularly 5 to 7, carbon atoms, the alkyl, alkenyl and alkinyl groups each including those having a straight or branched chain.
• alkyl, alkenyl, alkinyl, cycloalkyl and cycloalkenyl groups each may have one or more substituents.
• substituents include, in addition to an aryl group, a cyano group, a halogen atom, a heterocyclic group, a cycloalkyl group, a cycloalkenyl group, a spiro-compound residue and a bridged hydrocarbon compound residue, for example, those substituted through the carbonyl group, such as acyl, carboxy, carbamoyl, alkoxycarbonyl and aryloxycarbonyl groups, and those substituted through the hetero atom, for example, those substituted through the oxygen atom, such as hydroxy, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy and carbamoyloxy groups, those substituted through the nitrogen atom, such as nitro, amino (including dialkylamino and the like), sulfamonylamin
• alkyl group represented by R examples include, for example, methyl, ethyl, isopropyl, t-butyl, pentadecyl, heptadecyl, 1-hexylnonyl, 1,1'-dipentylnonyl, 2-chloro-t-butyl, trifluoromethyl, 1-ethoxytridecyl, 1-methoxyisopropyl, methanesulfonylethyl, 2,4-di-t-amylphenoxymethyl, anilino, 1-phenylisopropyl, 3-m-butanesulfonaminophenoxypropyl, 3-4'- ⁇ a-[4"(p-hydroxy- benzenesulfonyl)phenoxy]dodecanoylamino ⁇ phenylpropyl, 3- ⁇ 4'-[ ⁇ -(2",4"-di-t-amylphenoxy)butaneamido]phenyl
• the aryl group represented by R is preferably a phenyl gruop, and may have a substituent such as an alkyl, alkoxy or acylamino group.
• aryl group examples include phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecaneamido- phenyl, hexadecyl-oxyphenyl and 4'-[a-(4"-t-butylphenoxy)-tetoradecaneamido]phenyl groups.
• the heterocyclic group represented by R is preferably a 5- to 7-membered heterocyclic ring, and may be substituted or may be condensed.
• Examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-pyrimidinyl and 2-benzothiazonyl groups.
• the acyl group represented by R includes, for example, an alkylcarbonyl group such as acetyl, phenylacetyl, dodecanoyl and a-2,4-di-t-amylfenoxybutanoyl groups, and an arylcarbonyl group such as benzoyl, 3-pentadecycloxy- benzoyl and p-chlorobenzoyl groups.
• alkylcarbonyl group such as acetyl, phenylacetyl, dodecanoyl and a-2,4-di-t-amylfenoxybutanoyl groups
• arylcarbonyl group such as benzoyl, 3-pentadecycloxy- benzoyl and p-chlorobenzoyl groups.
• the sulfonyl group represented by R includes, for example, an alkylsulfonyl group such as methylsulfonyl and dodecylsulfonyl groups, and an arylsulfonyl group such as benzenesulfonyl and p-toluenesulfonyl groups.
• the sulfinyl group represented by R includes, for example, an alkylsulfinyl group such as ethylsulfinyl; octylsulfinyl and 3-fenoxybutylsulfinyl groups and an arylsulfinyl group such as phenylsulfinyl and m-penta- decylphenylsulfinyl groups.
• the phosphonyl group represented by R includes, for example, an alkylphosphonyl group such as butyloxyoctyl phosphonyl group, an alkoxyphosphonyl group such as octyloxyphosphonyl group, an aryloxyphosphonyl group such as phenoxyphosphonyl group and an arylphosphonyl group such as phenylphosphonyl group.
• the carbamoyl group represented by R includes, for example, those substituted with an alkyl or aryl (preferably phenyl) group, such as, N-methylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-pentadecyloctylethyl)carbamoyl, N-ethyl-N-dodecylcarbamoyl and N- ⁇ 3-(2,4-di-t-amylphenoxy)-propyl ⁇ carbamoyl group.
• an alkyl or aryl (preferably phenyl) group such as, N-methylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-pentadecyloctylethyl)carbamoyl, N-ethyl-N-dodecylcarbamoyl and N- ⁇ 3-(2,4-di-t-a
• the sulfamoyl group represented by R includes, for example, those substituted with an alkyl or aryl (preferably phenyl) group, such as N-propylsulfamoyl, N,N-diethylsulfamoyl, N-(2-pentadecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl and N-phenylsulfamoyl groups.
• an alkyl or aryl (preferably phenyl) group such as N-propylsulfamoyl, N,N-diethylsulfamoyl, N-(2-pentadecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl and N-phenylsulfamoyl groups.
• the spiro-compound residue represented by R includes, for example, spiro[3,3]heptan-1-yl and the like.
• the bridged hydrocarbon compound residue represented by R includes, for example, bicyclo[2,2,1]heptane-1-yl, tricyclo[3,3,1,1 3,7 ]decane-1-yl and 7,7-dimethyl-bicyclo-[2,2,1]heptane-1-yl.
• the alkoxy group reprented by R includes, for example, those substituted further with such a substituent(s) as is shown above with the alkyl group, such as methoxy, propoxy, 2-ethoxyethoxy, pentadecyloxy, 2-dodecyloxy- ethoxy and phenethyloxyethoxy.
• the aryloxy group represented by R is preferably a phenyloxy group, and includes, for example, those of which aryl nucleus is further subsituted with such a substituent(s) or an atom(s) as is shown above with the aryl group, such as phenoxy, p-t-butylphenoxy and m-pentadecylphenoxy groups.
• the heterocyclicoxy group represented by R is preferably one having a 5- to 7-membered heterocyclic ring, and includes those of which heterocyclic ring has a substituent, such as 3,4,5,6-tetrahydropyranyl-2-oxy and 1-phenyltetrazole-5-oxy groups.
• the siloxy group represented by R includes those substituted with an alkyl group, for example, trimethyl- siloxy, triethylsiloxy and dimethylbutylsiloxy groups.
• the acyloxy group represented by R includes, for example, alkylcarbonyloxy and arylcarbonyloxy groups, and further includes those having a substituent(s) such as acetyloxy, a-chloroacetyloxy and benzoyloxy groups.
• the carbamoyloxy group represented by R includes those substituted with an alkyl or aryl group, such as N-ethylcarbamoyloxy, N,N-diethylcarbamoyloxy and N-phenylcarbamoyloxy groups.
• the amino group represented by R includes those substituted with an alkyl or aryl (preferably phenyl) group, such as ethylamino, anilino, m-chloroanilino, 3-pentadecyloxycarbonylanilino and 2-chloro-5-hexa- decaneamidoanilino groups.
• an alkyl or aryl (preferably phenyl) group such as ethylamino, anilino, m-chloroanilino, 3-pentadecyloxycarbonylanilino and 2-chloro-5-hexa- decaneamidoanilino groups.
• the acylmaino.group represented by R includes alkylcarbonylamino and arylcarbonylamino (preferably phenylcarbonylamino) groups, and further includes those having a substituent(s) such as acetamido, a-ethylpropane- amido, N-pnenylacetamido, dodecaneamido, 2,4-di-t-amyl- phenoxyacetamido and a-3-t-butyl-4-hydroxyphenoxybutane- amido groups.
