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
  • G03C7/32—Colour coupling substances
  • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material

Definitions

• the present invention relates to a silver halide color photographic material and, more particularly, to a silver halide color photographic material that is capable of superior color reproduction.
• Color reproduction in color photography employing silver halide color photographic materials is commonly achieved by the subtractive processes.
• Common silver halide color photographic materials use yellow-dye forming couplers (hereinafter referred to simply as yellow couplers) in blue-sensitive emulsion layers, magenta-dye forming couplers (hereinafter referred to simply as magenta couplers) in green-sensitive emulsion layers, and cyan-dye forming couplers (hereinafter referred to simply as cyan couplers) in red-sensitive emulsion layers.
• yellow couplers in blue-sensitive emulsion layers
• magenta-dye forming couplers hereinafter referred to simply as magenta couplers
• cyan-dye forming couplers hereinafter referred to simply as cyan couplers
• spectral absorption characteristics of color-forming dyes While color reproduction depends on a number of factors, the most important one is the spectral absorption characteristics of color-forming dyes. In principle, the spectral absorption characteristics of color-forming dyes can be adjusted to some extent by changing the chemical structures of the dyes. However, the absorption characteristics that can be used in practical applications are considerably limited since they must be adapted to the color development process employed. While numerous compounds have been reviewed by many researchers, those which exhibit completely satisfactory spectral absorption characteristics are yet to be attained.
• Color-forming dyes may be considered to be preferable in terms of color reproduction if they have the following spectral absorption characteristics: the wavelength that produces a maximum spectral absorption in the visible range (said absorption is hereinafter referred to as the primary absorption) is appropriate; the shape of the primary absorption peak is appropriate; and the amount of unwanted absorptions that occur in addition to the primary absorption (such absorptions are hereinafter referred to as the secondary absorption). It is known that substantial improvement can be attained for the primary absorption by proper selection of coupler substituents or high-boiling point organic solvents for couplers and this requirement has been met almost completely in the state of the art.
• any secondary absorption by magenta and cyan dyes in the blue region will cause serious adverse effects on color reproduction and is commonly dealt with in the art by such methods as masking with colored couplers and the use of the inter- image effect.
• these methods are not always available; for instance, masking with colored couplers is available for production of intermediate images as in color negative films but not available for production of final images as in color reversal films and color papers. It is therefore desired to develop couplers that provide color-forming dyes that experience a minimum degree of the secondary absorption.
• magenta couplers that experience reduced secondary absorptions and they include: pyrazolinobenzimidazoles of the types described in German Patent Nos. 1,070,030 and 1,127,220; azoles of the types described in French Patent No. 2,075,583, U.S. Patent Nos. 3,705,896 and 3,725,067, British Patent No. 1,252,418, and Japanese Patent Application (OPI) Nos.
• azoles exhibit fairly satisfactory performance and are known to provide couplers that are very desirable for achieving good color reproduction as manifested by reduced secondary absorption and a sharp primary absorption peak.
• Phenolic and naphtholic compounds are generally used as cyan couplers and 2,5-diacylaminophenolic couplers are known to provide color-forming dyes that have desirable spectral absorption characteristics for color reproduction; for this particular type of cyan couplers, see U.S. Patent No. 2,895,826, and Japanese Patent Application (OPI) Nos. 112038/1975, 109630/1978, 163537/1980, 31953/1984, 100440/1984, 121332/1984, 124341/1984, 139352/1984, 146050/1984, 166956/1984.
• the present inventors conducted extensive studies in order to solve the aforementioned problems of the prior art. As a result, the inventors have found that particularly good color reproduction can be achieved if both the azolic magenta coupler and 2,5-diacylaminophenolic cyan coupler specified above are used and if the ratios of y-values attained by allowing three silver halide emulsion layers, which respectively contain a yellow dye-forming coupler, said magenta coupler and said cyan coupler, to form monochromatic colors independently are controlled to be at specific values.
• the present invention has been accomplished on the basis of this finding.
• One object, therefore, of the present invention is to provide a color photographic image that faithfully reproduces the colors of all scenes to be encountered in practical applications.
• Another object of the present invention is to provide a silver halide color photographic material that ensures the faithful reproduction of the colors of all scenes to be encountered in practical applications.
• a silver halide color photographic material that has on a support a silver halide emulsion layer containing a yellow-dye forming coupler of the general formula (I) shown below, a silver halide emulsion layer containing a magenta-dye forming coupler of the general formula (II) shown below, and a silver halide emulsion layer containing a cyan-dye forming coupler of the general formula (III) shown below, and which affords a magenta y to cyan y ratio of 0.85 - 1.00, and a yellow y to cyan y ratio of 0.83 - 1.00 when said photographic material is subjected to monochromatic exposure to blue, green and red light under the conditions specified below, then developed and processed under the conditions specified below, and subsequently subjected to measurement of cyan y, magenta y and yellow y values of the respective colors by the method specified below: (where R 1 is an alky
• the reflection density of the image formed on a developed and subsequently processed sample is measured with a densitometer that satisfies the geometric conditions for reflection density measurement specified in JIS 7612 - 1982 and which hqs interference filters that feature maximum transmission wavelengths of 644 nm, 546 nm and 436 nm for the measurement of cyan, magenta and yellow reflection densities, respectively, and each of which has a half-width of no greater than 18 nm; the y value for each color is calculated by the following formula: where E 1 and E 2 represent the amounts of exposure that are necessary to provide reflection densities of Dmin + 0.5 and Dmin + 1.8, respectively, Dmin signifying the reflection density of unexposed areas.
• Cyan y, magenta y and yellow y are defined as follows:
• the color photographic material of the present invention uses a yellow-dye forming coupler having the general formula (I) shown below, a magenta-dye forming coupler having the general formula (II) shown below, and a cyan-dye forming coupler having the general formula (III) shown below.
• R l is a straight-chained or branched alkyl group (e.g., butyl) or an aryl group (e.g., phenyl), with an alkyl group (e.g., t-butyl) being preferred;
• R 2 is an aryl group (preferably phenyl); the alkyl or aryl group represented by R 1 and R 2 may have a substituent, and an aryl group as R 2 is preferably substituted by, for example, a halogen atom or an alkyl group.
• the yellow coupler of formula (I) is preferably represented by the following general formula (IA): where R 1 and R 2 are each the same as defined for R I and R 2 in formula (I); and Z 1 ' is a group that can be eliminated upon reaction with the oxidized product of a color developing agent.
• the group that is represented by Z 1 ' in formula (IA) and which can be eliminated upon reaction with the oxidized product of a color developing agent is preferably represented by the following general formula (I-1) or (I-2).
