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Description  |
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FIELD OF THE
INVENTION
The present invention relates to a silver halide color photographic material having good color reproducibility, high sensitivity and good rapid processing aptitude, and more particularly, to a silver halide color photographic material for a color
print.
BACKGROUND OF THE INVENTION
With popularization of color photographic light-sensitive materials, it has become important to conduct color development processing rapidly, and to provide images of high quality.
In response to these requirements, various investigations of rapid processing for improvement in image quality, particularly improvement in color reproducibility, have been made with respect to photographic light-sensitive materials for color
prints.
It is known that a silver chloride emulsion which has a high silver chloride content is preferably employed as a silver halide emulsion for rapid processing, as described, for example, in International Patent Application (Laid Open) No. WO
87/04534 and JP-A-64-26837 (the term "JP-A" as used herein means an "unexamined published Japanese patent application").
Various investigations have also been made for improvement in color reproducibility. In particular, with respect to photographic light-sensitive materials for color prints, many attempts for improving the absorption spectra of cyan, magenta and
yellow colored dyes form colors have been made. For instance, pyrazoloazole type magenta couplers have been developed that are preferred from the standpoint of bright reproduction of magenta, red and blue series colors because they provide colored dyes
by a coupling reaction with an oxidation product of a developing agent, whose absorption spectra do not have subsidiary absorption in the short wavelength side and are very sharp, in comparison with 5-pyrazolone type magenta couplers conventionally
employed. These are described in detail, for example, in U.S. Pat. Nos. 4,500,630 and 4,540,654, JP-A-61-65245, JP-A-61-65246, JP-A-61-147254, and European Patent (OPI) Nos. 226,849 and 294,785.
Further, in connection with yellow couplers, many attempts for improving color reproduction by reducing undesirable absorption in the magenta side wavelength, by varying the kinds and positions of substituents in comparison with those
conventionally employed as described, for example, in JP-A-63-123047, and JP-A-63-241547.
When using these yellow couplers, however, it is necessary to employ them in relatively high content and hard gradation as compared with conventional yellow couplers, since the dyes formed have low visual sensitivity for human eyes. When these
yellow couplers are employed in silver halide color photographic materials for rapid processing having a high silver chloride content, sufficiently high gradation and color density are not always obtained. Particularly, when these photographic materials
are subjected to continuous development processing, as the amount of the photographic materials processed increases, sensitivity and gradation are remarkably decreased, causing a large problem in practical use.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a silver halide color photographic material which is excellent in color reproducibility, which has high sensitivity and which has a good rapid processing aptitude.
Another object of the present invention is to provide a silver halide color photographic material for a color print.
Other objects of the present invention will become apparent from the following detailed description and examples.
As a result of intensive investigations, it has now been found that these and other objects of the present invention are accomplished with a silver halide color photographic material comprising a support having thereon one or more layers having a
surface pH of 5.0 to 6.5, said layers comprising at least one silver halide emulsion layer comprising a gold-sensitized silver halide emulsion having a silver chloride content of at least 90 mol % and at least one coupler represented by formula (I).
##STR2## wherein R.sub.1 represents an aryl group or a tertiary alkyl group; R.sub.2 represents fluorine, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylthio group or an arylthio group; R.sub.3 represents
a group which is substituted for a hydrogen atom on the benzene ring; X represents hydrogen or a group capable of being cleaved upon a coupling reaction with an oxidation product of an aromatic primary amine developing agent; and l represents 0 or an
integer of 1 to 4, provided that plural R.sub.3 groups may be the same or different.
DETAILED DESCRIPTION OF THE INVENTION
The coupler represented by formula (I) employed in the present invention is now described in more detail.
In formula (I), the aryl group or the tertiary alkyl group for R.sub.1 may be substituted by an alkyl group, an aryl group, a halogen, an alkoxy group or an aryloxy group. R.sub.1 preferably represents an aryl group having from 6 to 24 carbon
atoms (for example, phenyl, p-tolyl, o-tolyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-butoxyphenyl, 4-octyloxyphenyl, 4-hexadecyloxyphenyl, or 1-naphthyl) or a tertiary alkyl group having from 4 to 24 carbon atoms (for example, tert-butyl, tert-pentyl,
tert-hexyl, 1,1,3,3-tetramethylbutyl, 1-adamantyl, 1,1-dimethyl-2-chloroethyl, 2-phenoxy-2-propyl, or bicyclo[2,2,2]octane-1-yl).