• the sulfonamido group represented by R includes alkylsulfonylamino and arylsulfonylamino groups, and further includes those having a substituent(s), such as methylsulfonylamino, pentadecylsulfonylamino, benzen- sulfonamido, p-toluenesulfonamido and 2-methoxy-5-t-amylbenzenesulfonamido groups.
• the imido group represented by R includes those which are open-chained or close-chained, and further includes those having a substituent(s), such as, succinimido, 3-heptadecylsuccinimido, phthalimido and glutarimido groups.
• the ureido group represented by R includes those substituted with an alkyl or aryl (preferably phenyl) group, such as N-ethylureido, N-methyl-N-decylureido, N-phenylureido and N-p-tolylureido groups.
• the sulfamoylamino group represented by R includes those substituted with an alkyl or aryl (preferably phenyl) group, such as N,N-dibutylsulfamoylamino, N-methylsulfamoylamino and N-phenylsulfamoylamino groups.
• the alkoxycarbonylamino group represented by R includes those having a substituent(s), such as methoxy- carbonylamino, methoxyethoxycarbonylamino and octadecyloxy- carbonylamino groups.
• the aryloxycarbonylamino group represented by R includes those having a substituent(s), such as phenoxy- carbonylamino and 4-methylphenoxycarbonylamino groups.
• the alkoxycarbonyl group represented by R includes those having a substituent(s),such as methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxy- carbonyl, ethoxymethoxycarbonyloxy and benzyloxycarbonyl groups.
• the aryloxycarbonyl group represented by R includes those having a substituent(s), such as phenoxycarbonyl, p-chlorophenoxycarbonyl and m-pentadecyloxyphenoxycarbonyl groups.
• the alkylthio group represented by R includes those having a substituent(s),such as ethylthio, dodecylthio, octadodecylthio, phenethylthio and 3-phenoxypropylthio groups.
• the arylthio group represented by R is preferably a phenylthio group, and includes those having a substituent(s), such as phenylthio, p-methoxyphenylthio, 2-t-octylphenylthio, 3-octadecylphenylthio, 2-carboxyphenylthio and p-acetaminophenylthio groups.
• the heterocyclicthio group, represented by R is preferably a 5- to 7-membered heterocyclicthio group, and includes those having a condensed ring or having a substituent(s).
• Examples of such heterocyclicthio group include 2-pyridylthio, 2-benzothiazolylthio and 2,4-diphenoxy-1,3,5-triazol-6-thio groups.
• the substituent represented by X that is capable of leaving upon reaction with the oxidized product of a color developing agent includes, for example, those substituted through the carbon, oxygen, sulfur or nitrogen atom . other than the halogen atom (chlorine, bromine or fluorine atom).
• the groups which are substituted through the carbon atom include, in addition to the carboxyl group, a group represented by the following formula: (wherein R 1 ' is the same in meaning as.said R; Z' is the same in meaning as said Z; and R 2 ' and R 3 ' each represents a hydrogen atom, an aryl, alkyl or heterocyclic group), a hydroxymethyl group and a triphenylmethyl group.
• the groups which are substituted through the oxygen atom include, for example, alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyloxalyloxy and alkoxyoxalyloxy groups.
• the alkoxy group includes those having a substituent(s), such as ethoxy, 2-phenoxyethoxy, 2-cyanoethoxy, phenethyloxy, and p-chlorobenzyloxy groups.
• the aryloxy group is preferably a phenoxy group, and includes those having a substituent(s).
• aryloxy group include phenoxy, 3-methylphenoxy, 3-dodecylphenoxy, 4-methanesulfoneamidophenoxy, 4-[a-(3'-pentadecylphenoxy)butaneamido]phenoxy, hexadecyl- carbamoylmethoxy, 4-cyanophenoxy, 4-methanesulfonyl- phenoxy, 1-naphthyloxy and p-methoxyphenoxy groups.
• the heterocyclicoxy group is preferably a 5- to 7-membered heterocyclicoxy group, and may be a condensed ring or include those having a substituent(s).
• Examples of such heterocyclicoxy group include I-phenyltetra- zolyloxy and 2-benzothiazolyloxy groups.
• the acyloxy group includes, for example, an alkylcarbonyloxy group such as acetoxy and butanoyloxy groups, an alkenylcarbonyloxy group such as a cinnamoyloxy group, and an arylcarbonyloxy group such as a benzoyloxy group.
• the sulfonyloxy group includes, for example, butane- sulfonyloxy and methanesulfonyloxy groups.
• the alkoxycarbonyloxy group includes, for example, ethoxycarbonyloxy and benzyloxycarbonyloxy groups.
• the aryloxycarbonyloxy group includes a phenoxy- carbonyloxy group and the like.
• the alkyloxalyloxy group includes, for example, a methyloxalyloxy group.
• the alkoxyoxalyloxy group includes an ethoxyoxalyl- oxy group and the like.
• the group which is substituted through the sulfur atom includes, for example, alkylthio, arythio, heterocyclicthio and alkyloxythiocarbonylthio groups.
• the alkylthio group includes butylthio, 2-cyano- ethylthio, phenetylthio and benzylthio groups.
• the arylthio group includes phenylthio, 4-methane- sulfoneamidophenylthio, 4-dodecylphenetylthio, 4- nonafluoropentaneamidophenetylthio, 4-carboxyphenylthio and 2-ethoxy-5-t-butylphenylthio groups.
• the heterocyclicthio group includes, for example, 1-phenyl-1,2,3,4-tetrazolyl-5-thio and 2-benzothiazolylthio groups.
• the alkyloxythiocarbonylthio group includes a dodecyloxythiocarbonylthio group and the like.
• the group which is substituted through the nitrogen atom includes, for example, one represented by the formula wherein R 4 ' and R 5 ' each represents a hydrogen atom, an alkyl, aryl, heterocyclic, sulfamoyl, carbamoyl, acyl, sulfonyl, aryloxycarbonyl or alkoxycarbonyl group, and R 4 ' and R 5 1 may cooperate to form a heterocyclic ring, provided that R 4 ' and R 5 ' are not hydrogen atoms at the same time.
• the alkyl group may be straight-chained or branched and is preferably one having 1 to 22 carbon atoms.
• the alkyl group may include those having a substituent(s).
• substituent include, for example, aryl, alkoxy, aryloxy, alkylthio, arylthio, alkylamino, arylamino, acylamino, sulfoneamido, imino, acyl, alkylsulfonyl, arylsulfonyl, carbamoyl, sulfamoyl, alkoxycarbonyl, aryloxycarbonyl, alkyloxycarbonylamino, aryloxycarbonylamino, hydroxy, carboxyl and ciano groups and halogen atom.
• alkyl group includes, for example, ethyl, octyl, 2-ethylhexyl and 2-chloroethyl group.
• the aryl group represented by R 4 ' or R 5 ' is preferably one having 6 to 32 carbon atoms, particularly a phenyl or naphtyl group, and may include those having a substituent(s).
• substituent includes a substituent for the alkyl group represented by R 4 ' or R 5 ' and an alkyl group.
