Silver halide color photographic material

FIELD OF THE INVENTION
The present invention relates to a silver halide color photographic material, which, as the case may be, will be hereinafter referred to simply as a photographic material.
BACKGROUND OF THE INVENTION
It is well known that a silver halide color photographic material contains coupler(s) and that the coupler(s) in the material is/are reacted with an oxidation product of an aromatic primary amine color developing agent, that has been formed by oxidation with the exposed silver halide in the material as an oxidizing agent, to form a color image composed of indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and the related dyes. In such a photographic system, subtractive color photography is used, and color images are formed of yellow, magenta and cyan dyes.
Of these, for producing cyan color images, phenol or naphthol couplers are generally used. However, since these couplers have unfavorable absorption in a green range, they have a serious problem that they noticeably lower the color reproducibility. Therefore, it is desired to overcome the problem.
As a means for overcoming the problem, heterocyclic compounds as described in U.S. Pat. Nos. 4,728,598 and 4,873,183 and European Patent 249,453A2 (corresponding to U.S. Pat. No. 4,818,672) have been proposed. However, these have a fatal problem that the coupling activity thereof is low. As couplers free from the problem, pyrroloazoles described in European Patent Laid-Open No. 0491197A1 (corresponding to U.S. Pat. No. 5,256,526) have been proposed. These couplers are excellent in point of the coupling activity of themselves and the color hue of the dyes to be formed therefrom. However, the pyrroloazotes disclosed in the patent had a problem that the color density of the dyes to be formed from them often fluctuates due to the fluctuation of the composition of the bleach-fixing solution (hereinafter referred to as "blix solution") to be used for processing the photographic materials containing the couplers. The fluctuation of the color density of the dyes formed was noticeable especially when the concentrations of thiosulfato ions and sulfito ions in the blix solution vary during continuous processing. The couplers had another problem with respect to the fastness of the color images to be formed therefrom in that the fastness of the image part having a relatively low color density is inferior to that of the image part having a high color density. For these reasons, it has been desired to improve the couplers in order to put them into practical use. In addition, the couplers had still another problem that they give a large cyan fog in the unexposed areas of the photographic materials during continuous .processing. Given the situation, it has been desired to improve the couplers so as to overcome the problems.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a silver halide color photographic material containing cyan coupler(s) having a high coupling activity to form dye(s) having an excellent color hue without fluctuation of the color density thereof to be caused by fluctuation of the composition of the blix solution used for processing the material.
Another object of the present invention is to provide a silver halide color photographic material containing cyan coupler(s) capable of forming color images where the fastness in the parts having a-low color density is improved.
A further object of the present invention is to provide a silver halide color photographic material containing cyan coupler(s) of causing little cyan color fog in the non-exposed areas of the material during continuous processing.
The above-mentioned objects of the present invention have been attained by a silver halide color photographic material comprising a support having provided thereon at least one layer containing at least one cyan coupler represented by formula (I) ##STR2## wherein R.sub.1 and R.sub.2 each represent a substituent except methyl group;
R.sub.3, R.sub.4, R.sub.5 and R.sub.6 each represent a hydrogen atom or a substituent;
Z represents a non-metallic atom or a non-metallic atomic group necessary for forming a ring, the non-metallic atomic group of Z may optionally be substituted by substituent(s); and
X represents a hydrogen atom, or a group of splitting off from the formula by coupling reaction with an oxidation product of an aromatic primary amine color developing agent.

DETAILED DESCRIPTION OF THE INVENTION
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and X in formula (I) will be explained in detail hereunder.
Where the substituents as referred to herein contain an aliphatic moiety or aliphatic moieties, the moiety or moieties may be linear, branched or cyclic (e.g., cycloalkyl), saturated or unsaturated (e.g., alkenyl), and substituted or unsubstituted, unless otherwise specifically indicated. The aliphatic moiety is preferably an alkyl group.
Where the substituents as referred to herein contain an aryl moiety or aryl moieties, the moiety or moieties may be substituted or unsubstituted, and monocyclic (e.g., phenyl) or condensed-cyclic (e.g., naphthyl). The aryl moiety is preferably a phenyl group.
Where the substituents as referred to herein contain a heterocyclic moiety or heterocyclic moieties, the hereto atoms constituting the ring of the heterocyclic moiety may be chosen from among nitrogen, oxygen and sulfur atoms, the ring is preferably 5-membered to 8-membered, the carbon and nitrogen atoms on the ring may be substituted or unsubstituted, and the ring may be monocyclic or condensed-cyclic.
The number of carbon atoms of the substituent as referred to herein indicates the total number of the carbon atoms constituting the substituent.
R.sub.1 and R.sub.2 each represent a substituent except methyl group.
R.sub.1 and R.sub.2 include, for example, a halogen atom (e.g., chlorine, bromine), an aliphatic group (e.g., linear or branched alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl group having from 2 to 36 carbon atoms; precisely, such as ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido}phenyl}propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3-(2,4-di-t-amylphenoxy)propyl), an aryl group (preferably having from 6 to 36 carbon atoms, e.g., phenyl, naphthyl, 4-hexadecoxyphenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl, 3-(2,4-tert-amylphenoxyacetamido)phenyl), a heterocyclic group (e.g., 3-pyridyl, 2-furyl, 2-thienyl, 2-pyridyl, 2-pyrimidyl, 2-benzothiazolyl), an alkoxy group (preferably having from 1 to 30 carbon atoms, e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), an aryloxy group (preferably having from 6 to 30 carbon atoms, e.g., phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), a heterocyclic-oxy group (e.g., 2-benzimidazolyloxy, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an alkyl-, aryl- or heterocyclic-thio group (preferably having from 1 to 36 carbon atoms, e.g., methylthio, ethylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-(4-tert-butylphenoxy)propylthio, phenylthio, 2-butoxy-5-tert-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,4-triazol-6-thio, 2-pyridylthio), an alkyl-, aryl- or heterocyclic-acyloxy group (preferably having from 2 to 30 carbon atoms, e.g., acetoxy, hexadecanoyloxy), a carbamoyloxy group (preferably having from 1 to 30 carbon atoms, e.g., N-ethylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (preferably having from 1 to 30 carbon atoms, e.g., trimethylsilyloxy, dibutylmethylsilyloxy), an alkyl- aryl- or heterocyclic-sulfonyloxy group (preferably having from 1 to 30 carbon atoms, e.g., dodecylsulfonyloxy), an acylamino group (preferably having from 2 to 30 carbon atoms, acetamido, benzamido, tetradecanamido, 2-(2,4-di-tert-amylphenoxyacetamido, 2-[4-(4 -hydroxyphenylsulfonyl)phenoxy)]decanamido, isopentadecanamido, 2-(2,4-di-t-amylphenoxy)butanamido, 4-(3-t-butyl-4-hydroxyphenoxy)butanamido), an alkylamino group (preferably having from 1 to 30 carbon atoms, e.g., methylamino, butylamino, dodecylamino, dimethylamino, diethylamino, methylbutylamino), an arylamino group (preferably having from 6 to 30 carbon atoms, e.g., phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidoanilino, N-acetylanilino, 2-chloro-5-[.alpha.-2-tert-butyl-4-hydroxyphenoxy)dodecylamido]anilino, 2-chloro-5-dodecyloxycarbonylanilino), an ureido group (preferably having from 2 to 30 carbon atoms, e.g., methylureido, phenylureido, N,N-dibutylureido, dimethylureido), a sulfamoylamino group (preferably having from 1 to 30 carbon atoms, e.g., N,N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), an alkenyloxy group (preferably having from 2 to 30 carbon atoms, e.g., 2-propenyloxy), a formyl group, an alkyl-, aryl- or heterocyclic-acyl group (preferably having from 1 to 30 carbon atoms, e.g., acetyl, benzoyl, 2,4-di-tert-amylphenylacetyl, 3-phenylpropanoyl, 4-dodecyloxybenzoyl), an alkyl-, aryl- or heterocyclic-sulfonyl group (preferably having from 1 to 30 carbon atoms, e.g., methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), an alkyl-, aryl- or heterocyclic-sulfinyl group (preferably having from 1 to 30 carbon atoms, e.g., octanesulfinyl, dodecylsulfinyl, phenylsulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), an alkyl-, aryl- or heterocyclic-oxycarbonyl group (preferably having from 2 to 30 carbon atoms, e.g. , methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenyloxycarbonyl, 2-pentadecyloxycarbonyl), an alkyl-, aryl- or heterocyclic-oxycarbonylamino group (preferably having from 2 to 30 carbon atoms, e.g., methoxycarbonylamino, tetradecyloxycarbonylamino, phenoxycarbonylamino, 2,4-di-tert-butylphenoxycarbonylamino), an alkyl-, aryl- or heterocyclic-sulfonamido group (preferably having from 1 to 30 carbon atoms, e.g., methanesulfonamido, hexadecansulfonamido, benzenesulfonamido, p-toluenesulfonamido, octadecanesulfonamido, 2-methoxy-5-tert-butylbenzenesulfonamido), a carbamoyl group (preferably having from 1 to 30 carbon atoms, e.g., N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-docecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl, N-[3-(2,4-di-tert-amylphenoxy)propyl]carbamoyl), a sulfamoyl group (preferably having from 1 to 30 carbon atoms, e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), a phosphonyl group (preferably having from 1 to 30 carbon atoms, e.g., phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a sulfamido group (preferably having from 1 to 30 carbon atoms, e.g., dipropylsulfamoylamino), an imido group (preferably having from 1 to 30 carbon atoms, e.g., N-succinimido, hydantoinyl, N-phthalimido, 3-octadecenylsuccinimido), an azolyl group (e.g., imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl), an alkyl- or aryl-substituted silyl group (preferably having 1 to 36 carbon atoms, e.g., trimethylsilyl, t-butyldiphenylsilyl), a hydroxyl group, a cyano group, a carboxyl group, a nitro group, a sulfo group, and an unsubstituted amino group.