In formula (I), the alkyl, aryl, alkoxy, aryloxy, dialkylamino, alkylthio or arylthio group for R.sub.2 may be substituted by an alkyl group, an aryl group, a halogen, an alkoxy group, an aryloxy group or an amino group and R.sub.2 preferably
represents fluorine, an alkyl group having from 1 to 24 carbon atoms (for example, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, n-octyl, n-hexadecyl, or benzyl), an aryl group having from 6 to 24 carbon atoms (for example, phenyl, p-tolyl, o-tolyl,
or 4-methoxyphenyl}, an alkoxy group having from 1 to 24 carbon atoms (for example, methoxy, ethoxy, butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, or methoxyethoxy), an aryloxy group having from 6 to 24 carbon atoms (for example, phenoxy, p-tolyloxy,
o-tolyloxy, p-methoxyphenoxy, p-dimethylaminophenoxy, or m-pentadecylphenoxy), a dialkylamino group having from 2 to 24 carbon atoms (for example, dimethylamino, diethylamino, pyrrolidino, piperidino, or morpholino), an alkylthio group having from 1 to
24 carbon atoms (for example, methylthio, butylthio, n-octylthio, or n-hexadecylthio, or an arylthio group having from 6 to 24 carbon atoms (for example, phenylthio, 4-methoxyphenylthio, 4-tert-butylphenylthio, or 4-dodecylphenylthio).
In formula (I), R3 preferably represents a halogen, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, an alkylsulfonyl
group, an arylsulfonyl group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, a nitro group, a heterocyclic group, a cyano group, an acyl group, an acyloxy group, an alkylsulfonyloxy group, or an arylsulfonyloxy group. These groups
may be substituted by a halogen, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyl group or an acyloxy group. In more detail R.sub.3 represents a halogen (for example, fluorine, chlorine,
bromine, or iodine), an alkyl group having from 1 to 24 carbon atoms (for example, methyl, tert-butyl, or n-dodecyl), an aryl group having from 6 to 24 carbon atoms (for example, phenyl, p-tolyl, or p-dodecyloxyphenyl), an alkoxy group having from 1 to
24 carbon atoms (for example, methoxy, n-butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, or methoxyethoxy), an aryloxy group having from 6 to 24 carbon atoms (for example, phenoxy, p-tert-butylphenoxy, or 4-butoxyphenoxy), an alkoxycarbonyl group having
from 2 to 24 carbon atoms (for example, ethoxycarbonyl, dodecyloxycarbonyl, or 1-(dodecyloxycarbonyl)ethoxycarbonyl), an aryloxycarbonyl group having from 7 to 24 carbon atoms (for example, phenoxycarbonyl, 4-tert-octylphenoxycarbonyl, or
2,4-di-tert-pentylphenoxycarbonyl), a carbonamido group having from 1 to 24 carbon atoms (for example, acetamido, pivaloylamino, benzamido, 2-ethylhexanamido, tetradecanamido, 1-(2,4-di-tert-pentylphenoxy)butanamido,
3-(2,4-di-tert-pentylphenoxy)butanamido, or 3-dodecylsulfonyl-2-methylpropanamido), a sulfonamido group having from 1 to 24 carbon atoms (for example, methanesulfonamido, p-toluenesulfonamido, or hexadecanesulfonamido), a carbamoyl group having from 1 to
24 carbon atoms (for example, N-methylcarbamoyl, N-tetradecylcarbamoyl, N,N-dihexylcarbamoyl, N-octadecyl-N-methylcarbamoyl, or N-phenylcarbamoyl), an alkylsulfonyl group having from 1 to 24 carbon atoms (for example, methylsulfonyl, benzylsulfonyl, or
hexadecylsulfonyl), an arylsulfonyl group having from 6 to 24 carbon atoms (for example, phenylsulfonyl, p-tolylsulfonyl, p-dodecylsulfonyl, or p-methoxysulfonyl), a ureido group having from 1 to 24 carbon atoms (for example, 3-methylureido,
3-phenylureido, 3,3-dimethylureido, or 3-tetradecylureido), a sulfamoylamino group having from 0 to 24 carbon atoms (for example, N,N-dimethylsulfamyolamino), an alkoxycarbonylamino group having from 2 to 24 carbon atoms (for example,
methoxycarbonylamino, isobutoxycarbonylamino, or dodecyloxycarbonylamino), a nitro group, a heterocyclic group having from 1 to 24 carbon atoms (for example, 4-pyridyl, 2-thienyl, phthalimido, or octadecylsuccinimido), a cyano group, an acyl group having
from 1 to 24 carbon atoms (for example, acetyl, benzoyl, or dodecanoyl), an acyloxy group having from 1 to 24 carbon atoms (for example, acetoxy, benzoyloxy, or dodecanoyloxy), an alkylsulfonyloxy group having from 1 to 24 carbon atoms (for example,
methylsulfonyloxy, or hexadecylsulfonyloxy), or an arylsulfonyloxy group having from 6 to 24 carbon atoms (for example, p-toluenesulfonyloxy, or p-dodecylphenylsulfonyloxy)
In formula (I), l preferably is 1 or 2.