• the aryl group include, for example, phenyl, 1-naphtyl and 4-methylsulfonyl- phenyl groups.
• the heterocyclic group represented by R 4 ' or R 5 ' is preferably a 5- or 6-membered ring, and may be a condensed ring or include those having a substituent(s).
• Examples of such heterocyclic group include 2-furyl, 2-quinolyl, 2-pyrimidyl, 2-benzothiazolyl and 2-pyridyl groups.
• the sulfamoyl group represented by R 4 ' or R 5 ' includes N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N -arylsulfamoyl and N,N-diarylsulfamoyl groups, and these alkyl and aryl groups may have such a substituent(s) as is mentioned with respect to the alkyl and aryl groups.
• Examples of such sulfamoyl group includes, for example, N,N-diethylsulfamoyl, N-methylsulfamoyl, N-dodecylsulfamoyl and N-p-tolylsulfamoyl groups.
• the carbamoyl group represented by R 4 ' or R 5 ' includes N-alkylcarbamoyl, N,N-dialkylcarbamoyl, N-arylcarbamoyl and N,N-diarylcarbamoyl groups, and these alkyl and aryl groups may have such a substituent(s) as is mentioned with respect to the alkyl and aryl groups.
• carbamoyl group examples include, for example, N,N-diethylcarbamoyl, N-methylcarbamoyl, N-dodecylcarbamoyl, N-p-cianophenylcarbamoyl and N-p-tolylcarbamoyl groups.
• the acyl group represented by R 4 ' or R 5 ' includes, for example, alkylcarbonyl, arylcarbonyl and hetero- cycliccarbonyl groups, and the alkyl, aryl and heter p- cyclic groups may have a substituent(s).
• Examples of such acyl group include, for example, hexafluorobutanoyl, 2,3,4,5,6-pentafluorobenzoyl, acetyl, benzoyl, naphtoyl and 2-furylcarbonyl groups.
• the sulfonyl group represented by R 4 ' or R 5 1 includes alkylsulfonyl, arylsulfonyl and heterocyclic- sulfonyl groups, and may have a substituent(s).
• Examples of such sulfonyl group include, for example, ethanesulfonyl, benzenesulfonyl, octanesulfonyl, naphthalenesulfonyl and p-chlorobenzenesulfonyl groups.
• the aryloxycarbonyl group represented by R 4 ' or R 5 1 may have such a substituent(s) as is mentioned with respect to the aryl group, and includes a phenoxycarbonyl group and the like.
• the alkoxycarbonyl group represented by R 4 ' or R 5 1 may have such a substituent(s) as is mentioned with respect to alkyl group, and includes methoxycarbonyl, dodecyloxycarbonyl and benzyloxycarbonyl groups.
• the heterocyclic ring which is formed through cooperation of R 4 ' and R 5 ' is preferably a 5- or 6- membered ring, may be saturated or unsaturated, may or may not be an aromatic ring, or may be a condensed ring.
• heterocyclic ring examples include, for example, N-phthalimido, N-succinimide, 4-N-urazolyl, 1-N-hydantoinyl, 3-N-2,4-dioxooxazolidinyl, 2-N-1,1-dioxo-3-(2H)-oxo-1,2- benzthiazolyl, 1-pyrrolyl, 1-pyrrolidinyl, 1-pyrazolyl, 1-pyrazolidinyl, 1-piperidinyl, 1-pyrrolinyl, 1-imidazolyl, 1-imidazolinyl, 1-indolyl, 1-isoindolinyl, 2-iso-indolyl, 2-isoindolinyl, 1-benzotriazolyl, 1-benzoimidazolyl, 1-(1,2,4-triazolyl), 1-(1,2,3-triazolyl), 1-(1,2,3,4-tetrazolyl), N-morpholinyl, 1,2,3,4-
• heterocyclic groups may be substituted by alkyl, aryl, alkyloxy, aryloxy, acyl, sulfonyl, alkylamino, arylamino, acylamino, sulfoneamino, carbamoyl, sulfamoyl, alkylthio, arylthio, ureido, alkoxycarbonyl, aryloxycarbonyl, imido, nitro, cyano, carboxyl groups as well as by a halogen atom and the like.
• the nitrogen-containing heterocyclic ring which is formed by Z or Z' includes pyrazol, imidazol, triazol and tetrazol rings, and may have such a substituent(s) as is mentioned with respect to R.
• the coupler formed is the so-called bis-type coupler, which is included in the present invention.
• the ring which is formed by Z, Z', Z" as well as by Z 1 to be stated later may be condensed with another ring (for example 5- to 7-membered cycloalkene).
• R 5 and R 6 , and in formula (VII), R 7 and R 8 may cooperate to form a ring (for example, 5- to 7-membered cycloalkene, or benzene), respectively.
• the coupler represented by formula (I) preferably includes, for example, those represented by the following formulas (III) to (VIII): wherein R 1 to R 8 and X are the same in meaning as R and X mentioned above.
• the coupler of formula (I) is preferably one represented by the following formula (IX): wherein R 1 , X and Z 1 are the same in meaning as R, X and Z in formula (I).
• magenta couplers represented by formulas (III) to (VIII) those represented by formula (III) are particularly preferable.
• R in formula (I) and R 1 in formulas (III) to (IX) are preferable when they satisfy the following requirement 1, the same R and R 1 are more preferable when they satisfy the following requirements 1 and 2, and the same R and R 1 are most preferable when they satisfy all of the following requirements 1, 2 and 3:
• R 9 , R 10 and R 11 each represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkinyl group, an aryl group,a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, carbamoyl group, a sulfamoyl gruop, a cyano group, a spiro-compound residue, a bridged hydrocarbon compound residue, an alkoxy group, an aryloxy group, a heterocyclicoxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an acylamino group, a
• R 9 and R 10 may cooperate to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene or heterocyclic ring), and further R 11 may cooperate with said ring to form a bridged hydrocarbon compound residue.
• a saturated or unsaturated ring e.g. cycloalkane, cycloalkene or heterocyclic ring
• the group represented by R 9 to R 11 may have a substituent(s). Examples of said group and said substituent(s) are the same as the examples of the group represented by R in formula (I) and the substituent(s) mentioned with respect thereto.
• Examples of the ring formed by the cooperation of, for example, R 9 and R 10' as well as of the bridged hydrocarbon compound residue which is formed by R 9 to R 11 and the substituent(s) which said residue may have, are the same as the examples of the cycloalkyl, cycloalkenyl and heterocyclic groups represented by R in formula (I), and the substituent(s) mentioned with respect thereto.
• the preferable substituent,(s) in (i) above is such that two of R 9 to R 11 are alkyl groups, and the other one is a hydrogen atom or an alkyl group.
• alkyl and cycloalkyl groups each may have a substituent(s). Examples of such alkyl and cycloalkyl groups as well as of their substituents are the same as the examples of the alkyl and cycloalkyl groups represented by R in formula (I) and the substituents mentioned with respect thereto.
• the couplers represented by formula (I) are preferably those having a group represented by the following formula (A): wherein R represents an alkylene group having 3 or more carbon atoms in the straight chain that is bonded to the hydrocarbon at 3-position of the coupler; and b R represents an alkyl group, a cycloalkyl group or an aryl group.
