EP0421453A1

EP0421453A1 - Silver halide color photographic material

Info

Publication number: EP0421453A1
Application number: EP90119111A
Authority: EP
Inventors: Keiji C/O Fuji Photo Film Co. Ltd. Mihayashi; Hajime C/O Fuji Photo Film Co. Ltd. Nakagawa; Mdasaharu C/O Fuji Photo Film Co. Ltd. Toriuchi; Tadahisa C/O Fuji Photo Film Co. Ltd. Sato; Koji C/O Fuji Photo Film Co. Ltd. Tamoto; Yuji C/O Fuji Photo Film Co. Ltd. Kume
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1989-10-05
Filing date: 1990-10-05
Publication date: 1991-04-10

Abstract

A silver halide color photographic material is provided comprising a support having thereon at least one light-sensitive silver halide emulsion layer comprising the combination of (1) at least one pyrazolaozole coupler and (2) a light-sensitive silver halide emulsion comprising chemically sensitized silver halide grains which have a distinct stratiform structure comprising silver bromoiodide containing 15 to 45 mol% of silver iodide with a total silver iodide content of more than 10 mol%.

The silver halide color photographic material has high sensitivity and excellent graininess.

Description

FIELD OF THE INVENTION

The present invention relates to a silver halide color photographic material. More particularly, the present invention relates to a silver halide color photographic material which contains a high silver iodide content silver halide emulsion and a pyrazoloazole coupler having excellent color reproducibility, an excellent graininess and preservability.