In formula (I), X preferably represents a group capable of being cleaved upon a coupling reaction with an oxidation product of an aromatic primary amine developing agent ("coupling-off" group) and includes halogen (for example, fluorine,
chlorine, bromine, or iodine), a heterocyclic group having from 1 to 24 carbon atoms which is connected to the coupling active position by a nitrogen included therein, an aryloxy group having from 6 to 24 carbon atoms, an arylthio group having from 6 to
24 carbon atoms (for example, phenylthio, p-tert-butylphenylthio, p-chlorophenylthio, or p-carboxyphenylthio), an acyloxy group having from 1 to 24 carbon atoms (for example, acetoxy, benzoyloxy, or dodecanoyloxy), an alkylsulfonyloxy group having from 1
to 24 carbon atoms (for example, methylsulfonyloxy, butylsulfonyloxy, or dodecylsulfonyloxy), an arylsulfonyloxy group having from 6 to 24 carbon atoms (for example, benzenesulfonyloxy, or p-chlorophenylsulfonyloxy), or a heterocyclicoxy group having
from 1 to 24 carbon atoms (for example, 3-pyridyloxy, or 1-phenyl-1,2,3,4-tetrazol-5-yloxy), and more preferably represents a heterocyclic group which is connected to the coupling active position by the nitrogen included therein, or an aryloxy group.
The heterocyclic group which is connected to the coupling active position by the nitrogen atom represented by X is preferably a 5-membered to 7-membered heterocyclic group which may be monocyclic or condensed, may contain one or more hetero atoms
selected from oxygen, sulfur, nitrogen, phosphorus, selenium and tellurium in addition to nitrogen, and may be substituted. Suitable examples of the heterocyclic ring include succinimide, maleinimide, phthalimide, diglycolimide, pyrrole, pyrazole,
imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolin-2-one, oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one,
benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, and 2-pyrazone.
Suitable examples of the substituents for the heterocyclic group include a hydroxy group, a carboxyl group, a sulfo group, and an amino group (for example, amino, N-methylamino, N,N-dimethylamino, N,N-diethylamino, anilino, pyrrolidino,
piperidino, or morpholino), in addition to the substituents for R.sub.3 described above.
The aryloxy group represented by X is preferably an aryloxy group having from 6 to 24 carbon atoms, which may be substituted with one or more substituents selected from those described for the heterocyclic group represented by X above. Of the
substituents, a carboxyl group, a sulfo group, a cyano group, a nitro group, an alkoxycarbonyl group, a halogen atom, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl group, an alkylsulfonyl group, an arylsulfonyl
group and an acyl group are preferred.
Examples of particularly preferred substituents represented by R.sub.1, R.sub.2, R.sub.3 and X in formula (I) in the present invention are now illustrated.
In formula (I), R.sub.1 is particularly preferably a 2- or 4-alkoxyaryl group (for example, 4-methoxyphenyl, 4-butoxyphenyl, or 2-methoxyphenyl) or a tert-butyl group. Most preferably, R.sub.1 is a tert-butyl group.
In formula (I), R.sub.2 is more preferably methyl, ethyl, an alkoxy group, an aryloxy group or a dialkylamino group. Particularly preferably, R.sub.2 is methyl, ethyl, an alkoxy group, an aryloxy group or a dimethylamino group and most
preferably R.sub.2 is an alkoxy group having from 1 to 4 carbon atoms.