R.sub.1 and R.sub.2 each are preferably an aliphatic group having from 2 to 30 carbon atoms, an aryl group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a halogen atom, an alkyl- or aryl-oxycarbonyl group, a carbamoyl group, or an alkyl- or aryl-substituted silyl group.
More preferably, R.sub.1 and R.sub.2 each are an aliphatic group having from 2 to 30 carbon atoms, an aryl group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, or an aryloxy group having from 6 to 30 carbon atoms. Especially preferably, they each are a branched alkyl group having from 3 to 30 carbon atoms. R.sub.1 and R.sub.2 may be the same or different, and they may be substituted by one or more substituents such as those mentioned hereinabove.
R.sub.3, R.sub.4, R.sub.5 and R.sub.6 each represent a hydrogen atom or a substituent. The substituents of R.sub.3, R.sub.4, R.sub.5 and R.sub.6 include a methyl group and those mentioned hereinabove for R.sub.1 and R.sub.2.
R.sub.3, R.sub.4 and R.sub.5 each are preferably a hydrogen atom, an alkyl group having from 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, or a group that is bonded to the formula via an ester group, an amido group or a silicon atom. The group bonded to the formula via an ester group includes an alkyl-, aryl- or heterocyclic-oxycarbonyl group. The group bonded to the formula via an amido group includes a carbamoyl group. The group bonded to the formula via an silicon atom includes an alkyl- or aryl-substituted silyl group. More preferably, R.sub.3, R.sub.4 and R.sub.5 each are a hydrogen atom, or an alkyl, aryl, alkoxy or aryloxy group having from 1 to 30 carbon atoms. Especially preferably, they are hydrogen atoms. R.sub.3, R.sub.4 and R.sub.5 may be the same or different, and they may be substituted by one or more substituents such as those mentioned hereinabove for R.sub.3 to R.sub.6.
R.sub.6 is preferably an alkyl group, an aryl group, a heterocyclic group, a carbamoyl group, an acylamino group, or an ureido group. More preferably, it is an aryl group. Especially preferably, it is an aryl group having at least a substituent at its ortho-position.
R.sub.6 is more preferably represented by the following formula ##STR3## where Rx and Ry each represent a substituent that may be chosen from among the substituents of R.sub.3 to R.sub.6 ; and m represents an integer of from 0 to 4.
The substituent Rx in the ortho-position is preferably a halogen atom, or a group that bonds to the phenyl nucleus via a hydrogen bond-accepting atom such as oxygen, nitrogen or sulfur atom, or a group containing such hydrogen bond-accepting atom(s) (e.g., methoxycarbonylmethyl, chloromethyl, methylthiomethyl, 2-N-methylpyrrole). More preferably, it is a group that bonds to the phenyl nucleus via an oxygen atom. Especially preferably, it is an alkoxy group having from 1 to 40 carbon atoms, or an aryloxy group having from 6 to 46 carbon atoms.
The compounds of the present invention include stereoisomers with respect to the substituents R.sub.1 to R.sub.5. Where the compounds of the present invention are used, either mixtures of such isomers or single isomers may be used.
In formula (I), Z represents an atom or an atomic group necessary for forming a 4-membered to 12-membered ring, preferably a 5-, 6-, 7- or 8-membered ring, along with the carbon atoms to which it is bonded. The divalent group Z which forms such a ring may be a divalent amino group, an ether bond, a thioether bond, an alkylene group, an alkenylene group, an-imino group, a sulfonyl group, or a carbonyl group, or a combination of two or more of them. The divalent amino group as Z is represented by ##STR4## wherein R represents a hydrogen atom, an alkyl group or an aryl group. These may have one or more substituents such as those mentioned hereinabove for R.sub.3 to R.sub.6. The divalent group of Z which forms .such a ring is preferably a divalent amino group, an ether bond, a thioether bond, an alkylene group, an alkenylene group, or an imino group. More preferably, it is an alkylene group or an alkenylene group. Most preferably, it is an alkylene group.
The ring to be formed by Z includes a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a 1,4-cyclohexadiene ring, a cycloheptane ring, a cyclooctane ring, an oxane ring, a piperidine ring, a 1,3-dioxane ring, a sulfolane ring and a thiane ring. The ring to be formed by Z is preferably a saturated, 6-membered carbon ring.
In formula (I), the moiety of: ##STR5## is preferably represented by the following formula: ##STR6## wherein R.sub.8 to R.sub.13 each represent a hydrogen atom or a substituent. As examples of the substituent, those mentioned hereinabove for R.sub.3 to R.sub.6 are referred to.
In formula (I), X represents a hydrogen atom or a group of splitting off from the formula when the coupler is reacted with an oxidation product of an aromatic primary amine color developing agent (the group is hereinafter simply referred to as a split-off group). As the split-off group, there are mentioned, for example, a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic-oxy group, an alkyl-, aryl- or heterocyclic-acyloxy group, an alkyl-, aryl- or heterocyclic-sulfonyloxy group, a dialkyl- or diaryl-phosphonoxy group, a dialkyl- or diaryl-phosphinoxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a heterocyclic-oxycarbonyloxy group, an alkyl-, aryl- or heterocyclic-sulfonyl group, an alkyl-, aryl- or heterocyclic-sulfinyl group, an alkyl-, aryl- or heterocyclic-carbonyl group, an alkyl-, aryl- or heterocyclic-acylamino group, an alkyl-, aryl- or heterocyclic-sulfonamido group, a carbamoylamino group, an alkyl-, aryl- or heterocyclic-thio group, an imido group, an arylazo group, and a 5-membered or 6-membered, nitrogen-containing heterocyclic group that bonds to the coupling position of the formula via its nitrogen atom. The alkyl, aryl and heterocyclic moieties in these split-off groups may be substituted by one or more substituents such as those mentioned hereinabove for R.sub.3 to R.sub.6. Where the moieties have two or more substituents, the substituents may be the same or different and they may have one or more substituents such as those mentioned hereinabove for R.sub.3 to R.sub.6.
More precisely, the split-off group includes a halogen atom (e.g., fluorine, chlorine, bromine), an alkoxy group (preferably having from 1 to 30 carbon atoms, e.g., ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), an aryloxy group (preferably having from 6 to 36 carbon atoms, e.g., 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), a heterocyclic-oxy group (preferably having from 1 to 36 carbon atoms, e.g., 5-phenyltetrazolyloxy, 2-benzothiazolyloxy), an alkyl-, aryl- or heterocyclic-acyloxy group (preferably having from 2 to 30 carbon atoms, e.g., acetoxy, tetradecanoyloxy, benzoyloxy), an alkyl-, aryl- or heterocyclic-sulfonyloxy group (preferably having from 1 to 30 carbon atoms, e.g., methanesulfonyloxy, toluenesulfonyloxy), a dialkyl- or diaryl-phosphonoxy group (preferably having from 1 to 30 carbon atoms, e.g., diethylphosphonoxy, diphenylphosphonoxy), a dialkyl- or diaryl-phosphinoxy group (preferably having from 1 to 30 carbon atoms, e.g., dimethylphosphinoxy), a heterocyclic-oxycarbonyloxy group (e.g., 5-phenyltetrazoiyloxycarbonyloxy, 2-benzothiazolyloxycarbonyloxy), an alkyl-, aryl- or heterocyclic-sulfonyl group (preferably having from 1 to 30 carbon atoms, e.g., toluenesulfonyl, methanesulfonyl, tetrazolylsulfonyl), an alkyl-, aryl- or heterocyclic-sulfinyl group (preferably having from 1 to 30 carbon atoms, e.g., phenylsulfinyl, i-propylsulfinyl, tetrazolylsulfinyl), an alkyl-, aryl- or heterocyclic-carbonyl group (e.g., acetyl, benzoyl, tetrazolylcarbonyl), an alkyl-, aryl- or heterocyclic-acylamino group (preferably having from 2 to 30 carbon atoms, e.g., dichloroacetylamino, heptafluorobutyrylamino), an alkyl-, aryl- or heterocyclic-sulfonamido group (preferably having from 1 to 30 carbon atoms, e.g., methanesulfonamido, trifluoromethanesulfonamido, p-toluenesulfonamido), an alkoxycarbonyloxy group (preferably having from 2 to 30 carbon atoms, e.g., ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably having from 7 to 36 carbon atoms, e.g., phenoxycarbonyloxy), an alkyl-, aryl- or heterocyclic-thio group (preferably having from 1 to 36 carbon atoms, e.g., ethylthio, 2-carboxyethylthio, dodecylthio, 1-carboxydodecylthio, phenylthio, perfluorophenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio), a carbamoylamino group (preferably having from 1 to 30 carbon atoms, e.g., N-methylcarbamoylamino, N-phenylcarbamoylamino), a 5-membered or 6-membered, nitrogen-containing heterocyclic group that bonds to the coupling position of the formula via its nitrogen atom (preferably having from 1 to 36 carbon atoms, e.g., imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), an imido group (preferably having from 1 to 30 carbon atoms, e.g., succinimido, hydantoinyl), and an arylazo group (preferably having from 6 to 36 carbon atoms, e.g., phenylazo, 4-methoxyphenylazo). As a matter of course, the split-off group may further be substituted by one or more substituents, such as those previously mentioned for R.sub.3 to R.sub.6. As a split-off group that bonds to the formula via a carbon atom, there are mentioned bis-type couplers to be obtained by condensation of 4-equivalent couplers with aldehydes or ketones. The split-off group of the present invention may contain a photographically useful group such as, for example, a development inhibitor or a development accelerator.