BACKGROUND OF THE INVENTION

Silver halide color photographic materials are desired to exhibit excellent colorability, color reproducibility, graininess and sharpness as well as little dependence on processing and excellent ageing stability. In order to meet these requirements, pyrazoloazole couplers have been proposed in U.S. Patent 4,540,654, and European Patent 226849A. However, these couplers are disadvantageous in that their dispersions become unstable with time. In particular, a mixture of an oil-in-water type coupler dispersion with a silver halide emulsion is prone to failure in coating with time as described in JP-A-63-296046 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"). These couplers are also disadvantageous in that their photographic properties are greatly dependent on developing conditions (time) as described in JP-A-1-102558. These couplers are further disadvantageous in that they cause a drastic change in the properties of the light-sensitive material after exposure as described in JP-A-1-108546 corresponding to EP-A-313083.
On the other hand, silver halide grains having a definite layer structure of silver halide containing 10 to 45 mol% of silver iodide therein and an average silver iodide content of 7 mol% or more are proposed in JP-A-60-143331 corresponding to U.S. Patent 4,668,614. Multilayer silver iodide grains having an average silver iodide content of 12 mol% or more are proposed in JP-A-58-181037 corresponding to U.S. Patent 4,477,564. These proposed emulsions can provide a high sensitivity and some improvement in graininess. However, these emulsions are disadvantageous when used in combination with conventional magenta couplers, since they give a low sensitivity or poor color reproducibility.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a silver halide color photographic material which provides an excellent color reproducibility.
It is a further object of the present invention to provide a silver halide color photographic material which exhibits little change in properties with time during the storage of coating solution and light-sensitive material in manufacture, and during the storage of the light-sensitive material between photographing and development.
It is another object of the present invention to provide a silver halide color photographic material which exhibits a high sensitivity and excellent graininess.
It is a further object of the present invention to provide a silver halide color photographic material exhibiting little change in photographic properties with fluctuation in processing conditions.
These and other objects of the present invention will become more apparent from the following detailed description and examples.
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 at least one light-sensitive silver halide emulsion layer comprising the combination of (1) at least one pyrazoloazole coupler and (2) a light-sensitive silver halide emulsion comprising chemically sensitized silver halide grains which have a distinct stratiform structure comprising silver bromoiodide containing 15 to 45 mol% of silver iodide with a total silver iodide content of more than 10 mol%.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is now described in greater detail.
The present pyrazoloazole coupler is preferably represented by formula (I):
wherein Ro represents hydrogen or a substituent; V represents hydrogen or a coupling-off group capable of being derived by a coupling reaction with an oxidation product of an aromatic primary amine developing agent; and Za, Zb and Zc, which may be the same or different each represents a methine group, a substituted methine group, = N- or -NH-, provided that one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond. When the Zb-Zc bond is a carbon-carbon double bond, it may be part of the aromatic ring. A plurality of pyrazoloazole couplers may be connected to each other via R_o or V to form a dimer or higher polymer, and when Za, Zb or Zc is a substituted methine group, a plurality of pyrazoloazole couplers may be connected to each other via the substituted methine group to form a dimer or higher polymer.
Magenta dye-forming couplers represented by formula (I) are now described in greater detail.
Polymeric compounds of formula (I) are compounds containing two or more groups represented by formula (I) per molecule. Such polymers include bis compounds and polymer couplers. Such a polymer may be a homopolymer containing only a monomer having a moiety represented by formula (I) (preferably a monomer containing vinyl group, hereinafter referred to as "vinyl monomer") or may be a copolymer with a noncoloring ethylenic monomer which does not undergo coupling reaction with an oxidation product of an aromatic primary amine developing agent.
Of them, the same homopolymer and copolymer as those comprising a monomer having a moiety represented by the general formulae (I-a) to (I-g) are preferred. Ro represents the same groups as those for R_S1 disclosed hereafter. V represents the same groups as those for V disclosed hereafter.
Preferred pyrazoloazole magenta couplers represented by formula (I) are represented by formulae (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), and (I-g):
Among the couplers represented by formulae (I-a) to (I-g), preferred couplers are represented by formulae (I-a), (I-d) and (I-e), and more preferred (I-d) and (I-e).