• the groups of formula (I-1) one that is represented by the following general formula (I-1') is particularly preferable: (where Z 1 " signifies a group of non-metallic atoms that are capable of forming a 4- to 7-membered ring); (where R 3 is an aryl, heterocyclic or acyl group, with an aryl group being preferred); and (where Z 1 "' signifies a group of non-metallic atoms that are capable of forming a 4- to 6-membered ring together with
• Yellow couplers of formula (I) that are particularly preferable for the purposes of the present invention are represented by the following general formula (I'): where R 4 and R 8 each represents a hydrogen atom, a halogen atom or an alkoxy group, R 4 and R 8 being preferably a halogen atom and a hydrogen atom, respectively; R 5 ; R 6 and R 7 independently are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxyl group, an alkoxycarbonyl group, a carbamyl group, a sulfon group, a sulfamyl group, an alkylsulfonamido group, an acylamido group, a ureido group, or an amino group, each of R 5 and R 6 being preferably a hydrogen atom and R 7 being preferably an alkoxycarbonyl, acylamido or alkylsul
• the yellow couplers of formula (I) may be used either independently or in admixture. They may also be used in combination with other yellow couplers.
• the yellow couplers are preferably added in amounts of 0.05 - 2 moles per mole of silver halide, with the range of 0.1 - 1 mole being more preferable. In terms of the amount present in one silver halide emulsion layer, the range of 1 x 10 -5 to 5 x 10 -2 moles per square meter is preferable and the range of 5 x 10 5 to 1 x 10 -2 mole per square meter is more preferable.
• Z represents a group of the non-metallic atoms necessary for forming a nitrogen-containing heterocyclic ring, provided that the ring formed by Z may have a substituent;
• X represents a hydrogen atom or a substituent capable of being eliminated upon reaction with the oxidation product of a color developing agent; and
• R is a hydrogen atom or 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 spire-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 s
• 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, .
• 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'-[ ⁇ -(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-benzothiazolyl 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 butylotyl phosphonyl group, an alkoxyphosphonyl group such as octyloxyphosphonyl group, an aryloxyphosphonyl group such as phenoxyphosphonyl group and an arylphosphonyl croup 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 substituentts),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 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 1- pentadecylphenoxy)butaneamido]phenoxy, hexadecyl- carbamoylmethoxy, 4-cyanophenoxy, 4-methanesulfonyl- phenoxy, I-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 ' 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 heterocyclic 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 S ' 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 ' 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 ' 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 1 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 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-
• 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 firmed 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 may cooperate to form a ring (for example, 5- to 7-membered cycloalkene, or benzene), respectively.
• a ring for example, 5- to 7-membered cycloalkene, or benzene
• the coupler represented by formula (II) is preferably one represented by the following formula (IIA): wherein R and Z are the same in meaning as R and Z in formula (II), respectively; and X' is a group capable of leaving upon reaction with the oxidized product of a color developing agent.
• the coupler represented by formula (II) preferably includes, for example, those represented by the following formulas (II-1) to (II-6): wherein R 1 to R 8 and X are the same in meaning as R and X mentioned above, respectively.
• the coupler of formula (II) is preferably one represented by the following formula (II-7): wherein R 1 , X and Z 1 are the same in meaning as R, X and Z in formula (II), respectively.
• magenta couplers represented by formulas (II-1) to (11-6) those represented by formula (II-1) are particularly preferably.
• R in fomula (II), (IIA) and R 1 in formulas (II-1) to (II-7) 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 and R 1 on the heterocyclic ring are those represented by the following formula (II-8) wherein 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.
• 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 sulfonamide group, an imido group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group or a heterocyclicthio group, provided that at least two of R 9 ,
• 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 Rg 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 (II) 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 (II), 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 I) and the substituents mentioned with respect thereto.
• a substituent(s) which the ring formed by Z in formula (II) and the ring formed by Z 1 in formula (II-7) each may have and a substituent(s) represented by each of R 2 to R 8 in formulas (II-1) to (II-5) are preferably those represented by the following formula (II-9): wherein R 1 represents an alkylene group; and R 2 represents an alkyl group, a cycloalkyl group or an aryl group.
• the alkylene group represented by R has 2 or more, preferably 3 to 6, carbon atoms in the straight chain, and includes those having a substituent.
• Example of the substituent include those shown as the substituents which the alkyl group may have when R in formula (II) is an alkyl group.
• the substituent is preferably a phenyl group.
• the alkyl group represented by R 2 may be one having a straight-chain or a branched-chain.
• alkyl group examples include methyl, ethyl, propyl, iso-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl and 2-hexyldecyl groups.
• the cycloalkyl group represented by R 2 is preferably one having a 5- or 6-membered ring, for example, a cyclohexyl group. 2
• alkyl and cycloalkyl groups represented by R include those having a substituent, for example, those exemplified as substituents for R 1.
• Examples of the aryl group represented by R 2 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 1 . When two or more substituents are present, they may be the same or different.
• More preferred couplers represented by formula (II) of the present invention are those represented by the following formula (II-10): wherein R 1 and R 2 are the same in meaning as R and R 2 in formula (II-9), and R and X are the same in meaning as R and X in formula (II), respectively.
• the coupler of the present invention is usually incorporated in an amount within the range of 1 x 10 -3 mole to 1 mole, preferably 1 x 10 -2 mole to 8 x 10 -1 mole, per mole of silver halide, and preferably, an amount within the range of 1 x 10 -5 mole/m 2 to 5 x 10 -2 mole/m2 more preferably 5 x 10 -5 mole/m 2 to 1 x 10 -2 mole/m 2 , per one silver halide emulsion layer.
• the coupler of the present invention may be used in alone or in combination and may be used in combination with any other type of magenta coupler.
• a cyan coupler represented by the general formula (III) is used in the present invention:
• R 21 is an alkyl or aryl group; the alkyl group may be straight-chained or branched and is illustrated by methyl, ethyl, iso-propyl, butyl, pentyl, . octyl, nonyl or tridecyl, and the aryl group is exemplified by phenyl or naphthyl.
• the alkyl or aryl group represented by R 21 may have one or more substituents and typical substituents that can be introduced in a phenyl group include the following: a halogen atom, an alkyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an alkylsulfonamido group, an arylsulfonamido group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminosulfonamido group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfinyl group, a sulfoxy group, a sulfo group, an aryloxy group, an alkoxy group, a carboxyl group, an alkylcarbonyl group and an ary
• the alkyl, aryl, heterocyclic or cycloalkyl group signified by R 22 in formula (III) may have one or more substituents.
• Typical substituents that can be introduced in a phenyl group include: a halogen atom, an alkyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an alkylsulfonamido group, an arylsulfonamido group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminosulfonamido group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfinyl group, a sulfoxy group, a sulfo group, an aryloxy group, an alkoxy group,
• R 22 Two or more of these substituents may be introduced in a phenyl group.