• the alkylene group represented by R has 3 or more, preferably 3 to 6, carbon atoms in the straight chain, and include those having a substituent.
• substituents include, in addition to an aryl group, a cyano group, a halogen atom, a heterocyclic group, a cycloalkyl group, a cycloalkenyl group, a spiro-compound residue and a bridged hydrocarbon compound residue, for example, those substituted through the carbonyl group, such as acyl, carboxy, carbamoyl, alkoxycarbonyl and aryloxycarbonyl groups, and those substituted through the hetero atom, for example, those substituted through the oxygen atom, such as hydroxy, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy and carbamoyloxy groups, those substituted through the nitrogen atom, such as nitro, amino (including dialkylamino and the like), sulfamonylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfoneamido, imido and
• the substituent is preferably a phenyl group.
• the alkyl group represented by R may be one having a straight-chain or a branched-chain.
• Example of such alkyl group includes methyl, ethyl, propyl, iso-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl and 2-hexyldecyl groups.
• the cycloalkyl group represented by R b is preferably one having a 5- or 6-membered ring, for example, a cyclohexyl group.
• the alkyl and cycloalkyl groups represented by R b include those having a substituent, for example, those exemplified as substituents for R a .
• Examples of the aryl group represented by R include phenyl and napthyl groups, and also include those having a substituent.
• substituents include, for example, alkyl groups having a straight chain or a branched chain and those exemplified as substituents for R a . When 2 or more substituents are present, they may be the same or different.
• More preferred couplers represented by formula (I) of the present invention are those represented by the following formula (B): wherein R and R b are the same in meaning as R and R b in formula (A), and R and X are the same in meaning as R and X in formula (I), respectively.
• the coupler of the present invention is usually incorporated in an amount within the range of 1x10 -3 mole to 1 mole, preferably 1x10 -2 mole to 8x10 -1 mole, per mole of silver halide.
• the coupler of the present invention may be used in combination with any other type of magenta coupler.
• Magenta dye image stabilizers to be used in combination with the coupler of the present invention are compounds such as 5-hydroxyindan, 5,5'-dihydroxy-1,1'- spirobiindan and 6,6'-dihydroxy-1,1'-spirobiindan represented by the following formula (II) which have both an effect of preventing the color fading due to light and an effect of preventing the discoloration due to light of magenta dye images: wherein R 1 and R 3 each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamido group, a cycloalkyl group or an alkoxycarbonyl group. Examples of these groups are the same as those mentioned for R in formula (I);
• R 2 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group. Examples of these groups are the same as those mentioned for R in formula (I) .
• These groups may be substituted by other substituents, respectively, such as, for example, alkyl, alkenyl, alkoxy, aryl, aryloxy, hydroxy, alkoxycarbonyl, aryloxycarbonyl, acylamino, carbamoyl, sulfonamido and sulfamoyl groups.
• R 2 and R 3 may cooperate to form a 5- or 6- membered hydrocarbon ring.
• This hydrocarbon ring may be substituted by a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an'alkenyl group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group; and
• Y represents the group of atoms necessary to form an indan ring.
• This indan ring may be substituted by a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group, and further may form a spiro ring.
• R 1 , R 2 and R 3 are the same in meaning as R 1 , R 2 and R 3 in formula ( II ); and R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group.
• R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 each may cooperate to form a hydrocarbon ring, which ring may be substituted by an alkyl group.
• R 2 represents a hydrogen atom, an alkyl group, a hycroxy group or a cycloalkyl group
• R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each represents a hydrogen atom, an alkyl group or a cycloalkyl group.
• magenta dye image stabilizers represented by formulas (II), and (XI) to (XIII) of the present invention can be synthesized in accordance with the method of synthesis described in J. Chem. Soc., 1962, pages 415 to 417, Japanese Patent Publication No. 32785/1984, and Bull. Chem. Soc., Japan, 1980, 53, pages 555 and 556.
• magenta dye image stabilizers of the present invention are disclosed in Japanese Patent Duplication No. 32785/1984, and are used as stabilizers for magenta dye images formed from pyrazolone, indazolone or cyanoacetyl type magenta couplers.
• these magenta dye image stabilizers are described to be particularly useful as stabilizers for magenta dye images formed from 5-pyrazolone type magenta couplers, but nothing is suggested as to the fact that these stabilizers are useful for magenta dye images formed from the magenta couplers of the present invention which differ in structure from such magenta coupler.
• magenta dye image stabilizer represented by formula (II) of the present invention is used in an amount of preferably 5 to 300 mol %, more preferably 10 to 200 mol %, per mole of the magenta coupler of the formula (I).
• magenta dye image stabilizer of the present invention may be used in combination with another magenta dye image stabilizer that is represented by the following formula (XIV), namely, a phenolic or phenylether compound: wherein R 4 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R 5 , R 6 , R 8 and R 9 are each a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group or an acylamino group; R 7 is an alkyl group, a hydroxyl group, an aryl group or an alkoxy group; R 4 and R 5 may be fused to form a 5- or 6-membered ring when R 7 represents a hydroxy or alkoxy group; R 4 and R 5 may be fused to form a methylenedioxy ring; and R 6 and R 7 may be fused to form a 5-membered carbon ring when R 4 represents an alkyl, aryl or hetero
• the phenolic or phenylether compound of formula (XIV) is preferably used in an amount not more than 200 mole % of the magenta dye image stabilizer of formula (II), with the amount not exceeding 140 mole % being more preferred.
• the phenolic compound and phenylether compound are effective in preventing the fading of the magenta dye image produced from the magenta coupler of the present invention, but they are little effective in preventing such magenta dye image from becoming discolored. Therefore, it is not preferred that the phenolic or phenylether compound is used in an excess amount with respect to the magenta dye image stabilizer of the present invention.
• magenta dye image formed from the magenta coupler of the present invention generally undergoes considerable fading upon exposure to light. Furthermore, discoloration resulting from exposure to light is so great that the color of the image changes from the pure magenta to yellowish magenta.
• the magenta dye image stabilizer of formula (II) is capable of exhibiting the effects unattainable by the phenolic or phenylether compound, i.e., prevention of fading and discoloration of the magenta dye image produced from the magenta coupler used in the present invention.
• magenta dye image stabilizer of formula (II) when used in admixture with the conventional magenta dye image stabilizer, i.e., phenolic or phenylether compound, said conventional stabilizer must be used in such an amount that the discoloration upon exposure to light is not remarkable.
• magenta coupler and magenta dye image stabilizer in accordance with the present invention are preferably used in the same photographic layer, but if desired, they may be incorporated in two different layers such that the stabilizer in a layer adjacent the one containing the magenta coupler.
• the silver halide photographic material of the present invention may be, for example, color negative and positive films and color photographic paper, but particularly when color photographic paper for viewing the printed color image directly is used, the effect of the present invention is produced strikingly.
• the silver halide photographic material of the present invention including such color photographic paper may be either for monochrome or multicolor use.