In formulae (I-a) to (I-g), R⁵¹, R⁵² and R⁵³ may be the same or different and each represents hydrogen a halogen atom, an alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group or aryloxycarbonyl group; and V represents hydrogen a halogen atom, carboxy group or a coupling-off group which is connected to the carbon atom in the coupling position via oxygen, nitrogen or sulfur, that undergoes separation upon coupling. R51, R⁵², R⁵³ or V may be a divalent group to form a bis compound.
These pyrazoloazole magenta couplers may be in the form of a polymer coupler containing a coupler group represented by formula (I-a), (I-b), (I-c), (I-d), (I-e), (I-f) or (I-g) present in the main chain or a side chain. In particular, polymers derived from vinyl monomers containing a portion represented by these general formulae are preferred. In this case, R⁵¹, R⁵², R⁵³ or V represents a vinyl group or connecting group.
More particularly, R⁵¹, R⁵² and R⁵³ each represents hydrogen, a halogen atom (e.g., chlorine, bromine), alkyl group (e.g., methyl, isopropyl, sec butyl, isobutyl, ethyl, cyclohexyl, 2-pentyl, 3-heptyl, propyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-amylphenoxy)propyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsul- fonylethyl, cyclopentyl, benzyl), alkenyl group (e.g., allyl, octadecenyl), aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), heterocyclic group (e.g., 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, alkoxy group (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), aryloxy group (e.g., phenoxy, 2-methylphenoxy, 4-t-butyl- phenoxy), heterocyclic oxy group (e.g., 2-benzimidazolyloxy), acyloxy group (e.g., acetoxy, hex- adecanoyloxy), carbamoyloxy group (e.g., N-phenylcarbamoyloxy, N-ethylcarbamoyloxy), silyloxy group (e.g., trimethylsilyloxy), sulfonyloxy group (e.g., dodecylsulfonyloxy), acylamino group (e.g., acetamido, benzamido, tetradecanamido, α-(2,4-di-t-amylphenoxy)butylamido, γ-(3-t-butyl-4-hydroxyphenoxy)-butylamido, α-{4-(4-hydroxyphenylsulfonyl)phenoxy}decanamido), anilino group (e.g., phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5-{α-(3-t-butyl-4-hydroxyphenoxy)dodecanamide}anilino), ureido group (e.g., phenylureido, methylureido, N,N-dibutylureido), imido group (e.g., N-succinimido, 3-benzylhydantoinyl, 4-(2-ethylhex- anoylamino)phthalimido), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino, N-methyl-N-decylsul- famoylamino), alkylthio group (e.g., methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenox- ypropylthio, 3-(4-t-butylphenoxy)propylthio), arylthio group (e.g., phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), heterocyclic thio group (e.g., 2-benzothiazolylthio), alkoxycarbonylamino group (e.g., methoxycarbonylamino, tetradecyloxycarbonylamino), aryloxycarbonylamino group (e.g., phenoxycarbonylamino, 2,4-di-tert-butylphenoxycarbonylamino), sulfonamido group (e.g., methanesulfonamido, hexadecansulfonamido, benzenesulfonamido, p-toluenesulfonamido, octadecansulfonamido, 2-methyloxy-5-t-butylbenzenesulfonamido), carbamoyl group (e.g., N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl, N-{3-(2,4-di-tert-amylphenoxy)propyl}carbamoyl), acyl group (e.g., acetyl, (2,4-di-tert-amylphenoxy)acetyl, benzoyl), sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dirpopylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), sulfonyl group (e.g., methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfinyl group (e.g., octanesulfinyl, dodecylsulfinyl, phenylsulfinyl), alkoxycarbonyl group (e.g., methoxycarbonyl, butyloxycarbonyl, dodecylcarbonyl, octadecylcarbonyl) or aryloxycarbonyl group (e.g., phenyloxycarbonyl, 3-pentadecyloxycarbonyl).
V represents hydrogen, a halogen atom (e.g., chlorine, bromine, iodine), a carboxy group or a group which is connected thereto via oxygen (e.g., acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxyl, 4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, a-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy); a group which is connected thereto via nitrogen (e.g., benzenesulfonamido, N-ethyltoluenesulfonamido, heptafluorobutanamido, 2,3,4,5,6-pentafluorobenzamido, octanesulfonamido, p-cyanophenylureido, N,N-diethylsulfamoylamino, 1-piperidyl, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl, 1-benzyl-ethoxy-3-hydantoinyl, 2N-1,1-dioxo-3(2H)-oxo-1,2-benzoisothiazolyl, 2-oxo-1.2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl, 3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6-bromo-benzotriazol-1-yl, 5methyl-1,2,3,4-triazol-1-yl, benzimidazolyl, 3-benzyl-1- hydrantoinyl, 1-benzyl-5-hexdecyloxy-3-hydantoinyl, 5- methyl.1.tetrazolyl), arylazo group (e.g., 4 methox- yphenylazo, 4-pivaolylaminophenylazo, 2-naphthylazo, 3-methyl-4-hydroxyphenylazo), or a group which is connected thereto via a sulfur atom (e.g., phenylthio, 2-carboxyphenylthio, 2-methoxy-5-t-octylphenylthio, 4- methanesulfonylphenylthio, 4-octanesulfonamidophenylthio, 2-butoxyphenylthio, 2-(2-hexanesulfonylethyl)-5-tert-octylphenylthio, benzylthio, 2-cyanoethylthio, 1-ethoxycarbonyltridecylthio, 5-phenyl-2,3,4,5-tetrazolyl- thio, 2-benzothiazolylthio, 2-dodecylthio-5-thiophenylthio, and 2-phenyl-3-dodecyl-1,2,4-triazolyl-5-thio).
In the couplers represented by formulae (I-a) and (I-b), R⁵² and R⁵³ may be connected to each other to form a 5- to 7-membered ring.
When R⁵¹, R⁵², R⁵³ or V is a divalent group to form a bis compound, R⁵¹, R⁵² and R⁵³ each preferably represents a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10-decylene, -CH₂CH₂O-CH₂CH₂-); a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene,
an -NHCO-R^54-CONH- group (in which R⁵⁴ represents a substituted or unsubstituted alkylene group or phenylene group) such as