• the group signified by R 22 are a polyfluoroalkyl group, an unsubstituted phenyl group and a phenyl group that has one or more substituents selected from a halogen atom, an alkyl group, an alkoxy group, an alkylsulfonamido group, an arylsulfonamido group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, all arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group and a cyano group.
• Z 2 signifies a hydrogen atom or a group that can be eliminated upon reaction with the oxidized product of a color developing agent.
• cyan coupler of formula (III) are represented by the following general formula (IIIA): where R 21 , R 22 and R 23 are each the same as defined for R 21 , R 22 and R 23 in formula (III), and Z 2 ' signifies a group that can be eliminated upon reaction with the oxidized product of a color developing agent.
• R 24 signifies a phenyl group which may have one or more substituents.
• substituents that can be introduced include the following: a halogen atom, an alkyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an alkylsulfonamido group, an arylsulfonamido group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group. Two or more of these substituents may be introduced in a phenyl group.
• R 24 are an unsubstituted phenyl group and a phenyl group that has one or more substituents selected from among a halogen atom (preferably fluorine, chlorine or bromine), an alkylsulfonamido group (preferably o-methylsulfonamido, p-octylsulfonamido or o-dodecylsulfonamido), an arylsulfonamido group (preferably phenylsulfonamido), an alkylsulfamoyl group (preferably butylsulfamoyl), an arylsulfamoyl (preferably phenylsulfamoyl), an alkyl group (preferably methyl or trifluoromethyl), and an alkoxy group (preferably methoxy or ethoxy).
• a halogen atom preferably fluorine, chlorine or bromine
• an alkylsulfonamido group
• R 25 signifies an alkyl or aryl group, each of which may have one or more substituents.
• R 25 is an alkyl when n 1 is 0 and an aryl when n 1 is 1 or more.
• R 25 is an alkyl group having 1 - 22 carbon atoms (preferably methyl, ethyl, propyl, butyl, octyl or dodecyl) when n 1 is 0, and an unsubstituted or substituted phenyl when n l is 1 or more.
• a substituted phenyl is a phenyl that has one or more substituents selected from among an alkyl group (preferably t-butyl, t-amyl or octyl), an alkylsulfonamido group (preferably butylsulfonamido, octylsulfonamido or dodecylsulfonamido), an arylsulfonamido group (preferably phenylsulfonamido), an aminosulfonamido group (preferably dimethylaminosulfonamido), and an alkyloxycarbonyl group (preferably methyloxycarbonyl or butyloxycarbonyl).
• an alkyl group preferably t-butyl, t-amyl or octyl
• an alkylsulfonamido group preferably butylsulfonamido, octylsulfonamido or dodec
• R 26 signifies an alkylene group which may be straight-chained or branched and have 1 - 20 carbon atoms, preferably 1 - 12 carbon atoms.
• R 27 signifies a hydrogen atom or a halogen atom (i.e., fluorine, chlorine, bromine or iodine) and a hydrogen atom is preferred.
• n 1 is 0 or a positive integer, and 0 or 1 is preferred.
• X 1 signifies a divalent group such as -O-, -CO-, -COO-, -OCO-, -S0 2 NR'-, -NR"SO 2 NR"'-, -S-, -SO-and -SO 2 -, wherein R', R" and R"' are each an alkyl group which may optionally have one or more substituents; preferable examples of X 1 are -O-, -S-, -SO-, and -S0 2 .
• Z 2 has the same meaning as defined for Z 2 in formula (III). If Z 2 signifies a group that can be eliminated upon reaction with the oxidized product of a color developing agent, it may be selected from those which are known in the art. Suitable examples are those which either modify the reactivity of couplers or leave couplers such as to work in an advantageous manner by performing such functions as the restraining of development or bleaching and color correction in coupler-containing coated layers or other layers in a silver halide color photographic material.
• Representative examples of the group that can be eliminated upon reaction with the oxidized product of a color developing agent include: a halogen atom typified by chlorine or fluorine, an alkoxy group, an aryloxy group, an arylthio group, a carbamoyloxy group, an acyloxy group, a sulfonyloxy group, a sulfonamido group, a heteroylthio group and a heteroyloxy group.
• Particularly preferable examples of Z 2 are a hydrogen atom and a chlorine atom.
• OPI Japanese Patent Application
• the cyan couplers of formula (III) may be synthesized by known methods such as those described in Japanese Patent Application (O P I) Nos. 31935/1984, 121332/1984, 124341/1984, 139352/1984, 100440/1984, 166956/1984, 146050/1984, 112038/1975, 109630/1978 and 163537/1980, and U.S. Patent No. 2,895,826.
• cyan couplers are used in silver halide emulsion layers in amounts of about 0.05 - 2 moles per mole of silver halide, and the range of 0.1 - 1 mole is preferable. In terms of the amount present in one silver halide emulsion layer, the range of 1 x 10 -5 to 5 x 10 -2 moles per square meter is preferable, with the range of 5 x 10 -5 to 1 x 1 0 -2 mole per square meter being more preferable.
• the cyan couplers of formula (III) may be used either independently or in admixture. They may also be used in combination with other types of cyan couplers. It is particularly preferable that the cyan couplers of formula (III) are used in combination with cyan couplers of the following general formula (IV): where R 28 is a straight-chained or branched alkyl group having 1 - 4 carbon atoms; R 29 is a ballast group; Z 2 has the same meaning as Z. 2 in formula (III); it is particularly preferable that R 28 is a straight-chained or branched alkyl group having 2 - 4 carbon atoms.
• R 28 signifies a straight-chained or branched alkyl group having 1 - 4 carbon atoms and this may have a substituent such as an acylamino group (e.g., acetylamino) or an alkoxy group (e.g., methoxy); R 28 is preferably an alkyl group having 2 - 4 carbon atoms.
• the ballast group signified by R 29 is an organic group whose size and shape are such that it provides the molecule of a coupler with a sufficient bulkiness to render the coupler substantially nondiffusible from the layer in which it is incorporated to another layer.
• Typical ballast groups are alkyl and aryl groups which have a total carbon number of 8 to 32. These alkyl and aryl groups may have substituents.
• Illustrative substituents for an aryl group include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carbosyl group, an acyl group, an ester group, a hydroxyl group, a cyano group, a nitro group, a carbamoyl group, a carbonamido group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, and a halogen atom. All of these substituents except an alkyl group may be used as substituents for an alkyl group.
• ballast groups are those which are represented by the following general formula (IV-1): where R 30 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; Ar is an aryl group such as phenyl and may have a substituent.