Preferably, X is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkyl- or aryl-thio group, and a 5-membered or 6-membered nitrogen-containing heterocyclic group that bonds to the coupling-active position in the formula via a nitrogen atom. More preferably, it is a hydrogen atom or a halogen atom. Especially preferably, it is a chlorine atom.
Cyan couplers of formula (I) may be dimers or higher polymers in which the group(s) of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and/or X are/is divalent group(s) to be bonded to dimer(s) or higher polymer(s) or to high molecular chain(s) to form homopolymers or copolymers. Such homopolymers or copolymers in which the group(s) is/are bonded to high molecular chain(s) are typically homopolymers or copolymers of addition-polymerizing ethylenic unsaturated compounds having cyan coupler residue(s) of formula (I). In these cases, the homopolymers or copolymers each may have one or more cyan coloring repeating units each having a cyan coupler residue of formula (I) in the polymer molecule and may contain one or more non-coloring ethylenic monomers as comonomer components to be copolymers. The cyan coloring repeating unit having a cyan coupler residue of formula (I) is preferably represented by the following formula (P): ##STR7## where R represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, or a chlorine atom;
A represents --CONH--, --COO--, or a substituted or unsubstituted phenylene group;
B represents a substituted or unsubstituted alkylene having from 1 to 30 carbon atoms, phenylene having from 6 to 36 carbon atoms or aralkylene group having from 7 to 37 carbon atoms;
L represents --CONH--, --NHCONH--, --NHCOO--, --NHCO--, --OCONH--, --NH--, --COO--, --OCO--, --CO--, --O--, --S--, --SO.sub.2 --, --NHSO.sub.2 --, or --SO.sub.2 NH--;
a, b and c each represent 0 or 1; and
Q represent a cyan coupler residue derived from a compound of formula (I) by removing a hydrogen atom from the group of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 or X in the respective formula.
As the polymers, preferred are copolymers comprising cyan coupler units of coloring monomers of formula (I) and non-coloring ethylenic monomers which do not couple with an oxidation product of an aromatic primary amine developing agent.
As non-coloring ethylenic monomers which do not couple with an oxidation product of an aromatic primary amine developing agent, for example, mentioned are acrylic acid, .alpha.-chloroacrylic acid, .alpha.-alkylacrylic acids (e.g., methacrylic acid) and amides or esters to be derived from these acrylic acids (e.g., acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetylacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, .beta.-hydroxy methacrylate), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g., styrene and derivatives thereof, such as vinyl toluene, divinylbenzene, vinylacetophenone and sulfoethylene), iraconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g., vinyl ethyl ether), maleates, N-vinyl-2-pyrrolidone, -N-vinylpyridine, and 2- and 4-vinylpyridines.
Of these, especially preferred are acrylates, methacrylates and maleates. In the present invention, the copolymers may contain two or more different non-coloring ethylenic monomers. For instance, mentioned are combination of methyl acrylate and butyl acrylate, combination of butyl acrylate and styrene, combination of butyl methacrylate and methacrylic acid, and combination of methyl acrylate and diacetoneacrylamide.
As well known in the field of polymer couplers, ethylenic unsaturated comonomers to be copolymerized with vinyl monomers corresponding to the above-mentioned formula (I) are so selected that the physical and/or chemical properties of the copolymers to be formed therefrom, such as the solubility of them, the compatibility of them with binders of photographic compositions such as gelatin, the flexibility of them as well as the thermal stability of them are favorably influenced by the selected comonomers.
For incorporating the couplers of the present invention into silver halide photographic materials, preferably into the red-sensitive silver halide emulsion layers of them, it is preferred that the couplers are in the form of so-called coupler-in-emulsion type ones. For this purpose, it is preferred that the total carbon number in the substituent R.sub.6 is from 1 to 50, more preferably from 4 to 30, especially preferably from 7 to 20. The total carbon number in the alkoxy moiety in the ester part in the couplers of the present invention is preferably from 3 to 50, more preferably from 4 to 30, especially preferably from 6 to 20.
Next, specific examples of the couplers of the present invention are mentioned below, which, however, are not intended to restrict the scope of the present invention. ##STR8##
The production of the compounds of the present invention will be mentioned below.
A general method for producing the compounds of the present invention may be represented by the following reaction scheme: ##STR9##
Compounds of formula (II) may be produced in accordance with the method described in European Patent Laid-Open No. 0491197A1 (corresponding to U.S. Pat. No. 5,256,526). The interesterification and the subsequent conversion into the 2-equivalent form (I) may also be effected in accordance with the method described in the same patent publication.
Next, some production examples of producing typical compounds of the present invention are mentioned below.
PRODUCTION EXAMPLE 1
Production of Compound (7) ##STR10##
Precisely, 3.00 g of compound (1), 7.78 g of compound (2) and 1.00 g of Ti(OiPr).sub.4 were dissolved in 4 ml of sulforane and heated at 170.degree. C. for 2 days. This was cooled, stirred with ethyl acetate and water and filtered through silica gel. The organic layer was separated and dried with MgSO.sub.4. This was concentrated, and 5 g of the thus-concentrated black oil was purified by silica gel column chromatography (using hexane/ethyl acetate=2/1) to obtain 0.91 g of an amorphous product of compound (3). The yield of the product was 20%.
Compound (2) was produced according to the method described in J.A.C.S., 79 (1957) 5019, ibid., 69 (1947) 2414.
1.02 g of reduced iron, 0.12 g of NH.sub.4 Cl, 22.5 ml of isopropyl alcohol (IPA) and 2.5 ml of water were stirred on a steam bath, and compound (3) that had been produced previously was added thereto along with 10 ml of IPA and then stirred vigorously. After 35 minutes, the finish of the reaction was confirmed by thin layer chromatography, and the reaction mixture was filtered through silica gel while hot. This was concentrated to obtain 0.87 g of pale brown crystals. 20 ml of DMF and 0.92 g of compound (4) were added thereto and stirred for a while at room temperature, and 0.16 ml of pyridine were added thereto slowly. Then, this was allowed to stand at room temperature overnight. This was extracted with ethyl acetate and dried with MgSO.sub.4. The concentrated residue was purified by column chromatography to obtain 0.45 g of an amorphous product of compound (5).
The thus-obtained compound (5) was easily chlorinated with one equivalent amount of SO.sub.2 Cl.sub.2 in CH.sub.2 Cl.sub.2 at room temperature. After this was purified through a column, 0.42 g of compound (7) was obtained.
PRODUCTION EXAMPLE 2
Production of Compound (53) ##STR11##
Precisely, 1.54 g of compound (1), 2.58 g of compound (2) and 0.32 g of Ti(OiPr).sub.4 were dissolved in 2 ml of sulforane and stirred under heat at 155.degree. C. for 6 hours. This was cooled, stirred along with ethyl acetate and water and filtered through Celite. The organic layer was separated, dried with MgSO4 and then concentrated to obtain 3.40 g of a brown oil. This was purified by silica gel column chromatography .(using hexane/ethyl acetate=20/1) to obtain 1.25 g of crystals of compound (53). The yield of the product was 64%.
The other compounds of the present invention may be produced in accordance with the same methods as mentioned above.