• the silver halide photographic material for multicolor use has a structure such that silver halide emulsion layers usually containing magenta, yellow and cyan couplers, respectively, as photographic couplers, and nonsensitive layers are superimporsed in appropriate number of layers and in appropriate sequence on the support in order to effect subtractive color reproduction, but such number of layers and sequence may be changed appropriately according to use object.
• the silver halide emulsion used in the silver halide photographic material of the present invention may be selected from among the silver halides commonly used in silver halide photography, such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide and silver chloroiodobromide.
• the silver halide grains used in the silver halide emulsions of the present invention may be those obtained by any of the acid method, neutral method, and ammoniacal method. These grains may be grown at one time or may be grown after preparing seed grains. The method of preparing seed grains and the method of growing them may be the same or different.
• halide ions and silver ions may admixed at the same time, or either one may be admixed with the other one present in the emulsion. Also, while considering the critical speed of growth of silver halide crystals, halide ions and silver ions may be added one by one or at the same time into a mixing bath while controlling the pH and pAg in said bath to grow the crystals.
• a silver halide solvent optionally, to control the grain size, shape, grain size distribution and speed of growth of the silver halide grains.
• the silver halide grains to be used in the silver halide emulsions of the present invention may have metal ions incorporated inside the grains and/or in the grain surfaces in the course of forming and/or growing the grains by using cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, or iron salt or its complex salt.
• Said grains may also be placed in an appropriate reduction atmosphere to have reduction-sensitized specks imparted inside the grains and/or into the grain surfaces.
• the silver halide emulsions of the present invention may be removed of unnecessary soluble salts after completion of the growth of the silver halide grains or may be left as they are containing such salts. In removing said salts; the method described in "Research Disclosure No. 17643" may be used.
• the silver halide grains to be used in the silver halide emulsions of the present invention may have a homogeneous structure throughtoug the crystal, or the structure of the core may be different from that of the shell. These silver halide grains may be of the surface type where latent images are predominantly formed on the grain surface or of the internal type where latent images are formed within the grain.
• the silver halide grains may be regular crystals or irregular crystals such as in'spherical or plane form.
• They may have any proportions of (100) and (111) planes, and may also be in composite form of these crystals or may be admixed with various crystal grains.
• the silver halide emulion of the present invention may be a mixture of two or more silver halide emulsions prepared separately.
• the silver halide emulsion of the present invention is chemically sensitized by an ordinary method, such as the sulfur sensitization using a compound containing sulfur capable of reaction with silver ions or using active gelatin, the selenium sensitization using a selenium compound, the reduction sensitization using reducible material, or the noble metal sensitization using gold and other noble metal compounds.
• an ordinary method such as the sulfur sensitization using a compound containing sulfur capable of reaction with silver ions or using active gelatin, the selenium sensitization using a selenium compound, the reduction sensitization using reducible material, or the noble metal sensitization using gold and other noble metal compounds.
• Such methods may be used each independently or in combination.
• the silver halide emulsion of the present invention may be spectrally sensitized by suitably selected sensitizing dye in order to provide sensitivity for the desired spectral wavelength regions.
• sensitizing dyes may be used either individually or in combination.
• the silver halide emulsion may contain, together with the sensitizer, a dye which itself has no spectral sensitizing action or a supersensitizer which, being a compound which substantially does not absorb visible light, strengthens the sensitizing action of the sensitizer.
• a compound known in the photographic industry as an antifoggant or stabilizer may be added to the silver halide emulsion of the present invention in the course of chemical ripening and/or upon completion of chemical ripening and/or after completion of chemical ripening but before coating of the silver halide emulsion.
• the binder (or protective colloid) advantageously used in the silver halide emulsion of the present invention is gelatin, but other hydrophilic colloids such as gelatin derivative, glaft polymer of gelatin with other polymer, protein, sugar derivative, cellulose derivative, and synthesized hydrophillic polymer may be used.
• the photographic emulsion layer and other hydrophilic colloidal layer(s) of the photographic material using the silver halide emulsion of the present invention are hardened by using hardeners either alone or in combination that bridge the binder (or protective colloid) molecules to enhance the film strength.
• the hardener is desirably added in such an amount as is capable of hardening the photographic material to the extent that there is no need to add the hardener in the processing solution, but such hardener may be added in the processing solution.
• a plasticizer can be added with a view to enhancing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloidal layer(s) of the photographic material using the silver halide emulsion of the present invention.
• a water-insoluble or hardly soluble synthesized polymer latex can be incorporated for the purpose of improving the dimentional stability of the photographic emulsion layer and other hydrophilic colloidal layer(s) of the photographic material using the silver halide emulsion of the present inventi
• a dye-forming coupler which forms a dye upon coupling reaction with the oxidized product of an aromatic primary amine developing agent (e.g., p-phenylenediamine derivative or aminophenol derivative) in the color developing processing.
• the color-forming coupler is usually selected so that a dye is formed which absorbs the spectral wavelength sensitive to the emulsion layer containing said dye; that is, a yellow dye-forming coupler is used in the blue-sensitive emulsion layer, a magenta dye-forming coupler in the green-sensitive emulsion layer, and a cyan dye-forming coupler in the red-sensitive emulsion layer.
• the respective couplers may be used in different combinations from those mentioned above according to the object.
• the yellow dye-forming coupler includes acylacetamido couplers (e.g. benzoylacetanilides and pivaloyl acetanilides), the magenta dye-forming coupler includes, in addition to the couplers of the present invention, 5-pyrazolone, pyrazolobenzimidazole, pyrazolotriazole and open chained acylacetonitrile couplers, and the cyan dye-forming coupler includes naphthol and phenol couplers.
• acylacetamido couplers e.g. benzoylacetanilides and pivaloyl acetanilides
• magenta dye-forming coupler includes, in addition to the couplers of the present invention, 5-pyrazolone, pyrazolobenzimidazole, pyrazolotriazole and open chained acylacetonitrile couplers
• the cyan dye-forming coupler includes naphthol and phenol couplers.
• These dye-forming couplers desirably have a group having 8 or more carbon atoms in the molecule that, being called a ballast group, renders the coupler non-diffusible.
• These couplers may be 4-equivalent couplers such that four silver ions need be reduced for the formation of one mole of dye, or may be 2-equivalent couplers such that only two silver ions suffice to be reduced for the formation of one mole of dye.
• Hydrophobic compounds such as dye-forming coupler that need not be adsorpted onto the silver halide crystal surfaces can be dispersed into the emulsion by means of solid dispersion, latex dispersion or oil-in-water drop type emulsion dispersion. Such dispersion method can be appropriately selected according to the chemical structure and the like of the hydrophobic compounds.
• the oil-in-water drop type emulsion dispersion method may be any conventional method of dispersing hydrophobic additives such as coupler, which usually comprises dissolving such hydrophobic additives in a high-boiling organic solvent having a boiling point higher than about 150°C by optionally using low-boiling and/or water-soluble organic solvents together, then emulsion-dispersing the dissolved hydrophobic additives by using a surfactant in a hydrophilic binder such as aqueous gelatin solution with such means of dispersion as a stirrer, homogenizer, colloid mill, flow-jet mixer or ultrasonic disperser, and thereafter adding the resulting dispersion into the hydrophilic colloidal layer.