• Illustrative substituents are an alkyl group, a hydroxyl group, an alkylsulfonamido group, etc.
• the most preferable substituent is a branched alkyl group such as t-butyl.
• the cyan couplers of formula (IV) may be synthesized by known methods such as those described in Japanese Patent Publication No. 11572/1974, Japanese Patent Application (OPI) Nos. 117249/1985, 205446/1985, 205447/1985 and 232550/1985, and U.S. Patent No. 4,540,657.
• the cyan coupler of formula (IV) may be used in any amount so long as its ratio to the amount of the cyan coupler of formula (III) will not exceed unity.
• the cyan coupler of formula (IV) is used in an amount which is preferably within the range of 100 - 20 mol%, more preferably 100 - 30 mol%, of the cyan coupler of formula (III).
• a particularly preferable combination of couplers used in the present invention is such that each of the yellow coupler of formula (I), magenta coupler of formula (II) and the cyan coupler of formula (III) is two-equivalent.
• the present invention has been accomplished on the basis of the finding that a silver halide color photographic material providing excellent color reproduction can be attained if the yellow, magenta and cyan couplers specified above are used and if said photographic material affords a magenta y to cyan y ratio of 0.85 - 1.00 and a yellow y to cyan y ratio of 0.83 - 1.00 when it is subjected to monochromatic exposure to blue, green and red light under the conditions specified below, then developed and processed under the conditions specified below, and subsequently subjected to measurement of cyan y, magenta y and yellow Y values of the respective colors by the method specified below.
• excellent color reproduction does not simply mean that the purity of primary colors improved to provide the reproduction of brilliant chromatic colors; it also means that desired reproduction is attained for all colors and density regions in the actual practice of color photography and that this is ensured under varying conditions of development and other steps of photographic processing.
• the ratio of magenta y to cyan y is preferably within the range of 0.87 - 0.97 and the ratio of yellow y to cyan y is preferably within the range of 0.85 - 0.97.
• the reflection density of the image formed on a developed and subsequently processed sample is measured with a densitometer that satisfies the geometric conditions for reflection density measurement specified in JIS 7612 - 1982 and which has interference filters that feature maximum transmission wavelengths of 644 nm, 546 nm and 436 nm for the measurement of cyan, magenta and yellow reflection densities, respectively, and each of which has a half-width of no greater than 18 nm; the y value for each color is calculated by the following formula: where E 1 and E 2 represent the amounts of exposure that are necessary to provide reflection densities of Dmin + 0.5 and Dmin + 1.8, respectively, Dmin signifying the reflection density of unexposed areas.
• Cyan y, magenta y and yellow y are defined as follows:
• this photographic material is subjected to exposure to red light, then developed and subsequently processed by the methods described before.
• red-sensitive emulsion in the third layer should ideally undergo exposure to allow only the cyan coupler to form a color dye.
• the blue-sensitive emulsion in the first layer and the green-sensitive emulsion in the second layer will also undergo exposure and, in response to this, the yellow and magenta couplers will also form their respective color dyes.
• the present invention relates in part to a technique of using specific cyan, magenta and yellow couplers, which is already described in several patents such as, for example, Japanese Patent Application (OPI) Nos. 222852/1985 and 229029/1985. They have reference to the color balance of dye images when faded or to the colors of individual dyes; however, none of these prior patents suggest the other part of the present invention which relates to a technique for providing improved color reproduction by attaining a balance between the y values of specific colors.
• OPI Japanese Patent Application
• the balance of y values is a factor that determines the color balance of a photographic image and it is particularly necessary that an appropriate balance of y values be attained in order to reproduce neutral colors. Therefore, theorectically, neutral colors can be reproduced in a desired manner by selecting an appropriate combination of the y values of cyan, magenta and yellow colors. However, it will require a great amount of labor to actually determine the desired combination by an empirical method, for example, on a trial-and-error basis.
• cyan, magenta and yellow couplers of formulas (I), (II) and (III), respectively are selected and light-sensitive silver halide emulsion layers containing these couplers are coated in superposition on a support such that the y values of the couplers can be controlled independently of one another to attain the ratios of y values that are within the ranges specified by the present invention.
• a silver halide color photographic material that is capable of excellent color reproduction can be produced, thereby contributing a significant advantage to the photographic industry.
• the silver halide color photographic material of the present invention is superior not only in the reproduction of neutral colors but also in the reproduction of monochromatic colors.
• One reason for this advantage is that as already mentioned, the photographic material of the present invention uses couplers that are desirable from the view-point of color reproduction. When samples of this photographic material were actually made, they were found to provide far superior reproduction of monochromatic colors than expected from the sole effects of the couplers. This unexpected advantage will most probably have resulted both from the combined use of the couplers specified by the present invention and from the limitation of the ratios of y values for the respective coupler-containing layers to be within the ranges also specified by the invention.
• the specified ratios of y values must be attained by properly adjusting the gradation of the three silver halide emulsions containing cyan, magenta and yellow couplers. While a variety of conventional techniques may be employed for gradation adjustment, the following method is preferably employed in the present invention.
• the basic means for implementing the preferred method of gradation adjustment consists of varying the coating weights of silver and couplers. Generally, a higher coating weight of silver or a coupler produces a hard gradation, and vice versa. This method enables gradation adjustment over the full range of exposure, i.e., from low to high exposure.
• the following table shows the conditions which are preferably employed in the practice of this method.
• a preferable alternative to the method for gradation adjustment that depends on the adjustment of the coating weights of silver and couplers consists of using a combination of silver halide emulsions that are sensitive to the same color but have different sensitivities in each of the silver halide emulsion layers containing the yellow, magenta and cyan couplers specified by the present invention.
• a plurality of such silver halide emulsions may be mixed together for incorporation in the same emulsion layer or they may be contained in separate emulsion layers that are sensitive to the same color.
• a plurality of silver halide emulsions that are sensitive to the same color and have substantially the same sensitivity but which have different levels of gradation may be used in combination.
• the second method which involves the combined use of silver halide emulsions is preferably carried out using monodispersed emulsions of the type to be described later in this specification since it allows for reliable and easy gradation design.
• Examples of the hetero ring that is formed by Zo include the following: an imidazoline ring, an imidazole ring, an imidazolone ring, a pyrazoline ring, a pyrazole ring, a pyrazolone ring, an oxazoline ring, an oxazole ring, an oxazolone ring, a thiazoline ring, a thiazole ring, a thiazolone ring, a selenazoline ring, a selenazole ring, a selenazolone ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a benzimidazole ring, a benzotriazole ring, an indazole ring, a benzoxazole ring, a benzothiazole ring, a benzoselenazole ring
• the heterocyclic residue represented by in formula (V) may have a substituent such as, for example, an alkyl group, an aryl group, an alkenyl group, a sulfamoyl group, a carbamoyl group or an acyl group.