The photographic material of the present invention may be one which has at least one layer containing the cyan coupler(s) of the present invention on a support. The layer of containing the cyan coupler(s) of the present invention may be a hydrophilic colloid layer on a support. An ordinary photographic material has at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on a support in this order, and the order of the constitutive layers on the support may be different from the said one. The material may contain an infrared-sensitive silver halide emulsion layer in place of at least one of the above-mentioned light-sensitive emulsion layers. These light-sensitive emulsion layers each may comprise a silver halide emulsion having a sensitivity to the respective wavelength range and a color coupler of forming a dye having a complementary color to the light to which the emulsion is sensitive, whereby color reproduction by subtractive color photography may be effected. The relationship between the light-sensitive emulsion layer and the color hue of the dye to be formed from the color coupler in the layer is not limited to the above-mentioned constitution but may be of any others.
Where the cyan couplers of the present invention are applied to photographic materials, they are preferably incorporated into the red-sensitive silver halide emulsion layer of the material.
The content of the cyan coupler(s) of the present invention in the photographic material may be from 1.times.10.sup.-3 mol to 1 mol, preferably from 2.times.10.sup.-3 mol to 3.times.10.sup.-1 mol, per mol of the silver halide in the layer containing the cyan coupler(s).
The cyan couplers of the present invention can be introduced into the photographic material by various known methods. Preferred is an oil-in-water dispersion method in which the coupler is dissolved in a high boiling point organic solvent (if desired, along with a low boiling point organic solvent) and the resulting solution is dispersed in an aqueous gelatin solution by emulsification and added to a silver halide emulsion.
Examples of high boiling point solvents to be used in an oil-in-water dispersion method which may be employed in the present invention are described in U.S. Pat. No. 2,322,027. As one polymer dispersion method, known is a latex dispersion method which may also be employed in the present invention. The process of such a latex dispersion method, the effect of the same and specific examples of latexes for impregnation to be used in the method are described in U.S. Pat. No. 4,199,363, German Patent OLS Nos. 2,541,274 and 2,541,230, JP-B-53-41091 and European Patent Laid-Open No. 029104. A dispersion method of using organic solvent-soluble polymers may also be employed in the present invention, which is described in PCT Laid-Open WO88/00723.
As examples of high boiling point organic solvents usable in the above-mentioned oil-in-water method, there are mentioned phthalates (e.g., dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate), phosphates or phosphonates (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, dioctylbutyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexylphenyl phosphonate), benzoates (e.g., 2-ethylhexyl benzoate, 2,4-dichlorobenzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N,N-diethyidodecanamide, N,N-diethyllaurylamide), alcohols or phenols (e.g., isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic esters (e.g., dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl citrate), aniline derivatives (e.g. , N,N-dibutyl-2-butoxy-5-tert-octylaniline), chlorinated paraffins (e.g., paraffins having chlorine content of from 10% to 80%), trimesates (e.g., tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (e.g., 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol 4-(4-dodecyloxyphenylsulfonyl)phenol), carboxylic acids (e.g., 2-(2,4-di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), and alkylphosphoric acids (e.g., di-(2-ethylhexyl)phosphoric acid, diphenylphosphoric acid). As auxiliary solvents usable along with the high boiling point organic solvents, there are mentioned, for example, organic solvents having a boiling point of approximately from 30.degree. C. to 160.degree. C., such as ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.
The proportion of the high boiling point organic solvent to be used in the case may be from. 0 to 10.0 times, preferably from 0 to 5.0 times, more preferably from 0.5 to 4.5 times, to the coupler.
As silver halide .emulsions and other elements (e.g., additives, etc.) of constituting the photographic material of the present invention, photographic layers of constituting the material (e.g., arrangement of layers), and methods of processing the material and additives usable in the processing methods, those described in the following patent publications, especially in European Patent 0,355,660A2, are preferably employed.
__________________________________________________________________________Photographic Elements JP-A 62-215272 JP-A 2-33144 EP 0,355,660A2__________________________________________________________________________Silver Halide Emulsions From page 10, right upper From page 28, right upper From page 45, line 53 to page column, line 6 to page 12, left column, line 16 to page 29, 47, line 3; and page 47, lines lower column, line 5; and right lower column, line 20 to 22 from page 12, right lower and page 30, lines 2 to 5 column, line 4 to page 13, left upper column, line 17Silver Halide Solvents Page 12, left lower column, -- -- lines 6 to 14; and from page 13, left upper column, line 3 from below to page 18, left lower column, last lineChemical Sensitizers Page 12, from left lower Page 29, right lower column, Page 47, lines 4 to 9 column, line 3 from below to line 12 to last line right lower column, line 5 from below; and from page 18, right lower column, line 1 to page 22, right upper column, line 9 from belowColor Sensitizers From page 22, right upper Page 30, left upper column, Page 47, lines 10 to 15(Color Sensitizing Methods) column, line 8 from below to lines 1 to 13 page 38, last lineEmulsion Stabilizers From page 39, left upper Page 30, from left upper Page 47, lines 16 to 19 column, line 1 to page 72, column, line 14 to right right upper column, last line upper column, line 1Development Promoters From page 72, left lower -- -- column, line 1 to page 91, right upper column, line 3Color Couplers (Cyan, From page 91, right upper From page 3, right upper Page 4, lines 15 to 27; fromMagenta and Yellow column, line 4 to page 121, column, line 14 to page 18, page 5, line 30 to page 8, lastCouplers) left upper column, line 6 left upper column, last line; line; page 45, lines 29 to 31; and from page 30, right and from page 47, line 23 to upper column, line 6 to page page 63, line 50 35, right lower column, line 11Coloring Enhancers From page 121, left upper -- -- column, line 7 to page 125, right upper column, line 1Ultraviolet Absorbents From page 125, right upper From page 37, right lower Page 65, lines 22 to 31 column, line 2 to page 127, column, line 14 to page 38, left lower column, last line left upper column, line 11Anti-fading Agents From page 127, right lower From page 36, right upper From page 4, line 30 to page(Color Image Stabilizers) column, line 1 to page 137, column, line 12 to page 37, 5, line 23; from page 29, line left lower column, line 8 left upper column, line 19 I to page 45, line 25; page 45, lines 33 to 40; and page 65, lines 2 to 21High Boiling Point and/or From page 137, left lower From page 35, right lower Page 64, lines 1 to 51Low Boiling Point Organic column, line 9 to page 144, column, line 14 to page 36,Solvents right upper column, last line left upper column, line 4 from belowDispersing Methods of From page 144, left lower From page 27, right lower From page 63, line 51 to pagePhotographic Additives column, line 1 to page 146, column, line 10 to page 28, 64, line 56 right upper column, line 7 left upper column, last line; and from page 35, right lower column, line 12, to page 36, right upper column, line 7Hardening Agents From page 146, right upper -- -- column, line 8 to page 155, left lower column, line 4Developing Agent Page 155, from left lower -- --Precursors column, line 5 to right lower column, line 2Development Inhibitor Page 155, right lower -- --Releasing Compounds column, lines 3 to 9Supports From page 155, right lower From page 38, right upper From page 66, line 29 to page column, line 19 to page 156, column, line 18 to page 39, 67, line 13 left upper column, line 14 left upper column, line 3Constitution of Photographic Page 156, from left upper Page 28, right upper column, Page 45, lines 41 to 52Layers column, line 15 to right lines 1 to 15 lower column, line 14Dyes From page 156, right lower Page 38, from left upper Page 66, lines 18 to 22 column, line 15 to page 184, column, line 12 to right right lower column, last line upper column, line 7Color Mixing Preventing From page 185, left upper Page 36, right lower column, From page 64, line 57 to pageAgents column, line 1 to page 188, lines 8 to 11 65, line 1 right lower column, line 3Gradation Adjusting Agents Page 188, right lower -- -- column, lines 4 to 8Stain Inhibitors From page 188, right lower Page 37, from left upper From page 65, line 32 to page column, line 9 to page 193, column, last line to right 66, line 17 right lower column, line 10 lower column, line 13Surfactants From page 201, left lower From page 18, right upper -- column, line 1 to page 210, column, line 1 to page 24, right upper column, last one right lower column, last line; and page 27, from left lower column, line 10 from below to right lower column, line 9Fluorine-containing From page 210, left lower From page 25, left upperCompounds (as antistatic column, line 1 to page 222, column, line 1 to page 27,agents, coating aids, left lower column, line 5 right lower column, line 9lubricants, and anti-blockingagents)Binders (hydrophilic From page 222, left lower Page 38, right upper column, Page 66, lines 23 to 28colloids) column, line 6 to page 225, lines 8 to 18 left upper column, last lineTackifiers From page 225, right upper -- -- column, line 1 to page 227, right upper column, line 2Antistatic Agents From page 227, right upper -- -- column, line 3 to page 230, left upper column, line 1Polymer Latexes From page 230, left upper -- -- column, line 2 to page 239, last lineMat Agents, Page 240, from left upper -- -- column, line 1 to right upper column, last linePhotographic Processing From page 3, right upper From page 39, left upper From page 67, line 14 to pageMethods (Processing steps column, line 7 to page 10, column, line 4 to page 42, 69, line 28and additives) right upper column, line 5 upper column, last line__________________________________________________________________________ Remarks: The cited specification of JPA-62-215272 is one as amended by th letter of amendment filed on March 16, 1987.