• a surfactant in a hydrophilic binder such as aqueous gelatin solution with such means of dispersion as a stirrer, homogenizer, colloid mill, flow-jet mixer or ultrasonic disperser, and thereafter adding the resulting dispersion into the hydrophil
• the high-boiling organic solvent is one having a boiling point higher than 150°C that does not react with the oxidized product of a developing agent, such as a phenol derivative, phthalate ester, phosphate ester, citrate ester, benzoate ester, alkylamido, fatty acid ester or trimesic acid ester.
• a developing agent such as a phenol derivative, phthalate ester, phosphate ester, citrate ester, benzoate ester, alkylamido, fatty acid ester or trimesic acid ester.
• Dispersion aids used in dissolving hydrophobic compounds in a low-boiling solvent alone or mixed with a high-boiling solvent and dispersing the dissolved hydrophobic compounds into water by using a mixer or ultrasonic disperser include anionic surfactants, nonionic surfactants and cationic surfactants.
• Anti-color foggants may be used in order to prevent occurrence of color stain, deterioration of sharpness and coarse graininess due to moving of the oxidized product of a developing agent or the electron transporting agent between the emulsion layers (the same color-sensitive layers and/or different color-sensitive layers) of the color photographic material of the present invention.
• the anti-color foggants may be incorporated in the emulsion layer itself or in the intermediate layer provided between adjacent emulsion layers.
• Image stabilizers can be incorporated in the color photographic material using silver halide emulsion layers of the present invention in order to prevent deterioration of color images.
• hydrophilic colloidal layers such as protective layer and intermediate layer of the photographic material of the present invention may have incorporated therein UV absorbers in order to prevent occurrence of fogging due to discharge resulting from the photographic material being charged by its friction or the like, or to prevent deterioration of images due to UV light.
• the color photographic material using a silver halide emulsion of the present invention can be provided with auxiliary layers such as filter layer, anti-halation layer and/or anti-irradiation layer. These auxiliary layers and/or the emulsion layers may have incorporated therein dyes flowing out of the color photographic material or being bleached during the color developing processing.
• Matting agents can be incorporated in the silver halide emulsion layers and/or other hydrophilic colloidal layers of the silver halide photographic material using a silver halide emulsion of the present invention, with a view to reducing the surface gloss to render writing in pencil possible and to preventing adhesion of photographic materials to each other.
• the light-sensitive material using the silver halide emulsion of the present invention may contain a lubricant that is capable of reducing its sliding friction.
• the light-sensitive material may also contain an antistat for the purpose of preventing static buildup.
• the antistat may be incorporated in an antistatic layer on the side of the support where no emulsion layer is formed.
• the antistat may be incorporated in an emulsion layer and/or a protective layer other than an emulsion layer which is on the side of the support where said emulsion layer is formed.
• Photographic emulsion layers and/or other hydrophilic colloidal layers in the light-sensitive material using the silver halide emulsion of the present invention may contain a variety of surfactants for attaining such purposes as improved coating property, prevention of antistatic buildup, improved slipping property, emulsification/ dispersion, antiblocking and improved photographic characteristics in terms of accelerated development, hard tone and sensitization.
• Photographic emulsion layers and other layers for making a light-sensitive material using the silver halide emulsion of the present invention may be coated onto flexible reflecting supports such as paper or synthetic paper laminated with baryta layer or a-olefin polymer, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, and rigid materials such as glass, metals and ceramics.
• flexible reflecting supports such as paper or synthetic paper laminated with baryta layer or a-olefin polymer, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, and rigid materials such as glass, metals and ceramics.
• the silver halide light-sensitive material of the present invention may be coated onto the support either directly or with one or more subbing layers formed thereon.
• the subbing layers are provided for improving the adhesive strength, anti-static property, dimensional stability, frictional resistance, hardness, anti-halation property, frictional characteristics and/or other characteristics of the surface of the support.
• a thickener may be used in order to facilitate the coating of the photographic material using the silver halide emulsion of the present invention.
• Particularly useful coating techniques are extrusion coating and curtain coating, both of which will enable simultaneous application of two or more layers.
• the light-sensitive material of the present invention may be exposed to electromagnetic waves in the spectral region to which the emulsion layers that make up the light-sensitive material have sensitivity.
• Any known light sources may be used and they include daylight (sunshine), tungsten lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, CRT flying spot, light from a variety of lasers, LED emitted light, and light emitted from fluorescent materials upon excitation by electron beams, X-rays, gamma-rays or alpha-rays.
• the exposure time may range from 1 millisecond to 1 second as is usually the case with cameras. Periods shorter than 1 microsecond, such as one ranging from 100 microseconds to 1 microsecond may be employed with CRTs or xenon flash lampls. Exposure longer than 1 second would also be possible.
• the exposure may be continuous or intermittent.
• the silver halide photographic material of the present invention may form an image by any techniques of color development that are known in the art.
• the color developer used to process this photographic material may contain any of the known aromatic primary amine color developing agents that are extensively used in various color photographic processes.
• Such developing agents include aminophenolic and p-phenylenediamine derivatives. These compounds are generally used in salt forms, such as hydrochlorides or sulfates, which are stabler than the free state. These compounds are used in concentrations that generally range from about 0.1 to about 30 g, preferably from about 1 g to about 1.5 g per liter of the color developer.
• Illustrative aminophenolic developing agents include o-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, and 2-oxy-3-amino-1,4-dimethylbenzene.
• N,N- dialkyl-p-phenylenediamine compounds wherein the alkyl or phenyl group may have a suitable substituent.
• these compounds the following are particularly advantageous: N,N'-di-ethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N- ⁇ -methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-S-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N'-diethylaniline, and 4-amino-N-(2-methoxyethyl)
• the color developer used in the processing of the photographic material of the present invention may contain a variety of additives that are commonly incorporated in color developers and such additives include alkali agents (e.g. sodium hydroxide, sodium carbonate and potassium carbonate), alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners.
• alkali agents e.g. sodium hydroxide, sodium carbonate and potassium carbonate
• alkali metal sulfites e.g. sodium hydroxide, sodium carbonate and potassium carbonate
• alkali metal sulfites e.g. sodium hydroxide, sodium carbonate and potassium carbonate
• alkali metal sulfites e.g. sodium hydroxide, sodium carbonate and potassium carbonate
• alkali metal sulfites e.g. sodium hydroxide, sodium carbonate and potassium carbonate
• the photographic material of the present invention is processed by a solution having the fixing ability. If this solution is a fixing bath, its use is preceded by a bleaching step.
• the bleaching agent used in the bleaching bath is a metal complex salt of an organic acid.
• This metal complex salt has the ability not only to oxidize metallic silver (i.e., formed as a result of development) into silver halide but also to ensure complete color formation by a color former.
• the structure of this metal complex salt is such that an organic acid such as an aminopolycarboxylic acid, oxalic acid or citric acid is coordinated to a metal ion such as iron, cobalt or copper.
• the organic acids most preferred for use in forming metal complex salts are polycarboxylic acids or aminopolycarboxylic acids.