or an -S-R⁵⁵-S- group (in which R⁵⁵ represents a substituted or unsubstituted alkylene group) such as -S-CH₂CH₂-S- and
V represents a group obtained by removing a substituent, such as hydrogen, from previously mentioned monovalent group to form a divalent group.
If the groups represented by formulae (I-a), (I-b), (I-c), (I-d), (I-e), (I-f) and (I-g) are contained in a vinyl monomer, examples of the connecting group represented by R⁵¹, R^S2, R⁵³ or V include at least one group selected from an alkylene group (e.g., a substituted or unsubstituted alkylene group such as methylene, ethylene, 1,10-decylene and -CH₂CH₂0CH₂CH₂-), phenylene group (e.g., a substituted or unsubstituted phenylene group such as 1,4-phenylene, 1,3-phenylene,
-NHCO-, -CONH-, -0-, -OCO-, and an aralkylene group (e.g.,

Preferred examples of such a connecting group include

-CONH-CH₂CH₂NHCO-, -CH₂CH₂O-CH₂CH₂-NHCO-, and
The vinyl group can contain substituents other than those represented by formulae (I-a), (I-b), (I-c), (I-d), (I-e), (I-f) or (I-g). Preferred examples of such substituents include hydrogen, chlorine and a C -4 lower alkyl group (e.g.,. methyl or ethyl).
The monomer containing groups represented by formulae (I-a), (I-b), (I-c), (I-d), (I-e), (I-f) and (I-g) may form a copolymer with a noncoloring ethylenic monomer which does not undergo a coupling reaction with an oxidation product of an aromatic primary amine developing agent.
Examples of the noncoloring ethylenic monomer which does not undergo a coupling reaction with an oxidation product of an aromatic primary amine developing agent include acrylic acid, a-chloroacrylic acid, α-alkylacrylic acid (e.g., methacrylic acid), an ester or amide derived from these acrylic acids (e.g., acrylamide, n-butyl acrylamide, t-butyl acrylamide, diaceton acrylamide, methacrylamide, 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, S-hydroxy methacrylate), methylene bisacrylamide, vinyl ester (e.g., vinyl acetate, vinyl propionate, vinyl laurate), acrylonitrile, methacrylonitrile, an aromatic vinyl compound (e.g., styrene, derivative thereof, vinyl toluene, divinyl benzene, vinyl acetophenone, sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g., vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine, and 2- and 4-vinyl pyridine. Two or more of these noncoloring ethylenically unsaturated monomers can be used in combination. Examples of such a combination include n-butyl acyrlate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, and methyl acrylate and diacetone acrylamide.
As well known in the field of polymer color couplers, the noncoloring ethylenically unsaturated monomer to be copolymerized with a solid water-insoluble monomer coupler can be selected so that the physical properties and/or chemical properties of the copolymer to be formed, solubility, compatibility with a binder for the photographic colloidal composition such as gelatin, flexibility, and thermal stability can be controlled.
The polymer coupler may be water-soluble or water-insoluble. Particularly preferred among these polymer couplers are polymer coupler latexes.
Particularly preferred pyrazoloazole magenta couplers represented by formulae (I-a) to (I-g) are those represented by formulae (I-d) and (I-e). In the pyrazoloazole magenta couplers represented by formulae (I-d) and (I-e), R⁵¹ preferably represents an alkyl group, aryl group, alkoxy group or aryloxy group, R⁵² preferably represents an alkyl group, aryl group, alkylthio group, arylthio group or heterocyclic thio group, and V preferably represents a halogen atom, aryloxy group, alkylthio group, arylthio group or heterocyclic group. Preferred among the substituents represented by R⁵² is alkyl group. In particular, R⁵² preferably is a group represented by formula (XV): -L₁-R⁵⁶ (XV) wherein L₁ represents a straight chain or branched alkylene group (e.g., -CH₂-, -CH₂CH₂-, -CH₂CH₂CH₂-,