In formula (I), R.sub.3 is most preferably an alkoxy group, a carbonamido group or a sulfonamido group and particularly preferably a carbonamido group.
In formula (I), X is particularly preferably a heterocyclic group connected to the coupling active position by a nitrogen contained therein or an aryloxy group.
The heterocyclic group reprsented by X is more preferably a group represented by formula (II): ##STR3## wherein Z represents ##STR4## wherein R.sub.4, R.sub.5, R.sub.8 and R.sub.9, which may be the same or different, each represents hydrogen, an
alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group; R.sub.6 and R.sub.7, which may be the same or different, each represents a halogen, an
alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group; R.sub.10 and R.sub.11, which may be the same or different, each represents hydrogen, an alkyl group or an aryl group, and R.sub.10 and R.sub.11 may
combine with each other to form a benzene ring; and R.sub.4 and R.sub.5, R.sub.5 and R.sub.6, R.sub.6 and R.sub.7 or R.sub.4 and R.sub.8 may combine with each other to form a ring (for example, cyclobutane, cyclohexane, cycloheptane, cyclohexene,
pyrrolidine, or piperidine).
Of the heterocyclic groups represented by formula (II), those represented by formula (II) wherein Z is ##STR5## are particularly preferred.
The total number of carbon atoms included in the heterocyclic group represented by formula (II) is generally from 2 to 24, preferably from 4 to 20, more preferably from 5 to 16.
Suitable examples of the heterocyclic group represented by formula (II) include a succinimido group, a maleinimido group, a phthalimido group, a 1-methylimidazolidine-2,4-dion-3-yl group, a 1-benzylimidazolidine-2,4-dion-3-yl group, a
5,5-dimethyloxazolidine-2,4-dion-3-yl group, a 5-methyl-5-propyloxazolidine-2,4-dion-3-yl group, a 5,5-dimethylthiazolidine-2,4dion-3-yl group, a 5,5-dimethylimidazolidine-2,4-dion-3-yl group, a 3-methylimidazolidinetrion-1-yl group, a
1,2,4-triazolidine-3,5-dion-4-yl group, a 1-methyl-2-phenyl-1,2,4-triazolidine-3,5-dion-4 yl group, a 1-benzyl-2-phenyl-1,2,4-triazolidine-3,5-dion-4-yl group, a 5-hexyloxy-1-methylimidazolidine-2,4-dion-3-yl group, a
1-benzyl-5-ethoxyimidazolidine-2,4-dion-3-yl group, and a 1-benzyl-5-dodecyloxyimidazolidine-2,4-dion-3-yl group.
Among these heterocyclic groups, an imidazolidine-2,4-dion-3-yl group (for example, 1-benzyl-1-imidazolidine-2,4-dion-3-yl) is most preferred.
Particularly preferred examples of the aryloxy group represented by X include a 4-carboxyphenoxy group, a 4-methylsulfonylphenoxy group, a 4-(4-benzyloxyphenylsulfonyl)phenoxy group, a 4-(4-hydroxyphenylsulfonyl)phenoxy group, a
2-chloro-4-(3-chloro-4-hydroxyphenylsulfonyl)phenoxy group, a 4-methoxycarbonylphenoxy group, a 2-chloro-4-methoxycarbonylphenoxy group, a 2-acetamido-4-methoxycarbonylphenoxy group, a 4-isopropoxycarbonylphenoxy group, a 4-cyanophenoxy group, a
2-[N-(2-hydroxyethyl)carbamoyl]phenoxy group, a 4-nitrophenoxy group, a 2,5-dichlorophenoxy group, a 2,3,5-trichlorophenoxy group, a 4-methoxycarbonyl-2-methoxyphenoxy group, and a 4-(3-carboxypropanamido)phenoxy group.
The coupler represented by formula (I) may form a polymer, including a dimer or higher oligomer connected through a di- or higher valent group at the substituent represented by R.sub.1, X or ##STR6## In such cases, the range of carbon atoms
defined for each substituent is not restricted.