In addition, the silver halide color photographic materials and the methods for processing them described in JP-A-5-34889, JP-A-4-359249, JP-A-4-313753, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433, JP-A-2-854, JP-A-1-158431, JP-A-2-90145, JP-A-3-194539, JP-A-2-93641, European Patent 0520457A2 are also preferably referred to.
Silver halides to be used for constituting the photographic material of the present invention include silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide and silver iodobromide. For the purpose of rapidly processing the photographic material, preferred is a silver chlorobromide emulsion having a silver chloride content of 90 mol % or more, preferably 95 mol % or more, especially preferably 98 mol % or more, or a pure silver chloride -emulsion, which does not substantially contain silver iodide.
For the purpose of improving the sharpness of the image to be formed on the photographic material of the present invention, it is preferred to incorporate a dye capable of being decolored by photographic processing, as described in European Patent 0,337,490A2 (especially oxonole dyes), into the hydrophilic colloid layer of the material in such an amount that the optical reflection density of the material at 680 nm may be 0.70 or more, or to incorporate a titanium oxide as surface-treated with a di-hydric to tetra-hydric alcohol (e.g., trimethylolethane) into the water-proof resin layer of the support of the material in an amount of 12% by weight or more, more preferably 14% by weight or more.
The photographic material of the present invention preferably contains a color image preservability improving compound, for example, one as described in European Patent 0,277,589A2, along with couplers. Incorporation of such a color image preservability improving compound into the material along with a pyrazoloazole magenta coupler is preferred.
Specifically, single or combined incorporation of a compound (F) described in European Patent 0,277,589A2, which may bind with the aromatic amine developing agent as remained in the photographic material after color development thereof by chemical bond between them to form a chemically inactive and substantially colorless compound and/or a compound (G) described in European Patent 0,277,589A2, which may bind with the oxidation product of an aromatic amine developing agent as remained in the photographic material after color development thereof by chemical bond between them to form a chemically inactive and substantially colorless compound into the photographic material of the present invention is preferred for the purpose of preventing formation of color dyes by reaction of the color developing agent or the oxidation product thereof as remained in the photographic material and couplers in the material during storage of the processed material to cause formation of stains in the processed material during storage thereof and also preventing any other harmful side effect of the remained agent and oxidation product of thereof.
The photographic material of the present invention also preferably contain a microbicide, such as one as described in JP-A-63-271247, for the purpose of preventing propagation of various fungi and bacteria in the hydrophilic colloid layer of the processed material which would deteriorate the image formed on the material.
As a support to be in the photographic material of the present invention, a white polyester support or a support having a white pigment-containing layer on the side to face with silver halide emulsion layers as coated thereover may be employed for displays. In order to improve the sharpness of the image to be formed, it is preferred to provide an anti-halation layer on the support on either of the side to face with silver halide emulsion layers as coated thereover or the opposite back side thereto. In particular, it is preferred to define the transmission density of the support-to fall within the range of from 0.35 to 0.8, in order that the display with the photographic material of the present invention be may seen either with a reflecting light or a transmitting light.
The photographic material of the present invention may be exposed either with visible rays or with infrared rays. For exposure of the material, either low intensity exposure or high intensity short-time exposure may be employed. In particular, in the latter case, a laser scanning exposure system is preferred where the exposure time is shorter than 10.sup.-4 second per pixel.
In exposure of the photographic material of the present invention, a band stop filer described in U.S. Pat. No. 4,880,726 is preferably used. Using it, rays of causing light stain may be removed so that the color reproducibility of the exposed material is improved noticeably.
Next, the present invention will be explained in more detail by means of the following examples, which, however, are not intended to restrict -the scope of the present invention.
EXAMPLE 1
Plural photographic constitutive layers each having the composition mentioned below were coated ever a paper support, of which the both surfaces had been laminated with polyethylene, to form a multi-layer color photographic paper (sample No. 109). Coating liquids were prepared in the manner mentioned below.
Preparation of Coating Liquid for Fifth Layer
20.0 g of cyan coupler (Compound (1) mentioned hereinabove), 30.0 g of color image stabilizer (Cpd-1), 5.0 g of color image stabilizer (Cpd-2), 8.0 g of color image stabilizer (Cpd-5), 1.0 g of color image stabilizer (Cpd-6), 10.0 g of color image stabilizer (Cpd-8), 1.0 g of color image stabilizer (Cpd-9), 15.0 g of color image stabilizer (Cpd-10), 1.0 g of color image stabilizer (Cpd-11), 35.0 g of solvent (Solv-2), 35.0 g of solvent (Solv-9) and 5.0 g of sodium dodecylbenzenesulfonate were dissolved in 80 ml of ethyl acetate, and the resulting solution was emulsified and dispersed in an aqueous 20% gelatin solution, using a high-speed stirring emulsifier.
On the other hand, silver chlorobromide emulsion C (5/5 (by mol of silver) mixture of large-size emulsion R.sub.1 of cubic grains with a mean grain size of 0.60 .mu.m and small-size emulsion R.sub.2 of cubic grains with a mean grain size of 0.48 .mu.m; the fluctuation coefficient of the grain size distribution of the two emulsions was 0.06 and 0.08, respectively; the silver halide grains in the both emulsions had 0.5 mol % of silver bromide locally on a part of the surface of each grain while having silver chloride on the remaining part of the surface thereof) was prepared. The emulsion contained the following red-sensitizing dye E in an amount of 1.0.times.10.sup.-4 mol per mol of silver in the large-size emulsion and 1.2.times.10.sup.-4 mol per mol of silver in the small-size emulsion. Chemical ripening of the emulsion was effected by sulfur sensitization and gold sensitization. The emulsified dispersion as previously prepared and the silver chlorobromide emulsion were blended to give a coating liquid for the fifth layer having the composition mentioned below.
The other coating liquids for the first to seventh layers were also prepared in the same manner as in preparation of the coating liquid for the fifth layer. As a gelatin hardening agent for each layer, added thereto was 1-hydroxy-3,5-dichloro-s-triazine sodium salt.
The respective layers contained 25.0 mg/m.sup.2, as a whole, of Cpd-14 and 50 mg/m.sup.2, as a whole, of Cpd-15.
Silver chlorobromide emulsions for the other light-sensitive emulsion layers Were prepared in the same manner as in preparation of the above-mentioned silver chlorobromide emulsion C, except that the size and the halogen composition of the silver halide grains were varied and the color-sensitizing dyes mentioned below were added.
Blue-sensitive Emulsion Layer
Sensitizing Dye A ##STR12## (2.0.times.10.sup.-4 mol per mol of silver halide to large-size emulsion; and 2.5.times.10.sup.-4 mol per mol of silver halide to small-size emulsion)
Sensitizing Dye B ##STR13## (2.0.times.10.sup.-4 mol per mol of silver halide to large-size emulsion; and 2.5.times.10.sup.-4 mol per mol of silver halide to small-size emulsion)
Green-sensitive Emulsion Layer
Sensitizing Dye C ##STR14## (4.0.times.10.sup.-4 mol per mol of silver halide to large-size emulsion; and 5.6.times.10.sup.-4 mol per mol of silver halide to small-size emulsion)
Sensitizing Dye D ##STR15## (7.0.times.10-5 mol per mol of silver halide to large-size emulsion; and 1.0.times.10.sup.-4 mol per mol of silver halide to small-size emulsion)
Red-sensitive Emulsion Layer
Sensitizing Dye E ##STR16## (1.0.times.10.sup.-4 mol per mol of silver halide to large-size emulsion; and 1.2.times.10.sup.-4 mol per mol of silver halide to small-size emulsion) In addition, the following compound was added in an amount of 2.6.times.10.sup.-3 mol per mol of silver halide. ##STR17##
To the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer was added 1-(5-methylureidophenyl)-5-mercaptotetrazole each in an amount of 2.5.times.10.sup.-3 mol, 4.0.times.10.sup.-3 mol and 2.5.times.10.sup.-4 mol, per mol of silver halide, respectively.
To the blue-sensitive emulsion layer and the green-sensitive emulsion Layer was added 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene each in an amount of 1.times.10.sup.-4 mol and 2.times.10.sup.-4 mol, per mol of silver halide, respectively.
For anti-irradiation, the following dyes were added to the respective emulsion layers, the coated amount being parenthesized. ##STR18## Layer Constitution
Compositions of the layers of constituting sample No. 109 are mentioned below, in which the numerical value indicates the amount coated (g/m.sup.2) and the amount of the silver halide coated is represented as silver therein.