• Particularly preferable mercapto heterocyclic compounds of the formula (V) are mercaptotriazole-based compounds which contain a triazole ring.
• controlled amounts of the compounds may be incorporated both in the silver halide emulsion layers and in adjacent layers with a view to maintaining an appropriate level of fogging and yet achieving the desired gradation.
• the gradation of low-density areas can be controlled to desired values and yet the fogging can be maintained at appropriate levels.
• Compounds of formula (V) are added to silver halide emulsion layers containing the yellow, magenta and cyan couplers specified by the present invention, and optionally in layers adjacent to these emulsion layers.
• the amounts in which such compounds are added are not critical so long as they can attain the intended effects; but usually they are added in a total amount of 5 x 10 6 to 5 x 1 0 3 g/m 2 in the coatings on a support.
• Compounds of formula (V) may be added by any of the methods commonly employed to incorporate photographic additives; for instance, they may be added in the form of solutions in water, an aqueous acidic or alkaline solution having a suitable pH, or in an organic solvent such as methanol or ethanol.
• a more preferable method for implementing the auxiliary means of gradation adjustment consists of using a compound represented by the following general formula (VI) and/or a compound represented by the following general formula (VII): (where R 31 , R 32 , R 33 and R 34 each signifies a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group,-an aryl group, a cycloalkyl group, a hetero ring, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkylacylamino group, an arylacylamino group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfonamido group, an arylsulfonamido group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyls
• each of R 31 to R 34 in formula (VI) may have a substituent such as an alkyl, aryl, aryloxy, alkylthio, cyano, acyloxy, alkoxycarbonyl, acyl, sulfamoyl, hydroxy, nitro, amino or a heterocyclic group; at least one of R 31 to R 34 is a group that has a total of at least 6 carbon atoms, inclusive of the substituents listed above.
• R 35 and R 36 are each a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group, provided that at least one of R 35 and R 36 is a group having a total of at least 6 carbon atoms.
• the alkyl group signified by R 35 or R 36 in formula (VI-1) may be illustrated by methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-amyl, i-amyl, n-octyl, n-dodecyl or n-octadecyl, with alkyl groups having 1 - 32 carbon atoms being particularly preferable.
• the alkenyl group signified by R 35 or R 36 may be illustrated by allyl, octenyl or oleyl, with alkenyl groups having 2 - 32 carbon atoms being particularly preferable.
• the aryl group signified by R 35 or R 36 may be exemplified by phenyl or naphthyl; the acyl group as R 35 or R 36 may be illustrated by acetyl, octanoyl or lauroyl; the cycloalkyl group as R 35 or R 36 may be illustrated by cyclohexyl or cyclopentyl; and examples of the heterocyclic group signified by R 35 or R 36 include imidazolyl, furyl, pyridyl, triazinyl and thiazolyl.
• At least one of R 35 and R 36 in formula (VI-1) is preferably a group that has a total of at least 8 carbon atoms; more preferably, both R 35 and R 36 are a group having a total of 8 - 18 carbon atoms, and most preferably, both R 35 and R 36 are the same group having a total of 8 - 18 carbon atoms.
• R 41 signifies an alkyl, which may be straight-chained or branched, having 1 - 5 alkyl groups; preferably, R 41 is an alkyl group having 2 - 5 carbon atoms.
• R 42 is a hydrogen atom or an alkyl group having 1 - 5 carbon atoms, which may be the same as any one of the alkyl groups listed for use as k 41 ; preferably, R 42 is an alkyl group having 1 - 5 carbon atoms, more preferably 2 - 5 carbon atoms.
• R 41 and R 42 are preferably the same group and, more preferably, R 42 is situated in the position para to R 41 .
• Each of the compounds of formulas (VI) and (VII) is effective for the purpose of preventing color fogging and controlling the gradation of low-density areas.
• these compounds are oil-soluble, they may be dissolved in appropriate high-boiling organic solvents and added as a dispersion of the oil-in-water type. In this case, the compounds may be dispersed simultaneously with or separately from the couplers. If the compounds are water-soluble, they may be added after dissolved in water-miscible organic solvents or aqueous alkaline solutions.
• the photographic material may suffer from a problem in its performance such as image stability in a light place.
• the amounts of compounds of formula (VI) and/or (VII) necessary to attain the desired gradation may be incorporated in the silver halide emulsion layers containing the yellow, magenta and cyan couplers specified by the present invention and/or in adjacent non-sensitive layers such as intermediate layers.
• both compounds of formulas (VI) and (VII) are preferably used because the relationship between gradation adjustment and photographic performance is sufficiently improved to expand the range over which desired gradation adjustment can be accomplished.
• compounds of formula (VI) and (VII) can be added but, in consideration of their effects on the storage stability of dye images and other aspects of photographic performance, compounds of formula (VI) are preferably added in a total amount of 1 x 10 -4 to 2 g/m 2 , more preferably 5 x 10 -3 to 1 g/m 2 , in the coatings on a support, and compounds of formula (VII) are preferably added in a total amount of 1 x 10 to 1.5 g/m 2 , more preferably 2 x 10 3 to 0.7 g/m 2 , in the coating on a support.
• the yellow, magenta and cyan couplers specified by the present invention are preferably used in combination with monodispersed emulsions for attaining the following purposes:
• microdispersed emulsions as used hereinabove means a silver halide emulsion that is composed of silver halide grains that have very small variations in grain shape, grain size, and silver halide composition as between individual grains.
• grain size distribution it is preferable that the coefficient of variation defined below will not exceed 0.20, and the advantages of the present invention will be attained in a more pronounced manner if that coefficient is 0.15 or below: where (where ri signifies the size of individual grains, and ni is the number of those grains).
• grain size is expressed as the diameter if a silver halide grain of interest is spherical, and as the diameter of an equivalent circle for the projected image of the grain if its shape is non-spherical.
• the grain shape distribution is preferably such that when silver halide brains of interest are observed under an electron microscope, the number of grains that have anomalous shapes is no more than 10, preferably no more than 1, for 1,000 grains found within the field of vision.
• the distribution of silver halide composition between grains may be evaluated on the basis of examination of the silver halide compositions of individual grains with an X-ray microanalyzer; preferably, at least 50% of the projected areas of all silver halide grains examined should have a deviation from the average composition that is not greater than 30%, preferably, not greater than 20%.
• Monodispersed emulsions having the features described above may be used independently or, if desired, in combination with other monodispersed emulsions or with polydispersed emulsions.
• the average grain size of the silver halide emulsions used in the present invention is not limited to any particular value but, in consideration of such factors as the progress of development, stability under varying conditions of processing and color reproduction, the silver halide emulsions preferably have an average grain size of 0.1 - 2 um, more preferably 0.2 - 1.5 pm.