Typical examples of polymer couplers formed from the coupler represented by formula (I) are a homopolymer and a copolymer each containing a monomer unit of an addition-polymerizable ethylenically unsaturated compound having a yellow dye forming
coupler residue (a yellow color forming monomer). More specifically, the polymer contains a yellow color forming repeating unit represented by formula (III) described below. A copolymer containing one or more kinds of yellow color forming repeating
units represented by formula (III) and a copolymer containing one or more kinds of non-color forming ethylenic monomers as comonomer components, are also within the scope of the invention. ##STR7## wherein R represents hydrogen, an alkyl group having
from 1 to 4 carbon atoms or chlorine; A represents --CONH--, --COO-- or a substituted or unsubstituted phenylene group; B represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted phenylene group or a substituted or
unsubstituted aralkylene group; 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 is 0 or 1; and Q represents a yellow
coupler moiety formed by removing a hydrogen atom from R.sub.1, X or ##STR8## of the compound represented by formula (I).
Of the polymers, copolymers composed of a yellow color forming monomer which provides a coupler unit represented by formula (III) and a non-color forming ethylenic monomer described below are preferred.
Suitable examples of the non-color forming ethylenic monomer which is incapable of coupling with the oxidation product of an aromatic primary amine developing agent include an acrylic acid (for example, acrylic acid, an .alpha.-chloroacrylic
acid, or an .alpha.-alkylacrylic acid such as methacrylic acid), an ester or amide derived from an acrylic acid (for example, acrylamide, methacrylamide, n-butylacrylamide, tert-butylacrylamide, diacetoneacrylamide, methyl acrylate, ethyl acrylate,
n-propylacrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, or .beta.-hydroxyethyl methacrylate), a vinyl ester (for
example, vinyl acetate, vinyl propionate, or vinyl laurate), acrylonitrile, metharylonitrile, an aromatic vinyl compound (for example, styrene and a derivative thereof, for example, vinyl toluene, divinyl benzene, vinyl acetophenone, or sulfo styrene),
itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, a vinyl alkyl ether (for example, vinyl ethyl ether), an ester of maleic acid, N-vinyl-2-pyrrolidone, N-vinyl pyridine, and 2- or 4-vinyl pyridine.
Of these monomers, an ester of acrylic acid, an ester of methacrylic acid and an ester of maleic acid are particularly preferred.
Two or more non-color forming ethylenic monomers as described above can be used together. For example, a combination of methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, or methyl acrylate
and diacetoneacrylamide can be used.
The ethylenically unsaturated monomer which is copolymerized with the vinyl monomer corresponding to the repeating unit represented by formula (III) can be selected so that the copolymer formed possesses good physical properties and/or chemical
properties, for example, solubility, compatibility with a binder such as gelatin in a photographic colloid composition, flexibility, or heat stability, as is well known in the field of polymer couplers.
The yellow polymer coupler according to the present invention can be synthesized in accordance with the synthesizing methods disclosed, for example, in JP-A-58-42044, JP-A-62-141552, JP-A-62-276548, JP-A-63-30855 and JP-A-2-108046.
The yellow polymer coupler used in the present invention can be prepared by dissolving an oleophilic polymer coupler obtained by polymerization of a vinyl monomer including the coupler unit represented by formula (III) described above, in an
organic solvent and then dispersing the solution in a latex form in an aqueous solution of gelatin or directly by an emulsion polymerization method.
When an oleophilic polymer coupler is dispersed in a latex form in an aqueous gelatin solution, the method described in U.S. Pat. No. 3,451,820 can be used. When an emulsion polymerization method is employed, the method described in U.S. Pat. Nos. 4,080,211 and 3,370,952 can be used.
Specific examples of R.sub.3 and X of the yellow dye forming couplers represented by formula (I) are set forth below, but the present invention is not to be construed as being limited thereto. ##STR9##
Specific examples of the yellow dye forming coupler represented by formula (I) are set forth below, but the present invention is not to be construed as being limited thereto. In formula (I) preferred positions of substitution for the group
R.sub.3 is the 4- or 5-position.