Support:
Polyethylene-laminated Paper (This contained white pigment (TiO.sub.2, 14% by weight) and bluish dye (ultramarine) in polyethylene below the first layer. The centerline surface roughness of the surface of the support to be coated with the first layer was 0.13 .mu.m.)
First Layer: Blue-sensitive Emulsion Layer
______________________________________Silver Chlorobromide Emulsion A (3/7 (by mol of 0.24silver) mixture of large-size emulsion of cubicgrains with a mean grain size of 0.88 .mu.m andsmall-size emulsion of cubic grains with a meangrain size of 0.70 .mu.m; the fluctuation coefficientof the grain size distribution of the twoemulsions was 0.08 and 0.10, respectively; thesilver halide grains in the both emulsions had 0.3mol % of silver bromide locally on a part of thesurface of each grain while having 0.1 mg, as awhole, of potassium hexachloroiridate(IV) and 1.0mg, as a whole, of potassium ferrocyanide in theinside and the local silver bromide phase in eachgrain)Gelatin 1.36Yellow Coupler (ExY) 0.65Color Image Stabilizer (Cpd-1) 0.16Color Image Stabilizer (Cpd-2) 0.08Color Image Stabilizer (Cpd-3) 0.08Solvent (Solv-1) 0.13Solvent (Solv-5) 0.13______________________________________
Second Layer: Color Mixing Preventing Layer
______________________________________Gelatin 0.80Color Mixing Preventing Agent (Cpd-4) 0.11Solvent (Solv-7) 0.03Solvent (Solv-2) 0.25Solvent (Solv-3) 0.25______________________________________
Third Layer: Green-sensitive Emulsion Layer
______________________________________Silver Chlorobromide Emulsion B (1/3 mixture (by 0.13mol of Ag) of large-size emulsion of cubic grainswith a mean grain size of 0.55 .mu.m and small-sizeemulsion of cubic grains with a mean grain size of0.39 .mu.m; the two emulsions each had a fluctuationcoefficient of the grain size distribution of 0.10and 0.08, respectively; they contained 0.8 mol % ofsilver bromide locally on a part of the surface ofeach grain, while having 0.2 mg, as a whole, ofpotassium hexachloroiridate(IV) and 1.0 mg, as awhole, of potassium ferrocyanide in the inside andthe local silver bromide phase in each grain; theyhad been subjected to optimum chemicalsensitization with a sulfur sensitizer and a goldsensitizer in the presence of a decomposate ofnucleic acid)Gelatin 1.40Magenta Coupler (ExM) 0.18Color Image Stabilizer (Cpd-5) 0.15Color Image Stabilizer (Cpd-2) 0.03Color Image Stabilizer (Cpd-6) 0.01Color Image Stabilizer (Cpd-7) 0.01Color Image Stabilizer (Cpd-8) 0.08Solvent (Solv-3) 0.20Solvent (Solv-4) 0.35Solvent (Solv-8) 0.35______________________________________
Fourth Layer: Color Mixing Preventing Layer
______________________________________Gelatin 0.65Color Mixing Preventing Agent (Cpd-4) 0.08Solvent (Solv-7) 0.02Solvent (Solv-2) 0.18Solvent (Solv-3) 0.18______________________________________
Fifth Layer: Red-sensitive Emulsion Layer
______________________________________Above-mentioned Silver Chlorobromide Emulsion C 0.13Gelatin 1.61Cyan Coupler (compound (1) mentioned above) 0.20Color Image Stabilizer (Cpd-1) 0.30Color Image Stabilizer (Cpd-2) 0.05Color Image Stabilizer (Cpd-5) 0.08Color Image Stabilizer (Cpd-6) 0.01Color Image Stabilizer (Cpd-8) 0.10Color Image Stabilizer (Cpd-9) 0.01Color Image Stabilizer (Cpd-10) 0.15Color Image Stabilizer (Cpd-11) 0.01Solvent (Solv-2) 0.35Solvent (Solv-9) 0.35______________________________________
Sixth Layer: Ultraviolet Absorbing Layer
______________________________________Gelatin 0.50Ultraviolet Absorbent (UV-1) 0.38Color Image Stabilizer (Cpd-5) 0.02Color Image Stabilizer (Cpd-12) 0.15______________________________________
Seventh Layer: Protective Layer
______________________________________Gelatin 1.00Acryl-modified Copolymer of Polyvinyl Alcohol 0.05(modification degree 17%)Liquid Paraffin 0.02Color Image Stabilizer (Cpd-13) 0.01______________________________________
The compounds used above are mentioned below. ##STR19##
Other samples (Nos. 101 to 108 and 110 to 115) were prepared in the same manner as in preparation of sample No. 108, except that the coupler in the fifth layer was varied to that indicated in Table A below.
The samples were exposed and then processed in the manner mentioned below.
Exposure
Using a sensitometer (FWH Model, manufactured by Fuji Photo Film Co.; with a color temperature of the light source of being 3200.degree. K.), sample No. 107 was exposed to such a degree that about 30% of the coated silver is developed to give gray color.
The exposed sample was processed with a paper processing machine in accordance with the process mentioned below, until the total amount of the replenisher to the color developer tank became two times the tank capacity.
______________________________________Process: Amount ofProcessing Replenisher TankStep Temperature Time (*) Capacity______________________________________Color 38.5.degree. C. 45 sec 73 ml 10 litersDevelopmentBlix 35.degree. C. 45 sec 60 ml 10 litersRinsing 1 35.degree. C. 20 sec -- 5 litersRinsing 2 35.degree. C. 20 sec -- 5 litersRinsing 3 30 to 35.degree. C. 20 sec 360 ml 5 litersDrying 70 to 80.degree. C. 60 sec______________________________________ (*) per m.sup.2 of sample being processed. (Rinsing was effected by threetank countercurrent cascade system from 3 t 1.)
Compositions of the processing solutions used above are mentioned below.
______________________________________ TankColor Developer Solution Replenisher______________________________________Water 700 ml 700 mlSodium 0.1 g 0.1 gTriisopropylnaphthalene(.beta.)sulfonateEthylenediaminetetraacetic Acid 3.0 g 3.0 gDisodium 1,2-Dihydroxybenzene-4,6- 0.5 g 0.5 gdisulfonateTriethanolamine 12.0 g 12.0 gPotassium Chloride 6.5 g --Potassium Bromide 0.03 g --Potassium Carbonate 27.0 g 27.0 gBrightening Agent (WHITEX 4B, made 1.0 g 3.0 gby Sumitomo Chemical Co.)Sodium Sulfite 0.1 g 0.1 gDisodium N,N- 10.0 g 13.0 gbis(sulfonatoethyl)hydroxylamineN-ethyl-N-(.beta.-methanesulfonamidoethyl)-3- 5.0 g 11.5 gmethyl-4-aminoaniline SulfateWater to make 1000 ml 1000 mlpH (25.degree. C.) 10.00 11.00______________________________________
______________________________________ TankBlix Solution Solution Replenisher______________________________________Water 600 ml 600 mlAmmonium Thiosulfate (700 g/liter) 100 ml 250 mlAmmonium Sulfite 20 g 100 gAmmonium 55 g 135 gEthylenediaminetetraacetato/Iron(III)Disodium Ethylenediaminetetraacetate 5 g 12.5 gAmmonium Bromide 40 g 75 gNitric Acid (67%) 30 g 65 gWater to make 1000 ml 1000 mlpH (25.degree. C.) 5.80 5.60______________________________________
Rinsing Solution
Ion-exchanged Water (having calcium and magnesium content of 3 ppm or less each).
Next, using the above-mentioned sensitometer, all the samples were stepwise exposed through a color-separation filter. The exposed samples were then processed, using the running solutions that had been prepared by the above-mentioned continuous-processing. The thus-processed samples were evaluated with respect to their photographic properties by the methods mentioned below.
Evaluation 1: Color Hue (Y/C)
The yellow density at the point giving a cyan density of 1.0 in the cyan-colored layer was measured, using a densitometer, X-Rite 310 Model (made by X-Rite Co.). The smaller the yellow density, the smaller the side-absorption and therefore the better the color hue.
Evaluation 2: Variation in Color Density Due to Fluctuation of Composition of Blix Solution Used
Using the running solutions, the exposed samples were processed by two methods. In one method, used was a fresh blix solution; while in the other method, used was a blix solution containing twice the amount of ammonium thiosulfite and twice the amount of ammonium sulfite. The decrease in the maximum cyan color density due to the change of the blix solutions used was represented by percentage.
Evaluation 3: Color Image Fastness
The processed samples were stored at 100.degree. C. for 2 days and at 80.degree. C. and 70% RH for 6 days. The decrease in the density of each sample before and after the storage was measured at the point having an initial density of 0.6. The decrease in the density was represented by percentage.
Evaluation 4: Color Fog
The cyan reflection density in the unexposed area in each sample was measured, using a densitometer X-Rite 310 Model.