• a substantially silver chlorobromide emulsion is a silver halide emulsion that contains silver halide grains whose silver halide composition is such that the content of silver iodide is less than 1 mol%, with the remainder being composed of silver chloride and silver bromide.
• the silver iodide content is preferably as low as possible; in particular, green- and red-sensitive silver halide emulsions should preferably have low silver iodide contents in order to suppress their sensitivity to blue light and to achieve better color reproduction. For the same reason, green- and red-sensitive silver halide emulsions preferably have the highest possible silver chloride content.
• the silver halide grains used in the present invention preferably have a silver chloride content of at least 5 mol%, more preferably at least 15 mol%.
• the silver halide grains used in the present invention may have a homogeneous structure throughout the grain, or the structure of the core may be different from that of the shell. In the latter case, the compositional change may be continuous or discontinuous.
• Soluble silver salts may be reacted with soluble halide salts by any techniques such as the normal mixing method, the revrese mixing method and the double-jet method, the last-mentioned method being preferable.
• Monodispersed silver halide grains may be prepared by the pAg controlled double-jet method which is described in Japanese Patent Application (OPI) No. 48521/1979 as one version of the double-jet method.
• silver halide solvents such as thioether, or crystal habit controlling agents such as mercapto- containing compounds and sensitizing dyes may also be used.
• the silver halide grains to be used in 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 freed of unnecessary soluble salts after completion of the growth of the silver halide grains or may be left as they are containing such salts.
• the silver halide grains used in the present invention may have any crystallographic shapes; they may be regular or irregular such as being spherical or tabular. These crystals may have any surfaces such as ⁇ 100 ⁇ , ⁇ 111 ⁇ and ⁇ 110 ⁇ planes and the proportions of these planes may assume any values.
• Grains that are particularly preferable for use in the present invention are octahedral, tetradecahedral and cubic grains that have regular crystallographic shapes whose surfaces are composed of ⁇ 100 ⁇ and/or ⁇ 111 ⁇ planes.
• the silver halide grains used in the present invention is chemically sensitized by an ordinary method, such as sulfur sensitization using a compound containing sulfur which is capable of reaction with silver ions or using active gelatin, selenium sensitization using a selenium compound, reduction sensitization using a reducing material, or noble metal sensitization using gold and other noble metal compounds. Such methods may be used either independently or in combination.
• the silver halide grains used in the present invention may be spectrally sensitized by suitably selected sensitizing dyes in order to provide sensitivity for the desired spectral wavelength regions.
• a compound known in the photographic industry as an antifoggant or stabilizer may be added to the silver halide grains to be used in 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 the coating of silver halide emulsions.
• Hydrophobic compounds such as the yellow, magenta and cyan couplers specified by the present invention may be dispersed into emulsions by means of vaious methods such as solid dispersion, latex dispersion or oil-in-water drop type emulsion dispersion. Such dispersion methods 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 couplers, which usually comprises dissolving such hydrophobic additives in a high-boiling organic solvent having a boiling point higher than about 150°C, with low-boiling and/or water-soluble organic solvents being optionally used together, then emulsion-dispersing the dissolved hydrophobic additives in the presence of a surfactant in a hydrophilic binder such as an 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 a hydrophilic colloidal layer of interest.
• a surfactant in a hydrophilic binder such as an aqueous gelatin solution with such means of dispersion as a stirrer, homogenizer, colloid mill, flow- jet mixer or ultrasonic disperser, and thereafter adding
• Dispersion aids may be used in dissolving hydrophobic compounds in low-boiling solvents used either alone or in combination with high-boiling organic solvents, then dispersing the dissolved hydrophobic compounds in water by mechanical means or with ultrasonic waves; suitable dispersion aids include anionic surfactants, nonionic surfactants and cationic surfactants.
• High-boiling organic solvents which are used as media for dispersing the yellow, magenta and cyan couplers specified by the present invention are preferably selected from among the compounds having dielectric constants'of no higher than 6.0 at 30°C. There are no particular lower limits for the dielectric constants of such compounds but they preferably have dielectric constants of at least 1.9.
• Illustrative compounds are those which have dielectric constants of no more than 6.0 such as esters (e.g. phthalate esters and phosphate esters), organic acid amides, ketones and hydrocarbon compounds. Phthalate esters and phosphate esters are more preferable.
• Two or more high-boiling organic solvents may be used in mixture and, in this case, the resulting mixture preferably has a dielectric constant of 6.0 or below.
• High-boiling organic solvents that can be used in combination in the present invention include dibutyl phthalate, dimethyl phthalate, tricresyl phosphate, tributyl phosphate, etc.
• Phthalate esters that may be used advantageously in the present invention are represented by the following general formula (VIII): where R 51 and R 52 each signifies an alkyl, alkenyl or aryl group, provided that the total number of carbon atoms in the group signified by R 51 or R 52 ranges from 9 to 32, preferably from 16 to 24.
• the alkyl group signified by R 51 or R 52 in formula (VIII) may be straight-chained or branched.
• the alkyl, alkenyl or aryl group signified by R 51 or R 52 may have one or more substituents; substituents for the alkyl or alkenyl group include a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkoxycarbonyl group, etc.; substituents for the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkoxycarbonyl group, etc. Two or more of these substituents may be introduced in the alkyl, alkenyl or aryl group.
• Phosphate esters that may be used advantageously in the present invention are represented by the following general formula (IX): where R 53 , R 54 or R 55 each signifies an alkyl, alkenyl or aryl group, provided that the total number of carbon atoms in the group signified by R 53 , R 54 or R 55 ranges from 24 to 54.
• the alkyl, alkenyl or aryl group signified by R 53 , R 54 or R 55 in formula (IX) may have one or more substituents; preferably, R 53 , R 54 and R 55 are each an alkyl group such as 2-ethylhexyl, n-octyl, 3,5,5-trimethylhexyl, n-nonyl, n-decyl, sec-decyl, sec-dodecyl or t-octyl.
• These high-boiling organic solvents are generally used in amounts ranging from 10 to 150 wt%, preferably from 20 to 100 wt%, of each of the couplers specified by the present invention.
• Image stabilizers may be incorporated in the silver
• halide color photographic material of the present invention in order to prevent deterioration of color images.