__________________________________________________________________________ ##STR10## No. R.sub.1 R.sub.2 (R.sub.3).sub.l X __________________________________________________________________________ Y-1 t-C.sub.4 H.sub.9 OCH.sub.3 (32) [5]
(4) Y-2 t-C.sub.4 H.sub.9 OCH.sub.3 (32) [5] (5) Y-3 t-C.sub.4 H.sub.9 CH.sub.3 (31) [5] (2) Y-4 t-C.sub.4 H.sub.9 ##STR11## (32) [5] (5) Y-5 t-C.sub.4 H.sub.9 ##STR12## (32) [5] (4) Y-6 t-C.sub.4 H.sub.9 OCH.sub.3 (33) [5] (8) Y-7
t-C.sub.4 H.sub.9 OC.sub.2 H.sub.5 (33) [5] (7) Y-8 t-C.sub.4 H.sub.9 OCH.sub.3 (31) [5] (23) Y-9 t-C.sub.4 H.sub.9 ##STR13## (40) [5] (19) Y-10 t-C.sub.4 H.sub.9 OC.sub.8 H.sub.17 -n (45) [4] (5) Y-11 t-C.sub.4 H.sub.9 OC.sub.8
H.sub.17 -n (45) [5] (5) Y-12 t-C.sub.4 H.sub.9 OCH.sub.3 (42) [5] (4) Y-13 t-C.sub.4 H.sub.9 ##STR14## (30) [5] (10) Y-14 t-C.sub.4 H.sub.9 OC.sub.16 H.sub.33 -n -- (15) Y-15 t-C.sub.4 H.sub.9 OCH.sub.2 CH.sub.2 OCH.sub.3 (34) [5] (8) Y-16 t-C.sub.4 H.sub.9 CH.sub.3 (43) [5] (9) Y-17 t-C.sub.4 H.sub.9 C.sub.2 H.sub.5 (47) [5] (8) Y-18 t-C.sub.4 H.sub.9 OCH.sub.3 (46) [5] (2) Y-19 t-C.sub.4 H.sub.9 OC.sub.8 H.sub.17 -n (45) [4], (5) (45) [5] Y-20 t-C.sub.4 H.sub.9
OCH.sub.3 (31) [5] (19) Y-21 t-C.sub.4 H.sub.9 ##STR15## (36) [4] (18) Y-22 t-C.sub.4 H.sub.9 ##STR16## (41) [5] (11) Y-23 t-C.sub.4 H.sub.9 ##STR17## (37) [5] (3) Y-24 t-C.sub.4 H.sub.9 OC.sub.2 H.sub.5 (37) [5] (1) Y-25 t-C.sub.4
H.sub.9 CH.sub.3 (38) [5] (2) Y-26 t-C.sub.4 H.sub.9 C.sub.2 H.sub.5 (38) [5] (2) Y-27 t-C.sub.4 H.sub.9 CH.sub.3 (33) [5] (2) Y-28 ##STR18## OCH.sub.3 (42) [5] (4) Y-29 ##STR19## ##STR20## (40) [5] (4) Y-30 ##STR21## CH.sub.3 (43)
[5] (2) Y-31 ##STR22## Y-32 ##STR23## Y-33 ##STR24## Y-34 ##STR25## __________________________________________________________________________
In the above table, a figure in parentheses () denotes the number of specific example of X or R described above, and a figure in brackets [ ] denotes the substitution position on the anilide group.
The yellow dye forming couplers according to the present invention can be employed individually or as a mixture of two or more thereof. Further, they may be employed in a mixture with known yellow dye forming couplers.
The yellow coupler according to the present invention can be employed in any layer of the light-sensitive material, but preferably in a light-sensitive silver halide emulsion layer or a layer adjacent thereto, and more preferably in a
light-sensitive silver halide emulsion layer.
The yellow coupler according to the present invention can be synthesized by conventionally known synthesis methods. Specific examples of synthesis methods are described in JP-A-63-123047.
The amount of the yellow coupler according to the present invention used in the light-sensitive material is generally from 1.times.10.sup.-5 to 1.times.10.sup.-2 mol/m.sup.2, preferably from 1.times.10.sup.-4 to 5.times.10.sup.-3 mol/m.sup.2, and
more preferably from 2.times.10.sup.-4 to 1.times.10.sup.-3 mol/m.sup.2.
The "surface pH of the layer Of the silver halide color photographic material" according to the present invention as used herein is the pH of all photographic layers obtained by applying coating solutions to a support and can be adjusted by
controlling the pH of a coating solution, but the surface pH is not necessarily the same as the pH of the coating solution. This is due to some of the compositions in the coating solution which may change the surface pH depending on drying conditions.
The surface pH of the layer can be determined by the following method as described in JP-A-61-245153. More specifically, (1) on the surface of the silver halide emulsion layer side of the light-sensitive material, 0.05 ml of pure water is
dropped, and (2) three minutes after, the surface pH of the layer is measured by a conventional surface pH measuring electrode (e.g., GS-165F manufactured by Toadenpa).