• the polycarboxylic acids or aminopolycarboxylic acids may be in the form of alkali metal salts, ammonium salts or water-soluble amine salts.
• polycarboxylic acids or aminopolycarboxylic acids are lited below:
• the bleaching bath used in processing the color photographic material of the present invention may contain a variety of additives, and preferred additives are rehalogenating agents such as alkali or ammonium halides (e.g., potassium bromide, sodium bromide, sodium chloride and ammonium bromide), metal salts and chelating agents.
• rehalogenating agents such as alkali or ammonium halides (e.g., potassium bromide, sodium bromide, sodium chloride and ammonium bromide), metal salts and chelating agents.
• Any other additives that are conventionally incorporated in bleaching baths may also be used and they include pH buffers (e.g., borate, oxalate, acetate, carbonate and phosphate salts), alkylamines and polyethylene oxides.
• the fixing bath and bleach-fixing bath may also contain one or more pH buffers that are selected from among sulfites (e.g., ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite), and a variety of acids or salts (e.g., boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium bisulfite, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide).
• sulfites e.g., ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite
• acids or salts e.g., boric acid
• thiosulfates, thiocyanates, sulfites or other salts may be incorporated either in the bleach-fixing bath or in the replenisher that is fed to said blix bath.
• air or oxygen may be blown into a tank containing the bleach-fixing bath or its replenisher.
• a suitable oxidant such as hydrogen peroxide, bromate or persulfate may be added into the tank.
• Color photographic materials containing the magenta coupler of the present invention and a magenta dye image stabilizer represented by formula (II) are improved in the fastness of magenta dye images particularly against light, heat and humidity; that is, the discoloration and fading of color against light as well as the occurrence of yellow stain in the background due to light, heat and humidity are satisfactorily prevented.
• Gelatin (15.0 mg/100 cm 2 ) and comparative magenta coupler (I) (6.0 mg/100 cm2) were dissolved and dispersed in dibutyl phthalate (5.0 mg/100 cm 2 ) together with 2,5-di-tert-octylhydroquinone (0.8 mg/100 cm 2 ).
• the dispersion was mixed with a silver chlorobromide emulsion (containing 80 mol % of silver bromide) and the mixture was coated onto a paper support laminated with polyethylele on both surfaces, so as to provide a silver deposit of 3.8 mg/100 cm2.
• the so formed emulsion layer was dried to prepare sample No. 1.
• sample No. 1 a conventional magenta dye image stabilizer (PH-13) was added in an amount equimolar to that of the magenta coupler, thereby preparing sample No. 2.
• PH-13 magenta dye image stabilizer
• Sample Nos. 3, 6 and 9 were prepared as in the case of sample No. 1 except that comparative magenta coupler (I) was replaced by A-5, A-7 and A-96, three of the triazole type magenta couplers defined in the present invention.
• Sample Nos. 4, 7 and 10 were prepared by modifying sample Nos. 3, 6 and 9 with PH-13 added in an amount equimolar to that of the magenta coupler.
• Sample Nos. 5, 8 and 11 were prepared by modifying sample Nos. 3, 6 and 9 with HI-3, a magenta dye image stabilizer within the scope of the invention, added in an amount equimolar to that of the magenta coupler.
• the processing solutions used had the following compositions.
• Each of the processed samples was placed under illumination in a xenon fadeometer for 8 days so as to examine the light fastness of the dye image and Y staining in the background.
• Another set of the processed samples were left for 14 days in a hot and humid atmosphere (60°C x 80% RH) so as to examine the resistance of the dye image to moisture and Y staining in the background. The results are shown in Table 1.
• the light fastness and moisture resistance of each sample were evaluated on the following bases.
• Sample Nos. 12 - 27 were prepared as in,Example 1 except that the combinations of magenta coupler and magenta dye image stabilizer were changed to those indicated in Table 2. These samples were processed as in Example 1 and subsequently tested for their light-fastness and moisture resistance as in Example 1. The results are shown in Table 2.
• Comparative coupler (2) (In Table 2, sample Nos. 25, 26 and 27 each used HI compound and PH compound at a molar ratio of 2:1, and the total amount of dye image stabilizers is equimolar to that of the magenta coupler used therein.)
• sample Nos. 12 and 13 using the conventional four-equivalent 3-anilino-5-pyrazolone type coupler in combination with magenta dye image stabilizers within the scope of the invention and sample Nos. 16, 17, 18 and 19 using the combination of magenta couplers falling within the scope of the invention and commonly employed magenta dye image stabilizers were unable to give satisfactory results in all aspects of discoloration, fading and Y-staining in the background in the light-fastness test and Y-staining in the moisture resistance test.
• the intended results were obtained only when the magenta couplers within the scope of the invention were combined with magenta dye image stabilizers within the scope of the invention.
• Sample Nos. 25, 26 and 27 using the coupler of the present invention in combination with a dye image stabilizer within the scope of the present invention and a conventional dye image stabilizer are clearly observed to be somewhat improved in discoloration in the light-fastness test and to exhibit a synergistic effect in residual dye percentage.
• a paper support laminated with polyethylene on both sides was coated with the following photographic layers in sequence, with the first layer (blue-sensitive silver halide emulsion layer) positioned closest to the support. As a result, sample No. 28 of multi-colored silver halide photographic material was obtained.
• This layer was formed by coating 6.8 mg/100 cm 2 of a-pivaloyl-(2,4-dioxo-l-benzylimidazolidin-3-yl)-2-chloro-5-[y-(2,4-di-t-amylphenoxy)butylamido]acetanilide (yellow coupler), 3.2 mg/100 cm 2 , in terms of silver, of a blue-sensitive silver chlorobromide emulsion (85 mol % silver bromide), 3.5 mg/100 cm 2 of dioctyl phthalate and 13.5 mg/100 cm 2 of gelatin.
• This layer was formed by coating 0.5 mg/100 cm 2 of 2,5-di-t-octylhydroquinone, 0.5 mg/100 cm 2 of dinonyl phthalate and 9.0 mg/100 cm 2 of gelatin.
• This layer was formed by coating 3.5 mg/100 cm 2 of magenta coupler A-36 (a magenta coupler included in the scope of the invention), 2.5 mg/100 cm 2 , in terms of silver, of a blue-sensitive silver chlorobromide emulsion (80 mol % silver bromide), 3.0 mg/100 cm 2 of dioctyl phthalate and 12.0 mg/100 cm 2 of gelatin.
• magenta coupler A-36 a magenta coupler included in the scope of the invention
• 2.5 mg/100 cm 2 in terms of silver, of a blue-sensitive silver chlorobromide emulsion (80 mol % silver bromide), 3.0 mg/100 cm 2 of dioctyl phthalate and 12.0 mg/100 cm 2 of gelatin.
• This layer was formed by coating 7.0 mg/100 cm 2 of 2-(2-hydroxy-3-sec-butyl-5-t-butylphenyl)benzotriazole (UV absorber ), 6.0 mg/100 cm 2 of dibutyl phthalate, 0.5 mg/100 cm 2 of 2,5-di-t-octylhydroquinone and 12.0 mg/ 100 cm 2 of gelatin.