• Image stabilizers that are preferably used in the present invention include: the compounds represented by the general formula (A) on page 101 of the specification of Japanese Patent Application No. 117493/1985 (specifically exemplified by A-I to A-32 on pages 109 - 116), the compounds represented by the general formula (B) on page 117 of the same specification (specifically exemplified by B-1 to B-55 on pages 123 - 127), the compounds represented by the general formula (C) on page 128 of the same specification (specifically exemplified by C-1 to C-17 on pages 133 and 134), the compounds represented by the general formula (D) on page 128 of the same specification (specifically exemplified by D-1 to D-11 on pages 135 and 136), the compounds represented by the general formula (E) on page 137 (specifically exemplified by E-1 to E-42 on pages 143 - 147), the compounds represented by the general formula (F) on page 148 of the same specification (specifically exemplified by
• image stabilizers may be incorporated in any layer but they are preferably incorporated in a silver halide emulsion layer containing the magenta coupler of formula (II) specified by the present invention. There is also no particular limitation on the amount in which the image stabilizers are added but the preferable range is from 2 to 16 mg/dm 2 .
• Gelatin is advantageously used as a binder (or protective colloid) for emulsion layers that contain the silver halide grains used in the present invention.
• hydrophilic colloids may be used and they include gelatin derivatives, graft polymers of gelatin with other high-molecular weight substances, proteins, sugar derivatives, cellulosic derivatives, and synthetic hydrophilic high-molecular weight substances such as homo- and copolymers.
• Photographic emulsion layers and other hydrophilic colloidal layers in the silver halide color photographic material of the present invention are hardened with hardeners that are used either alone or in combination to bridge the molecule of the binder (or protective colloid) to provide an enhanced 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 layers and/or other hydrophilic colloidal layers in the light-sensitive material of the present invention.
• dispersions (latices) of water-insoluble or slightly water-soluble synthetic polymers may be incorporated in photographic emulsion layers and other hydrophilic colloidal layers in the light-sensitive material using the silver halide emulsions of the present invention.
• the silver halide color photographic material of the present invention which is typically used as color paper is intended to achieve color reproduction by the subtractive processes and, hence, has such a structure that silver halide emulsion layers containing the magenta, yellow and cyan couplers specified by the present invention, as well as non-light-sensitive layers are coated in superposition on a support, with the number and sequence of layers being appropriately changed according to the importance of a certain aspect of performance and the specific object of use.
• the silver halide color photographic material of the present invention comprises, in order from the support side, a yellow-dye image forming layer, an intermediate layer, the magenta-dye image forming layer of the present invention, an intermediate layer, a cyan-dye image forming layer, an intermediate layer, and a protective layer, which are coated as separate layers on the support.
• hydrophilic colloidal layers such as protective layers and intermediate layers in the color photographic material of the present invention may have incorporated therein UV absorbers in order to prevent the occurrence of fogging due to discharge resulting from the photographic material being charged by friction or the like, or to prevent the deterioration of images due to UV light.
• the silver halide color photographic material of the present invention can be provided with auxiliary layers such as filter layers, anti-halation layers and/or anti-irradiation layers. These auxiliary layers and/or the emulsion layers may have incorporated therein dyes that will flow out of the color photographic material or which will be bleached during development or subsequent processing.
• Matting agents may be incorporated in silver halide emulsion layers and/or other hydrophilic colloidal layers in the silver halide color photographic material of the present invention, with a view to attaining such purposes as reducing the surface gloss of the light-sensitive material, enhancing the writability in pencil, and preventing the adhesion of light-sensitive materials to each other.
• the silver halide color material of the presentinven- tion may contain a lubricant that is capable of reducing its sliding friction.
• the silver halide color 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.
• Photographic emulsion layers and/or other hydrophilic colloidal layers in the light-sensitive material using the silver halide emulsions 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 gradation and sensitization.
• Photographic emulsion layers and other layers for making the silver halide photographic material of the present invention may be coated onto flexible reflecting supports such as baryta paper, paper laminated with a-olefin polymers, and synthetic paper, 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 baryta paper, paper laminated with a-olefin polymers, and synthetic paper, 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.
• reflective supports are preferable and may be exemplified by paper that is laminated with a polymer such
• the silver halide color photographic material of the present invention may be coated onto the suppot 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, wear 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 silver halide color photographic material 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 silver halide photographic material of the present invention may be exposed to electromagnetic waves in the spectral region to which the emulsion layers that make up the photographic 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 lamps. 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 present invention provides a silver halide color photographic material that ensures the reproduction of the colors of all scenes to be encountered in the actual practice of color photography.
• Samples (Nos. 1 to 8) of silver halide color photographic material having the basic composition shown in Table 1 were prepared by common procedures. In order to control the ratios of y values for the three colors, cyan, magenta and yellow, the coating weights of silver and coupler in the third layer of each sample were varied as shown in Table 2.
• UV-1 Ultraviolet absorber
• Sample Nos. 1 to 8 were processed under the conditions to be described below and the values for cyan, magenta and yellow colors obtained by monochromatic exposure to red, green and blue light were determined for each sample. Thereafter, the ratio of the y value of the yellow coupler containing layer to the y value of the cyan coupler containing layer (Y/C) and the ratio of the y value of the magenta coupler containing layer to the y value of the cyan coupler containing layer (M/C) were calculated for each sample and the results are shown in Table 2.
• the reflection density of the image formed on a developed and subsequently processed sample is measured with a densitometer that satisfies the geometric conditions for reflection density measurement specified in JIS 7612 - 1982 and which has interference filters that feature maximum transmission wavelengths of 644 nm, 546 nm and 436 nm for the measurement of cyan, magenta and yellow reflection densities, respectively, and each of which has a half-width of no greater than 18 nm; the Y value for each color is calculated by the following formula: where E 1 and E 2 represent the amounts of exposure that are necessary to provide reflection densities of Dmin + 0.5 and Dmin + 1.8, respectively, Dmin signifying the reflection density of unexposed areas.
• Cyan y, magenta y and yellow y are defined as follows:
• the standard color chips, 5R, 5YR, 5Y, 5GY, 5G, 5BG, 5B, 5PB, 5P and 5RP, that were prepared in accordance with JIS Z 8721 were shooted under daylight to make color negative films on Sakura Color SR-100 with KONIKA FS-1.
• the negatives were printed on sample Nos. 1 to 8, with color correcting filters being adjusted such that a patch for an achromatic color chip having a V value (a measure of lightness) of 40 would reproduce a substantially neutral color.
• V value a measure of lightness
• the tone of the patch giving the highest chroma at each level of lightness was measured for each color specimen with a color analyzer, Model 607 of Hitachi, Ltd. Based on the measured values, L", u' and v' values were determined by the method specified in JIS Z 8729 and the u' and v' values of the patch corresponding to an L * value of about 40 were plotted on a chromaticity diagram.
• the area of the region bounded by the plots on the chromaticity diagram was determined to obtain a region of color reproduction.
• the area of this region was used as a measure of evaluation of color reproduction; the larger this area, the better the color reproduction that was attained.