The adjustment of the surface pH of the layer can almost be attained by adjusting the pH of the coating solution as described above and can be conducted using an acid (for example, sulfuric acid, or citric acid) or an alkali (for example, sodium
hydroxide, or potassium hydroxide), if desired.
The surface pH of the layer of the photographic material according to the present invention is in a range from about 5.0 to about 6.5, preferably from about 5.5 to about 6.3.
The color photographic light-sensitive material according to the present invention includes a support having coated thereon 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. In a conventional color printing paper, the light-sensitive layers are usually provided on a support in the order described above, but they can be provided in a different order. Further, an
infrared-sensitive silver halide emulsion layer may be employed in place of at least one of the above described emulsion layers. Each of the light-sensitive emulsion layers contains a silver halide emulsion having sensitivity in a respective wavelength
region and a color coupler which forms a dye of complementary color to the light to which the silver halide emulsion is sensitive, that is, yellow, magenta and cyan dyes to blue, green and red light, respectively. Thus, color reproduction by a
subtractive process can be performed. However, the relationship of the light-sensitive layer and hue of dye formed from the coupler may be varied from that described above, if desired.
The silver halide emulsion used in the present invention is preferably a high silver chloride content emulsion which has a high silver chloride content ratio adapted for rapid processing. The silver chloride content ratio in such a high silver
chloride content emulsion is at least 90 mol %, preferably at least 95 mol %.
Of such high silver chloride content emulsions, those having a structure wherein a localized phase of silver bromide is present in the interior and/or on the surface of silver halide grains in a stratified form or in a non-stratified form are
preferred. With respect to the halogen composition of the localized phase, it is preferred that the silver bromide content is at least 10 mol %, and more preferably exceeding 20 mol %. The localized phase may exist in the interior of the grain, or at
the edge, corner or plane of the surface of the grain. One preferred example is a grain with epitaxial growth at the corner.
For the purpose of minimizing the reduction in sensitivity when pressure is applied to the photographic light-sensitive material, it is also preferred to use uniform structure type grains, wherein the distribution of halogen composition is narrow
in a high silver chloride content emulsion having a silver chloride content of at least 90 mol %.
Further, for the purpose of reducing the amount of replenisher for a developing solution, it is effective to further increase the silver chloride content of a silver halide emulsion. In such a case, an almost pure silver chloride may be used
wherein the silver chloride content is from 98 mol % to 100 mol %.
The average grain size of silver halide grains in the silver halide emulsion used in the present invention (the grain size being defined as the diameter of a circle having the same area as the projected area of the grain and being averaged by
number) is preferably from 0.1 .mu.m to 2 .mu.m.
Moreover, it is preferred to employ a mono-dispersed emulsion which has a grain size distribution such that the coefficient of variation (obtained by dividing the standard deviation of the grain size distribution with the average grain size) is
not more than 20%, particularly not more than 15%. Further, it is preferred to employ two or more of the above described monodispersed emulsions in the same layer as a mixture or in the form of superimposed layers for the purpose of obtaining wide
latitude.
The silver halide grains contained in the photographic emulsion may have a regular crystal form such as cubic, tetradecahedral or octahedral, or an irregular crystal form such as spherical or tabular, or may have a composite form of these crystal
forms. Also, a mixture of grains having various crystal forms may be used. Of these emulsions, those containing grains having the above described regular crystal form in an amount of at least 50%, preferably at least 70%, and more preferably at least
90% are advantageously used in the present invention.
Further, a silver halide emulsion wherein tabular silver halide grains having an average aspect ratio (diameter corresponding to circle/thickness) of at least 5, preferably at least 8, accounts for at least 50% of the total projected area of the
silver halide grains may be preferably used in the present invention.
The silver chlorobromide emulsion used in the present invention can be prepared in any suitable manner, for example, by the methods as described in P. Glafkides, Chemie et Physique Photographique, (Paul Montel 1967), G.F. Duffin, Photographic
Emulsion Chemistry, (Focal Press 1966), and V.L. Zelikman et al., Making and Coating Photographic Emulsion, (Focal Press 1964). That is, any of an acid process, a neutral process, and an ammonia process can be employed.