and R⁵⁶ represents an aryl group [e.g., 4-(4-dodecyloxybenzenesulfonamido)phenyl, 4-{2-[4-hydroxyphenyl- sulfonyl)phenoxy]tetradecanamido, 4-methanesulfonamidophenyl, phenyl], a sulfonamido group {e..g., [4-dodecylbenzenesulfonamido, 4-tetradecyloxybenzenesulfonamido, hexadecansulfonamido, 5-(2-octyloxy-5-t-octylbenzenesulfonamido)-2-octyloxybenzenesulfonamido, toluenesulfonamido), a carbonamido group {e.g., benzamido, 4-[2-(2,4-di-t-pentylphenoxy)butanamido] benzamido, 3-dodecansulfonamidobenzamido}, an arylsulfonyl group [e.g., benzenesulfonyl, toluenesulfonyl, 4-dodecyloxybenzenesulfonyl, 4-(4-dodecyloxyben- zenesulfonamido)benzenesulfonyl, 2-butoxy-5-t-octylbenzenesulfonyl, 4-dodecylbenzenesulfonyl] or alkylsulfonyl group (e.g., methanesulfonyl, decanesulfonyl, dodecanesulfonyl, tetradecanesulfonyl, hexadecanesul- fonyl, octadecanesulfonyl, 2-ethylhexanesulfonyl, 2-hexyldecanesulfonyl, 3-dodecyloxypropanesulfonyl, cyclohexanesulfonyl, 2-dodecanesulfonylethanesulfonyl, or a-toluenesulfonyl).
Specific examples of the magenta dye-forming coupler represented by formula (A) are set forth below, but the present invention is not to be construed as being limited thereto.
The synthesis of the magenta coupler represented by formula [I] can be accomplished by any conventional method as described in JP-A-59-162548, JP-A-59-171956, JP-A-60-33552, and JP-A-61-65245, U.S. Patents 3,519,429, 3,558,319, 3,725,067, 3,935,015, 4,241,168, 4,351,897, 4,367,282, and 4,540,654, and WO-86-1915 or any method similar thereto.
The coupler represented by formula [I] can be incorporated in any layer in the silver halide photographic material, and is preferably in the same layer as the present emulsion grains or layers adjacent thereto.
The amount of the coupler represented by formula [I] to be incorporated is in the range of 0.001 to 1.0 g/m², preferably 0.03 to 0.7 g/m², more preferably 0.1 to 0.5 gim².
The silver halide grains used in the present invention are now described in greater detail.
The light-sensitive silver halide emulsion layer contains silver bromoiodide containing 15 to 45 mol% of silver iodide present therein in a definite stratiform structure and chemically sensitized silver halide grains having a total silver iodide content of more than 10 mol%.
The definite stratiform structure of the grains can be judged by X-ray diffractiometry. Examples of the application of X-ray diffractiometry to silver halide grains are described in H. Hirsch, Journal of Photographic Science , vol. 10, pp. 129-, (1962). When the lattice constant is determined by the halogen composition, a diffraction peak occurs at a diffraction angle satisfying Black's law (2dsin 0 = nx).
Methods for the measurement of X-ray diffraction are further described in Kiso Bunseki Kagaku Koza 24 , "X-ray Diffraction", Kyoritsu Shuppan, and Introduction to X-Ray Diffraction , (Rigaku Denki K.K.). In a measurement, Cu is used as a target and Ka-ray of Cu is also used as a standard radiation source (tube voltage: 40 kv; tube current: 60 mA is determined to obtain a diffractiometry curve on a plane (220) of silver halide. In order to enhance the resolution of the measuring apparatus, it is necessary that the measuring precision be confirmed with the width of the slit (dispersing slit, light-receiving slit),the time constant of the apparatus, the scanning speed of the goniometer, and recording speed properly selected, with silicon or the like used as standard specimen.
In the present definite stratiform structure, when the diffraction intensity vs. diffraction angle curve on the (220) plane of silver halide is obtained at a diffraction angle (28) of 38 to 42 with Kp-ray of Cu, there occur at least two maximum diffractions, i.e., a diffraction peak corresponding to a high iodide content layer containing 15 to 45 mol% of silver iodide and a diffraction peak corresponding to a low iodine content layer containing 8 mol% or less of silver iodide, and a minimum diffraction therebetween, the intensity of the diffraction peak corresponding to the high iodine content layer being 1/10 to 3/1, preferably 1/5 to 3/1, particularly 1/3 to 3/1 of that of the diffraction peak corresponding to the low iodine content layer.
In the present emulsion having a substantially two definite stratiform structures, the intensity of the minimum diffraction occurring between the two maximum diffrection peaks is preferably 90% or less, more preferably 80% or less, particularly 60% or less of that of the weakest of the two or more maximum diffractions.
Methods for resolving a diffraction curve consisting of two diffraction components are well known. These methods are described in Jikken Butsuri Koza 11, Lattice Defect , Kyoritsu Shuppan.
Another useful analysis is to use a curve analyzer produced by E.I. Du Pont de Nemours & Co. Inc., assuming that the diffraction curve is a Gauss' function or Lorentz's function.
In the case of an emulsion comprising two grains with different halogen compositions without a definite stratiform structure, the X-ray diffractiometry also provides two diffraction peaks.
Such an emulsion cannot provide excellent photographic properties as obtained in the present invention.
In order to judge if a silver halide emulsion is one according to the present invention or one containing two different silver halide grains as mentioned above, the EPMA (Electron Probe Micro Analyzer) method can be used in addition to the X-ray diffractiometry.