• Table 2 shows that improved color reproduction was attained when the two ratios of y values, Y/C and M/C, were controlled to be within the ranges specified for the present invention by adjusting the coating weights of silver and couplers.
• Sample Nos. 9 to 14 of silver halide color photographic material were prepared as in Example 1 except that the first and third layers shown in Table 1 were modified as follows:
• Table 3 shows that improved color reproduction was attained when the two ratios of y values, Y/C and M/C, were controlled to be within the ranges specified for the present invention by adjusting the mixing proportions of two silver halide emulsions that were sensitive to the same color but which had different sensitivities.
• each of the four emulsions was monodispersed in that it was substantially free from any anomalously shaped grains and was uniform in grain size and morphology.
• EM-1 and EM-2 were chemically ripened with sodium thiosulfate and a sensitizing dye D-1 (for its structure, see below), and upon completion of the chemical ripening, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added so as to make blue-sensitive emulsions, EMB-3 and EMB-4.
• a part of EM-3 was chemically ripened with sodium thiosulfate and a sensitizing dye D-2 (for its structure, see below), and upon completion of the chemical ripening, 4-hydroxy--6-methyl-1,3,3a,7-tetrazaindene and a compound of formula (V) (No. 13; 20 mg/mole of silver halide) were added so as to make a green-sensitive emulsion, EMG-1.
• Emulsion EM-4 was chemically ripened with sodium thiosulfate and a sensitizing dye D-3 (for its structure, see below), and upon completion of the chemical ripening, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added so as to make a red-sensitive emulsion, EMR-1.
• a comparative sample of silver halide color photographic material was prepared; the composition of this sample, referred to as Sample No. 15, is identified in Table 5 below.
• the blue-sensitive emulsion in the first layer was composed of a mixture of EMB-3 and EMB-4 so as to provide an appropriate gradation in the low-density areas.
• the three sensitizing dyes, D-1, D-2 and D-3 had the following structures:
• Comparative yellow coupler, CY-1, comparative magenta coupler, CM-1, and ultraviolet absorber, UV-2, shown in Table 5 had the following structures:
• UV-2 Ultraviolet absorber
• Comparative sample Nos. 16 to 24 and sample Nos. 25 to 27 of the present invention were prepared as in the preparation of Sample No. 15 except that the yellow, magenta and cyan couplers and silver deposit for the first, third and fifth layers were changed to those indicated in Table 6.
• the ratio of EMB-3 to EMB-4 in terms of silver was held constant.
• Sample Nos. 15 to 27 thus prepared were processed as in Example 1 and the y values for cyan, magenta and yellow colors obtained by monochromatic exposure to red, green and blue light were determined for each sample. Thereafter, the ratio of the y value of the yellow-coupler containing layer to the y value of the cyan-coupler containing layer (Y/C) and the ratio of the y value of the magenta-coupler containing layer to the y value of the cyan-coupler containing layer (M/C) were calculated for each sample and the results are shown in Table 6.
• The.advantages of the present invention were confirmed visually on actual prints that were prepared from color negative films.
• the negatives had been obtained by shooting actual scenes (several objects having different degrees of lightness and color tone) on Sakura Color SR 100 with KONIKA FS-1, followed by a predetermined scheme of development and subsequent processing.
• the reproduction of neutral colors and chromatic colors on the prints was evaluated visually by the following criteria. The results are shown in Table 7.
• Table 7. shows the following: sample Nos. 25 to 27 prepared in accordance with the present invention achieved good reproduction of not only neutral colors but also monochromatic colors; and the advantages of the present invention could fully be confirmed by visual checking of prints prepared in the actual practice of color photography. It is therefore clear that a silver halide color photographic material prepared in accordance with the present invention produces color pictures that reproduce shaper monochromatic images and which have a good balance between neutral colors.
• Comparative sample Nos. 28 to 30 and sample Nos. 31 to 42 of the present invention were prepared as in Example 3 except that the cyan, magenta and yellow couplers were changed to those shown in Table 8.
• the coating weight of silver ie, silver deposit
• the ratios of y values would be within the ranges specified by the present invention.
• Table 8 shows that sample Nos. 31 to 42 prepared in accordance with the present.invention attained better color reproduction than comparative sample Nos. 28 to 30. Comparison between sample Nos. 39, 40, 41 and 42 shows that particularly good results are obtained by using a cyan coupler-of formula (IV) in combination with a cyan coupler of formula (III).
• Sample No. 43 was prepared by the same method as used for preparing sample No. 41 in Example 5, except that C-29 and C-36 were used as cyan couplers, compound No. 59 as a magenta coupler and Y-31 as a yellow coupler, and that the silver deposits for the respective emulsion layers were adjusted to attain ratios of y values that were within the ranges specified by the present invention.
• Sample Nos. 44 and 45 were prepared by the same method as used for preparing sample No. 43, except that sample No. 44 used EMG-2 as the green-sensitive emulsion in the third layer while sample No. 45 used EMG-2 in the third layer. These two emulsions were the same as EMG-1 except that the amount of compound No. 13 of formula (V) that was added upon completion of chemical ripening was reduced to 0 mg and 10 mg, respectively, per mole of silver halide.
• Sample No. 46 was prepared by the same method as used for preparing sample No. 46 except that compound No. 13 of formula (V) was incorporated in the fourth layer for a coating weight of 0.018 m g/ m 2 .
• Sample Nos. 47 and 48 were prepared by the same method as used for preparing sample No. 43 except that compound No. 4 of formula (VI) was changed to 0 mg/m and 0. 0 2 g/ m 2 , respectively.
• Sample No. 49 was prepared by the same method as used for preparing sample No. 43 except that compound No. 3 of formula (VII) was additionally incorporated in the third layer in an amount of 0.00 5 g/ m 2 .
• Table 9 shows that sample Nos. 45, 46, 48 and 49 exhibited even better. color reproduction because they employed the auxiliary technique of gradation adjustment described in this specification. However, sample Nos. 44 and 47 did not use any of the compounds of formulas (V), (VI) and (VII) and their ability to reproduce neutral colors in low-density areas was somewhat unsatisfactory although they were superior in respect of the area of color reproduction.
• sample No. 46 or 49 The seven samples were also subjected to evaluation of both resistance to fogging in an active color developing solution (ie, with reduced potassium bromide content) and stability of dye images under exposure to light (ie, exposure to sunshine for 30 days). Compared with sample No. 43, sample Nos. 44, 45 and 47 were slightly inferior in terms of resistance to fogging in the active developing solution, and sample No. 48 was somewhat unsatisfactory with respect to the storage stability of dye images under daylight. None of these problems occurred to either sample No. 46 or 49.

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• 1986
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