Soluble silver salts and soluble halogen salts can be reacted by techniques such as a single jet, process, a double jet process, and a combination thereof. In addition, a reversal mixing process can be used in which silver halide grains are
formed in the presence of an excess of silver ions. As one double jet process, a controlled double jet process in which the pAg in a liquid phase where silver halide is formed is maintained at a predetermined level can be employed. This process gives a
silver halide emulsion in which the crystal form is regular and the grain size is nearly uniform.
During the step of formation or physical ripening of silver halide grains of the silver halide emulsion used in the present invention, various kinds of multi-valent metal ion impurities can be introduced. Suitable examples of the compounds
include cadmium salts, zinc salts, lead salts, copper salts, thallium salts, salts or complex salts of Group VIII elements, for example, iron, ruthenium, rhodium palladium, osmium, iridium, and platinum. Particularly, above-described Group VIII elements
are preferably used. The amount of the compound added can be varied over a wide range depending on the purpose, but it is preferably used in a range from 10.sup.-9 to 10.sup.-2 mol per mol of silver halide.
The silver halide emulsions used in the present invention are usually subjected to chemical sensitization and spectral sensitization.
For the chemical sensitization, a sulfur sensitization method (e.g., using an unstable sulfur compound), a noble metal sensitization method, (e.g., using an gold sensitization), and a reduction sensitization method are employed individually or in
combination. The compounds preferably used in chemical sensitization include those as described in JP-A-62-215272, page 18, right lower column to page 22, right upper column.
Gold sensitizers are used in the present invention are now described in greater detail.
The gold sensitizer used may be a mono-valent gold compound or a tri-valent gold compound, and various gold compound can be employed. Representative examples of the gold sensitizers include chloroauric acid, potassium chloroaurate, auric
trichloride, potassium auricthiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichloro gold, and rhodanine gold salt.
The amount of the gold sensitizer to be added is preferably from 1.times.10.sup.-7 to 5.times.10.sup.-4 mol, more preferably from 5.times.10.sup.-7 to 5.times.10.sup.-5 mol, per mol of silver halide in the emulsion.
The addition of the gold sensitizer can be conducted at any stage of the production of silver halide emulsion, but preferably is in the period from the completion of the formation of silver halide grains to the completion of chemical
sensitization.
Spectral sensitization is performed for the purpose of imparting spectral sensitivity in the desired wavelength range to the emulsion of each layer of the photographic light-sensitive material of the present invention. According to the present
invention, the spectral sensitization is conducted by adding a spectral sensitizing dye which is a dye capable of absorbing light of a wavelength range corresponding to the desired spectral sensitivity. Suitable examples of the spectral sensitizing dyes
used include those as described, for example, in F.H. Harmer, Heterocyolic compounds-Cyanine dyes and related compounds, John Wiley & Sons (New York, London) (1964). Specific examples of the sensitizing dyes preferably employed are described in
JP-A-62-215272, page 22, right upper column to page 38.
The silver halide emulsions used in the present invention can contain various compounds or precursors thereof for preventing the occurrence of fog or for stabilizing photographic performance during the production, storage and/or photographic
processing of photographic light-sensitive materials. Specific examples of the compounds preferably used are described in JP-A-62-215272, page 39 to page 72.
The silver halide emulsion used in the present invention may be a surface latent image type emulsion wherein latent images are formed mainly on the surface of grains, or an internal latent image type emulsion wherein latent images are formed
mainly in the interior of grains.
In the color photographic light-sensitive material according to the present invention, a yellow coupler, a magenta coupler and a cyan coupler which form yellow, magenta and cyan colors respectively upon coupling with the oxidation product of an
aromatic primary amine type color developing agent are ordinarily employed.
Cyan couplers and magenta couplers which are preferably used in the present invention include those reprsented by formulae (C-I), (C-II), (M-I), or (M-II): ##STR26##
In formulae (C-I) or (C-II), R.sub.21, R.sub.22 and R.sub.24 each represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R.sub.23, R.sub.25, and R.sub.26 each represents hydrogen, a halogen, an aliphatic group, an
aromatic group, or an acylamino group or, when these groups are linked, R.sub.23 and R.sub.22 represent a non-metallic atomic group necessary for forming a nitrogen-containing 5-membered or 6-membered ring; Y.sub.1 and Y.sub.2 each represents hydrogen or
a group capable of being released upon a coupling reaction with an oxidation product of a color developing agent; and n is 0 or 1.
R.sub.25 in formula (C-II) preferably represents an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl g | | |