In this method, a specimen comprising emulsion grains well dispersed so as to be kept away from each other is irradiated with an electron beam. X-ray analysis by electron beam excitation enables elementary analysis of minute portions.
In this method, the intensity of characteristic X-ray of silver and iodide emitted by each lattice can be obtained to determine the halogen composition of each grain.
When the halogen composition of at least 50 grains are confirmed by EPMA method, it can be determined whether the emulsion is one according to the present invention or not.
In the present emulsion, the iodine content between grains is preferably uniform.
The iodine content distribution between grains as determined by EPMA method preferably has a relative standard deviation of 50% or less, more preferably 35% or less.
In another preferred iodine distribution between grains, the logarithm of grain size and the iodine content show a positive relationship. In other words, large size grains have a high iodine content while small size grains have a low iodine content. An emulsion having such a relationship gives excellent results in view of graininess. This coefficient of correlation is preferably in the range of 40% or more, more preferably 50% or more.
In the core portion, silver halide other than silver iodide may be silver bromochloride or silver bromide. Preferably, the proportion of silver bromide is high. The silver iodide content is in the range of 15 to 45 mol%, preferably 25 to 45 mol%, more preferably 30 to 45 mol%. The most preferable silver halide in the core portion is silver bromoiodide containing 30 to 45% of silver iodide.
The composition of the outermost layer is a silver halide containing 8 mol% or less of silver iodide, preferably 6 mol% or less of silver iodide.
In the outermost layer, the silver halide other than silver iodide may be silver chloride, silver bromochloride or silver bromide. Preferably, the proportion of silver bromide is high. In particular, the outermost layer comprises silver bromoiodide or silver bromide containing 0.5 to 6 mol% of silver iodide.
In the entire halogen composition of the core-shell grains, the total silver iodide content is more than 10 mol%, preferably in the range of 10.5 to 25 mol%, more preferably 12 to 20 mol%.
One of the reasons why the silver halide emulsion of the present invention exhibits excellent graininess is that a high iodine content is obtained without lowering the development activity, increasing light absorption. Another reason for the excellent graininess is that the definite stratiform structure having a high iodine content layer in the core and a low iodine content layer in the outermost portion improves the efficiency of forming latent images.
The present silver halide grains have a average grain size of 0.05 to 3.0 µm, 0.1 to 1.5 µm, more preferably 0.2 to 1.3 u.m, particularly 0.3 to 1.0 u.m.
The term "average grain" size of silver halide grain as used herein means the geometrical average of grain sizes, as well known in the art, as described in T.H. James, The Theory of the Photographic process , 3rd ed., page 39, (Macmillan, 1966). The grain size is calculated in terms of the diameter of a sphere as described in Masafumi Arakawa, Ryudo Sokutei Nyumon , Funtai Kogakukaishi, vol. 17, pp. 299-313, (1980). For example, the grain size can be measured by a coal tar counter process, single grain light scattering process, or laser light scattering process.
The present silver halide grains having a definite stratiform structure may have a regular crystal form such as a hexagon, octagon, dodecagon and tetradecagon or an irregular crystal form such as a sphere, potato shape and tabular, and are preferably tabular twin grains having an aspect ratio of 1.2 to 8, particularly 1.5 to 5.
In regular crystals, grains having a (111) plane in a proportion of 50% or more are particularly preferred. In irregular crystals also, grains having a (111) plane in a proportion of 50% or more are particularly preferred. The area proportion of the (111) plane can be determined by Kuberka Munc's dye absorption method. In this method, a dye which is preferentially adsorbed by either the (111) plane or (100) plane and spectrally differs from association on (111) plane to that on (100) plane is selected. Such a dye is then added to an emulsion. By specifically examining the spectrum with respect to the added amount of the dye, the area proportion of the (111) plane can be determined.
The emulsion of the present invention is prepared according to the method disclosed in U.S. Patent 4,668,614 and the similar method thereof.
The present emulsion can be incorporated in any layer in the silver halide photographic material, and is preferably present in a green-sensitive emulsion layer. In the present invention, the green-sensitive emulsion layer preferably consists of two or more layers having different sensitivities. The emulsion according to the invention is particularly preferably incorporated in layers other than the lowest sensitivity layer.
The magenta coupler represented by formula [I] is incorporated in the same layer as the silver halide emulsion according to the invention. The amount of the magenta coupler incorporated in the light-sensitive material is in the range of 0.005 to 1.0 g/m², preferably 0.01 to 0.5 g/m², more preferably 0.05 to 0.4 g/m².
In the present invention, a compound represented by formula (A) is preferably present in at least one layer:

Q-SM^I (A)

wherein Q represents a heterocyclic group substituted with at least one moiety selected from the group consisting of -So₃M², -COOM², -OH and -NR^lR² directly or via a connecting group such as an alkylene group (e.g., methylene, ethylene 1,4-butylene), an arylene group (e.g., 1,4-phenylene, 1,3-phenylene), and combination thereof (e.g., represents hydrogen, an alkaline metal,
M¹ and M² each quaternary ammonium or quaternary phosphonium; and R' and R² each represents hydrogen or a substituted or unsubstituted alkyl group.
Without being bound by theory, it is considered that the compound of formula (A) has a function of making a definite stratiform structure, when the compound is used during a preparation of emulsion and acts to provide a high sensitivity, a decreased fog and an improvement in preservability.
A light-sensitive material containing the compound of formula (A) is disclosed as a silver halide color photographic material containing a heterocyclic mercapto compound containing at least one group selected from -SO₃H, -COOH, -OH and -NH₂ in JP-B-58-9939 (the term "JP-B" as used herein means an "examined Japanese patent publication").
Specific examples of the heterocyclic group represented by Q in formula (A) include oxazole ring, thiazole ring, imidazole ring, selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, pentazole ring, pyrimidine ring, thiadia ring, triazine ring, thiadiazine ring, and such rings condensed with other carbon rings or heterocyclic groups, such as a benzothiazole ring, benzotriazole ring, benzimidazole ring, benzoxazole ring, benzoselenazole ring, naphthoxazole ring, triazaindolidine ring, diazaindolidine ring, and tetraazaindolidine ring.
Particularly preferred mercapto heterocyclic compounds represented by formula (A) are those represented by formulae (B) and (C):