• This layer was formed by coating 4.2 mg/100 cm of 2-[a-(2,4-di-t-pentylphenoxy)butanamido]-4,6-dichloro-5-ethylphenol, 3.5 mg/100 cm 2 of tri-2-ethylhexyl phosphate and 11.5 mg/100 cm 2 of gelatin.
• This layer was formed by coating 8.0 mg/100 cm 2 of gelatin.
• Sample Nos. 29 to 37 were prepared by modifying sample No. 28 with magenta dye image stabilizers of the present invention that were incorporated in the 3rd layer in the amounts indicated in Table 3. Sample Nos. 29 to 37 were processed as in Example 1 and subjected to a light-fastness test under illumination in a xenon fedeometer for 15 days. The test results are shown in Table 3.
• Sample Nos. 29 to 37 experienced a very small amount of discoloration in the magenta image as a result of exposure to light as compared with sample No. 28. Furthermore, these samples of the present invention suffered an extremely small degree of discoloration and fading in the magenta dye. Therefore, they struck a good color balance between yellow, cyan and magenta couplers and displayed a highly yellow, cyan and magenta couplers and displayed a highly satisfactory color reproduction.
• Gelatin (15.0 mg/100 cm 2 ) and magenta coupler 144 of the present invention were dispersed in tricresylphosphate together with 2,5-di-tert-octyl- hydroquinone (0.8 mg/100 cm 2 ).
• the dispersion was mixed with a silver chlorobromide emulsion (containing 80 mol % of silver bromide) and the mixture was coated onto a paper support laminated with polyethylene on both surfaces, so as to provide a silver deposit of 3.8 mg/100 cm 2 .
• the so formed emulsion layer was dried to prepare sample No. 38.
• a magenta dye image stabilizer PH-13 was added in an amount equimolar to that of the magenta coupler, thereby preparing sample No. 39.
• Sample Nos. 42 and 46 were prepared as in the case of sample No. 38 except that magenta coupler A-144 was replaced by A-150 and A-168, two of the magenta couplers defined in the present invention.
• Sample Nos. 43 and 47 were prepared by modifying sample Nos. 42 and 46, respectively, with PH-13 added in an amount equimolar to that of the magenta coupler.
• Sample Nos. 40, 44 and 48 were prepared by modifying sample Nos. 39, 43 and 47 with HI-25, a magenta dye image stabilizer within the scope of the invention, in place of PH-13, added in an amount equimolar to that of the magenta coupler.
• Sample Nos. 41, 45 and 49 were prepared by modifying sample Nos. 39, 43 and 47 with PH-13 and HI-25 added at a ratio of 1:2 and in a total amount equimolar to that of the magenta coupler.
• the processing solutions used had the following compositions.
• the light fastness of each sample was evaluated on the following bases.
• the density of the dye remaining after each of the tests on light fastness and moisture resistance was indicated as a percentage of the initial density (1.0).
• the ratio of yellow density to magenta density as measured before testing for an initial density of 1.0 was subtracted from the value after testing. The greater the value obtained, the greater the discoloration from the pure magenta to a yellowish magenta coupler.
• Sample Nos. 41, 45 and 49 prepared by using the magenta coupler and magenta dye image stabilizer of the present invention in combination with a conventional magenta dye image stabilizer were improved much in light fastness of the magenta dye images as compared with sample Nos. 40, 44 and 48.
• a paper support laminated with polyethylene on both sides was coated with the following photographic layers in sequence from the support to obtain sample No. 50 of multi-colored silver halide photographic material.
• This layer was formed by coating 6.8 mg/100 cm 2 of ⁇ -pivaloyl- ⁇ -(2,4-dioxo-1-benzylimidazolidin-3-yl)-2-chloro-5-[y-(2,4-di-t-amylphenoxy)butylamido]acetanilide (yellow coupler), 3.2 mg/100 cm 2 , in terms of silver, of a blue-sensitive silver chlorobromide emulsion (85 mol % silver bromide), 3.5 mg/100 cm 2 of dibutyl phthalate and 13.5 mg/100 cm 2 of gelatin.
• This layer was formed by coating 0.5 mg/100 cm 2 of 2,5-di-t-octylhydroquinone, 0.5 mg/100 cm 2 of dibutyl phthalate and 9.0 mg/100 cm 2 of gelatin.
• This layer was formed by coating 3.5 mg/100 cm 2 of magenta coupler 150 of the invention, 2.5 mg/100 cm 2 , in terms of silver, of a blue-sensitive silver chlorobromide emulsion (80 mol % silver bromide), 3.0 mg/100 cm 2 of dibutyl phthalate and 12.0 mg/100 cm 2 of gelatin.
• This layer was formed by coating 7.0 mg/100 cm 2 of 2-(2-hydroxy-3-sec-butyl-5-t-butylphenyl)benzotriazole (UV absorber), 6.0 mg/100 cm 2 of dibutyl phthalate, 0.5 mg/100 cm 2 of 2,5-di-t-octylhydroquinone and 12.0 mg/100 cm 2 of gelatin.
• This layer was formed by coating 4.2 mg/100 cm 2 of 2-[a-(2,4-di-t-pentylphenoxy)butanamido]-4,6-dichloro-5-ethylphenol (cyan coupler), 3.0 mg/100 cm 2 , in terms of silver, of red-sensitive silver chlorobromide emulsion (80 mol % silver bromide), 3.5 mg/100 cm 2 of tricresyl phosphate and 11.5 mg/100 cm 2 of gelatin.
• This layer was formed by coating 8.0 mg/100 cm 2 of gelatin.
• Sample Nos. 51 to 59 were prepared by modifying sample No. 50 with magenta dye image stabilizers of the present invention that were incorporated in the 3rd layer in the amounts indicated in Table 5. Sample Nos. 51 to 59 were processed as in Example 4 and subjected to a light-fastness test under illumination in a xenon fadeometer for 15 days. The test results are shown in Table 5.
• magenta dye image stabilizers in accordance with the present invention are effective in stabilizing the dye image formed by the magenta coupler of the present invention and that this effectiveness is increased as the amounts in which these stabilizers are incorporated are increased.
• Sample Nos. 51 to 59 as compared with sample No. 50, experienced a very small amount of discoloration in the magenta image as a result of exposure to light. Furthermore, these samples of the present invention suffered an extremely small degree of discoloration and fading in the magenta dye, and even after the light-fastness test, they struck a good color balance between yellow, cyan and magenta couplers and displayed a highly satisfactory color reproduction.
• magenta coupler and magenta dye image stabilizer of the present invention were used as indicated in Table 6, wherein the magenta couplers were dispersed in tricresyl phosphate (8.0 mg/100 cm 2 ) together with 2,5-di-tert-octyl-hydroquinone (0.8 mg/100 cm 2 ).
• magenta couplers were dispersed in tricresyl phosphate (8.0 mg/100 cm 2 ) together with 2,5-di-tert-octyl-hydroquinone (0.8 mg/100 cm 2 ).

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• 1985
  • 1985-10-09 EP EP85307230A patent/EP0182486A1/de not_active Withdrawn

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