The data of the thus-tested sample Nos..101 to 115 are shown in Table A below.
TABLE A__________________________________________________________________________ Variation in Color Density due to fluctuation Image Fastness Color Hue of composition of 80.degree. C., 70%Sample No. Coupler (Y/C) blix solution used 100.degree. C. RH Color Fog Remarks__________________________________________________________________________101 comparative compound (1)* 0.180 11 76 73 0.140 comparative sample102 comparative compound (2)* 0.180 10 76 73 0.140 comparative sample103 comparative compound (3)* 0.180 10 76 73 0.100 comparative sample104 comparative compound (4)* 0.180 11 76 73 0.100 comparative sample105 comparative compound (5)* 0.290 2 75 76 0.090 comparative sample106 compound (53) 0.175 1 81 80 0.100 sample of the invention107 compound (54) 0.170 1 90 89 0.090 sample of the invention108 compound (4) 0.170 1 90 90 0.088 sample of the invention109 compound (1) 0.170 0 90 90 0.088 sample of the invention110 compound (7) 0.170 1 90 90 0.090 sample of the invention111 compound (8) 0.170 1 91 90 0.090 sample of the invention112 compound (18) 0.170 0 91 90 0.090 sample of the invention113 compound (22) 0.170 1 90 90 0.090 sample of the invention114 compound (23) 0.170 1 90 90 0.090 sample of the invention115 compound (38) 0.170 1 90 90 0.090 sample of the__________________________________________________________________________ invention
The comparative compounds used above are mentioned below. ##STR20##
In view of the chemical equivalency of the coupler used and of the molar extinction coefficient of the dye to be formed, the amount of silver in the fifth layer in sample Nos. 101, 102, 105, 106 and 107 was 1.5 times the same in the fifth layer in sample No. 108, and the amount of the coupler in the fifth layer in sample No. 105 was 2 times the same in the fifth layer in sample No. 108. In the other samples, the amount of the coupler in the fifth layer was the same molar amount of the coupler in sample No. 108.
From Table A, it is noted that the samples of the present invention gave color images having excellent color hue and image fastness but having reduced cyan color fog. It is also noted therefrom that the samples of the present invention containing a cyan coupler having a split-off group at its 5-position are better than the others.
EXAMPLE 2
The first to twelfth layers mentioned below were coated on a 220 .mu.m-thick paper support, of which the both surfaces had been laminated with polyethylene, to for a color photographic material (sample No. 208). The polyethylene below the first layer on the support contained 15% by weight of anatase-type titanium oxide as a white pigment, along with a small amount of ultramarine as a bluish dye. The chromaticity of the surface of the support was comprised of 89.0, -0.18 and -0.73, respectively, when represented by the trichromatic system (L*, a*, b*).
Layer Constitution
Compositions of the layers of constituting sample No. 208 are mentioned below, in which the numerical value indicates the amount coated (g/m.sup.2) and the amount of the silver halide coated is represented as silver therein.
______________________________________First Layer: Gelatin LayerGelatin 0.30Second Layer: Anti-halation LayerBlack Colloidal Silver 0.07Gelatin 0.50Third Layer: Low-sensitivity Red-sensitive LayerSilver Chloroiodobromide Emulsion color-sensitized 0.03with red-sensitizing dyes (ExS-1, 2, 3) (I-in-coretype, cubic core/shell grains, having a silverchloride content of 1 mol %, a silver iodidecontent of 4 mol %, a mean grain size of 0.3 .mu.mand a grain size distribution of 10%)Silver Iodobromide Emulsion color-sensitized with 0.03red-sensitizing dyes (ExS-1, 2, 3) (cubic grains,having a silver iodide content of 4 mol %, a meangrain size of 0.5 .mu.m and a grain sizedistribution of 15%)Gelatin 1.00Cyan Coupler (Compound (1) mentioned above) 0.08Anti-fading Agent (1/1/1 mixture of Cpd-2', 3', 4') 0.12Coupler Dispersing Medium (Cpd-6') 0.03Coupler Solvent (1/1/1 mixture of Solv-1', 2', 3') 0.06Development Accelerator (Cpd-13') 0.05Fourth Layer: High-sensitivity Red-sensitive LayerSilver Iodobromide Emulsion color-sensitized with 0.07red-sensitizing dyes (ExS-1, 2, 3) (I-in-coretype, tabular grains, having an aspect ratio of 8,a silver iodide content of 6 mol %, a mean grainsize of 0.8 .mu.m and a grain size distribution of20%)Gelatin 1.00Cyan Coupler (Compound (1) mentioned above) 0.12Anti-fading Agent (1/1/1 mixture of Cpd-2', 3', 4') 0.15Coupler Dispersing Medium (Cpd-6') 0.03Coupler Solvent (1/1/1 mixture of Solv-1', 2', 3') 0.10Fifth Layer: InterlayerMagenta Colloidal Silver 0.02Gelatin 1.00Color Mixing Preventing Agent (Cpd-7', 16') 0.08Solvent for Color Mixing Preventing Agent 0.16(Solv-4', 5')Polymer Latex (Cpd-8) 0.10Sixth Layer: Low-sensitivity Green-sensitive LayerSilver Chloroiodobromide Emulsion color-sensitized 0.04with green-sensitizing dye (ExS-4) (I-in-coretype, cubic core/shell grains, having a silverchloride content of 1 mol %, a silver iodidecontent of 2.5 mol %, a mean grain size of 0.28 .mu.mand a grain size distribution of 8%)Silver Iodobromide Emulsion color-sensitized with 0.06green-sensitizing dye (ExS-4) (cubic grains,having a silver iodide content of 2.5 mol %, a meangrain size of 0.48 .mu.m and a grain sizedistribution of 12%)Gelatin 0.80Magenta Coupler (1/1 mixture of ExM-1, 2) 0.10Anti-fading Agent (Cpd-9') 0.10Anti-staining Agent (1/1 mixture of Cpd-10', 11') 0.01Anti-staining Agent (Cpd-5') 0.001Anti-staining Agent (Cpd-12') 0.01Coupler Dispersing Medium (Cpd-6') 0.05Coupler Solvent (Solv-4', 6') 0.15Seventh Layer: High-sensitivity Green-sensitive LayerSilver Iodobromide Emulsion color-sensitized with 0.10green-sensitizing dye (ExS-4) (even-core type,tabular grains, having an aspect ratio of 9, asilver iodide content of 3.5 mol %, a mean grainsize of 1.0 .mu.m and a grain size distribution of21%)Gelatin 0.80Magenta Coupler (1/1 mixture of ExM-1, 2) 0.10Anti-fading Agent (Cpd-9') 0.10Anti-staining Agent (1/1 mixture of Cpd-10, 11) 0.01Anti-staining Agent (Cpd-5') 0.001Anti-staining Agent (Cpd-12') 0.01Coupler Dispersing Medium (Cpd-6') 0.05Coupler Solvent (Solv-4', 6') 0.15Eighth Layer: Yellow Filter LayerYellow Colloidal Silver 0.14Gelatin 1.00Color Mixing Preventing Agent (Cpd-7') 0.06Solvent for Color Mixing Preventing Agent 0.15(Solv-4', 5')Polymer Latex (Cpd-8') 0.10Ninth Layer: Low-sensitivity Blue-sensitive LayerSilver Chloroiodobromide Emulsion color-sensitized 0.07with blue-sensitizing dyes (ExS-5, 6) (I-in-coretype, cubic core/shell grains, having a silverchloride content of 2 mol %, a silver iodidecontent of 2.5 mol %, a mean grain size of 0.38 .mu.mand a grain size distribution of 8%)Silver Iodobromide Emulsion color-sensitized with 0.10blue-sensitizing dyes (ExS-5, 6) (cubic grains,having a silver iodide content of 2.5 mol %, a meangrain size of 0.55 .mu.m and a grain sizedistribution of 11%)Gelatin 0.50Yellow Coupler (1/1 mixture of ExY-1, 2) 0.20Anti-staining Agent (Cpd-5') 0.001Anti-fading Agent (Cpd-14') 0.10Coupler Dispersing Medium (Cpd-6') 0.05Coupler Solvent (Solv-2') 0.05Tenth Layer: High-sensitivity Blue-sensitive LayerSilver Iodobromide Emulsion color-sensitized with 0.25blue-sensitizing dyes (ExS-5, 6) (tabular grains,having an aspect ratio of 14, a silver iodidecontent of 2.5 mol %, a mean grain size of 1.4 .mu.mand a grain size distribution of 21%)Gelatin 1.00Yellow Coupler (1/1 mixture of ExY-1, 2) 0.40Anti-staining Agent (Cpd-5') 0.002Anti-fading Agent (Cpd-14') 0.10Coupler Dispersing Medium (Cpd-6') 0.15Coupler Solvent (Solv-2') 0.10Eleventh Layer: Ultraviolet Absorbing LayerGelatin 1.50Ultraviolet Absorbent (1/1/1/1 mixture of Cpd-1', 1.002', 4', 15')Color Mixing Preventing Agent (Cpd-7', 16') 0.06Dispersing Medium (Cpd-6') 0.30Ultraviolet Absorbent Solvent (Solv-1', 2') 0.15Anti-irradiation Dye (Cpd-17', 18') 0.02Anti-irradiation Dye (Cpd-19', 20') 0.02Twelfth Layer: Protective LayerFine Silver Chlorobromide Grains (having a silver 0.07chloride content of 97 mol % and a mean grain sizeof 0.2 .mu.m)Modified Poval 0.02Gelatin 1.50Gelatin Hardening Agent (1/1 mixture of H-1, 2) 0.17______________________________________
The layers each contained Alkanol XC (made by Du Pont Co.) and sodium alkylbenzenesulfonate as emulsification and dispersion aids, succinate and Magefac F-120 (made by Dai-Nippon Ink Co. ) as coating aids and Cpd-24', 25' and 26' as antiseptics, in addition to the above-mentioned components. The silver halide layers and the colloidal silver-containing layers each contained Cpd-21', 22' and 23' as stabilizers. The compounds used in this example are shown below. ##STR21##
TABLE B______________________________________SampleNo. Cyan Coupler Remarks______________________________________201 comparative compound (1)* comparative sample202 comparative compound (2)* comparative sample203 comparative compound (3)* comparative sample204 comparative compound (4)* comparative sample205 compound (53) sample of the invention206 compound (54) sample of the invention207 compound (4) sample of the invention208 compound (1) sample of the invention209 compound (7) sample of the invention210 compound (8) sample of the invention211 compound (18) sample of the invention212 compound (22) sample of the invention213 compound (23) sample of the invention214 compound (38) sample of the invention______________________________________
The comparative compounds used above are mentioned below. ##STR22##
In view of the chemical equivalency of the coupler used and of the molar extinction coefficient of the dye to be formed, the amounts of silver in the third and fourth layers in sample Nos. 201, 202, 204, 205 and 206 were 1.5 times the same in those layers in sample No. 208, and the amounts of the coupler in the third and fourth layers in sample No. 204 were 2 times the same in those layers in sample No. 208. In the other samples, the amounts of the coupler in the third and fourth layers was the same molar amount of the coupler in sample No. 208.
The thus-prepared silver halide color photographic material, sample No. 208 was exposed to such a degree that about 30% of the coated silver is developed to give gray color. The exposed sample No. 208 was processed in accordance with the process mentioned below, using an automatic developing machine, until the total amount of the replenisher to the machine became 3 times the tank capacity.
______________________________________Process:Processing Tank Amount ofStep Temperature Time Capacity Replenisher______________________________________First 75 sec 38.degree. C. 8 liters 330 ml/m.sup.2DevelopmentFirst Rinsing 45 sec 33.degree. C. 5 liters --(1)First Rinsing 45 sec 33.degree. C. 5 liters 5000 ml/m.sup.2(2)Reversal 15 sec 100 luxExposureColor 135 sec 38.degree. C. 15 liters 330 ml/m.sup.2DevelopmentSecond 45 sec 33.degree. C. 5 liters 1000 ml/m.sup.2RinsingBlix (1) 60 sec 38.degree. C. 7 liters --Blix (2) 60 sec 38.degree. C. 7 liters 220 ml/m.sup.2Third Rinsing 45 sec 33.degree. C. 5 liters --(1)Third Rinsing 45 sec 33.degree. C. 5 liters --(2)Third Rinsing 45 sec 33.degree. C. 5 liters 5000 ml/m.sup.2(3)Drying 45 sec 75.degree. C.______________________________________
The first rinsing and the third rinsing each were effected by countercurrent cascade system. Preferably, a rinsing water was applied to the first rinsing tank (2), while the overflow therefrom was led to the first rinsing tank (1). In the same way, a rinsing water was applied to the third rinsing tank (3), while the overflow therefrom was led to the third rinsing tank (2) and the overflow therefrom to the third rinsing tank (1).
Compositions of the processing solutions used above are mentioned below.
______________________________________ Tank Replen-First Developer Solution isher______________________________________Pentasodium Nitrilo-N,N,N- 1.0 g 1.0 gtrimethylenephosphonatePentasodium Diethylenetriamine- 3.0 g 3.0 gpentaacetatePotassium Sulfite 30.0 g 30.0 gPotassium Thiocyanate 1.2 g 1.2 gPotassium Carbonate 35.0 g 35.0 gPotassium Hydroquinone-mono- 25.0 g 25.0 gsulfonate1-Phenyl-4-hydroxymethyl-4- 2.0 g 2.0 gmethyl-3-pyrazolidonePotassium Bromide 0.5 g --Potassium Iodide 5.0 mg --Water to make 1000 ml 1000 mlpH (adjusted with HCl or KOH) 9.60 9.70______________________________________
______________________________________ Tank Replen-Color Developer Solution isher______________________________________Benzyl Alcohol 15.0 ml 15.0 mlDiethylene Glycol 12.0 ml 14.0 ml3,6-Dithia-1,8-octanediol 0.20 g 0.25 gPentasodium Nitrilo-N,N,N- 0.5 g 0.5 gtrimethylenephosphonatePentasodium Diethylenetriamine- 2.0 g 2.0 gpentaacetateSodium Sulfite 2.0 g 2.5 gHydroxylamine Sulfate 3.0 g 3.6 gN-ethyl-N-(.beta.-methanesulfon- 5.0 g 8.0 gamidoethyl)-3-methyl-4-amino-aniline.3/2 Sulfate.MonohydrateBrightening Agent (diaminostil- 1.0 g 1.2 gbene compound)Potassium Bromide 0.5 g --Potassium Iodide 1.0 mg --Water to make 1000 ml 1000 mlpH (adjusted with HCl or KOH) 10.25 10.40______________________________________
______________________________________Blix Solution (tank solution and replenisher Tankwere the same) Solution______________________________________Disodium Ethylenediamine-tetraacetate 5.0 gDihydrateAmmonium Ethylenediamine- 80.0 gtetraacetato/Fe(III) MonohydrateSodium Sulfite 15.0 gAmmonium Thiosulfate (750 g/liter) 150 ml2-Mercapto-1,3,4-triazole 0.5 gWater to make 1000 mlpH (adjusted with acetic acid or aqueous 6.50ammonia)______________________________________
Sample Nos. 201 to 214 were exposed in the same manner as in Example 1 and then processed also in the same manner as in Example 1, using the running solutions that had been prepared by the above-mentioned continuous-processing. The processed samples were evaluated in the same manner as in Example 1. The test results showed that the color hue and the image fastness of the color images formed in the samples of the present invention are excellent while the cyan color fog in the processed samples of the present invention is little.
EXAMPLE 3
Sample Nos. 301 to 314 were prepared in the same manner as in preparation of sample No. 101 in Example 1 in JP-A-5-134351, except that the cyan coupler in the third layer was changed to that indicated in Table C below.
These samples were processed in the same manner as in Examples 1 and 2 in JP-A-5-134351.
The processed samples were evaluated with respect to the color hue and the image fastness of the images formed and also to the cyan fog in the unexposed area. The test results showed that the samples containing the cyan coupler of the present invention were superior to those containing the comparative coupler.
TABLE C______________________________________SampleNo. Cyan Coupler Remarks______________________________________301 comparative compound (1)* comparative sample302 comparative compound (2)* comparative sample303 comparative compound (3)* comparative sample304 comparative compound (4)* comparative sample305 compound (53) sample of the invention306 compound (54) sample of the invention307 compound (4) sample of the invention308 compound (1) sample of the invention309 compound (7) sample of the invention310 compound (8) sample of the invention311 compound (18) sample of the invention312 compound (22) sample of the invention313 compound (23) sample of the invention314 compound (55) sample of the invention______________________________________
The comparative compounds used above are mentioned below. ##STR23##
In view of the chemical equivalency of the coupler used and of the molar extinction coefficient of the dye to be formed, the amount of silver in the third layer in sample Nos. 308 to 314 was 1/1.5 times the same in the third layer in sample No. 301, and the amount of the coupler in the third layer in sample Nos. 302 to 314 was 2 times the same in the third layer in sample No. 301.
Advantage of the invention
According to the present invention, obtained is a color photographic material capable of forming a color image having excellent color hue and color fastness. The color fog in the unexposed area of the material is little.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without depanting from the sprit and scope thereof.

Number	Name	Date
4728598	Bailey et al.	Mar 1988
4818672	Masukawa et al.	Apr 1989
4873183	Tachibana et al.	Oct 1989
5256526	Suzuki et al.	Oct 1993
5270153	Suzuki et al.	Dec 1993

Number	Date	Country
0491197	Jun 1992	EPX
0518238	Dec 1992	EPX
0545300	Jun 1993	EPX

Silver halide color photographic material

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