In formula (B), Y and Z, which may be the same or different, each represents nitrogen or CR^4- (in which R⁴ represents hydrogen, a substituted or unsubstituted alkyl group or substituted or unsubstituted aryl groups. R³ represents an organic group, such as a C₁-₂₀ alkyl group (e.g., methyl, ethyl, propyl, hexyl, dodecyl, octadecyl), and a C₆-₂₀ aryl group (e.g., phenyl group, naphthyl group), substituted by at least one group selected from the group consisting of -SO₃M², -COOM², -OH and -NR¹R², wherein M², R' and R² are as defined in formula (A), L' represents a connecting group selected from the group consisting of
and n is 0 or 1, and M is as defined in formula (A).
These alkyl groups and aryl groups can be further substituted by a halogen atom (e.g., F, Cl, Br), alkoxy group (e.g., methoxy, methoxyethoxy), aryloxy group (e.g., phenoxy), alkyl group (when R² is an aryl group), aryl group (when R² is an alkyl group), amido group (e.g., acetamido, benzoylamido), carbamoyl group (e.g., unsubstituted carbamoyl, phenylcarbamoyl, methyl carbamoyl), sulfonamido group (e.g., methanesulfonamido, phenylsulfonamido), sulfamoyl group (e.g., unsubstituted sulfamoyl, methyl sulfamoyl, phenyl sulfamoyl), sulfonyl group (e.g., methyl sulfonyl, phenyl sulfonyl), sulfinyl group (e.g., methyl sulfinyl, phenyl sulfinyl), cyano group, alkoxycarbonyl group (e.g., methoxy carbonyl), aryloxycarbonyl group (e.g., phenoxy carbonyl), and other substituents such as a nitro group.
When R³ is substituted by two or more substituents (-S))₃M, -COOM², -OH and -NR^lR²), they may be the same or different.
In formula (C), X represents sulfur, oxygen or
R⁵ represents hydrogen, a substituted or unsubstituted alkyl group or substituted or unsubstituted aryl group.
L² represents -CONR⁶, -NR⁶CO-, -SO₂NR⁶-, -NR⁶SO₂-, -OCO-, -COO-, -S-, -NR^6-, -CO-, -SO-, -OCOO-, -NR⁶CONR⁷-, -NR⁶COO-, -OCONR⁶- or -NR⁶S0₂NR^7- (in which R⁶ and R⁷ each represents hydrogen, a substituted or unsubstituted alkyl group or substituted or unsubstituted aryl group).
R³, M¹ and M² are as defined in formulae (A) and (B); and n is 0 or 1.
The substituents for the alkyl group and aryl group represented by R⁴, R^S, R⁶ and R⁷ may be the same as those for R³.
In formulae (B) and (C), R³ is particularly preferably -SO₃M² or -COOM².
Specific examples of preferred compound represented by formula (A) are set forth below, but the present invention is not to be construed as being limited thereto.
The compound represented by formula (A) is known and can be synthesized by any suitable method as described in U.S. Patents 2,585,388, 2,541,924, and 3,017,270, JP-B-42-21842, JP-B-49-8334, and JP-B-40-28496, JP-A-53-50169, JP-A-55-59463, JP-A-50-89034, JP-A-53-28426, and JP-A-55-21007, British Patents 1,275,701, and 940,169, D.A. Berges et al., Journal of the Heterocyclic Chemistry , vol. 15, No. 981, 1978, The Chemistry of Heterocyclic Chemistry , Imidazole and Derivatives, part I, pp. 336-339, Chemical Abstract , 58 , No. 7921 (1963), page 394, E. Hoggarth, Journal of Chemical Society , pp. 1160-1167, (1949), S.R. Saudler, W. Karo, Organic Functional Group Preparation , Academic Press, pp. 312-315, (1968), M. Chamdon et al., Bulletin de la Societe Chimique de France , 723 (1954), D.A. ShirIey,D.W. Alley, J. Amer.Chem.Soc. , 79 , 4922 (1954), A. Wohl, W. Marchwald, Ber., Journal of German Chemical Society , vol. 22, page 568 (1889), Journal of American Chemical Society , 44 , pp. 1502-1510, Advances in Heterocyclic Chemistry , 9 , pp. 165-209 (1968), West German Patent 2,716,707, The Chemistry of Heterocyclic Compounds Imidazole and Derivatives , vol.1, page 384, Organic Synthesis , IV., 569 (1963), Ber., 9 , 465 (1976), and Journal of American Chemical Society , 45 , 2390 (1923).
The compound represented by formula (A) is incorporated in a silver halide emulsion layer, or a hydrophilic colloidal layer (e.g., interlayer, surface protective layer, yellow filter layer, or antihalation layer).
The compound represented by formula (A) is preferably incorporated in a silver halide emulsion layer or a layer adjacent thereto.
The amount of the compound represented by formula (A) to be incorporated is in the range of 1 x 10-⁷ to 1×10^-3 mol/m², preferably 5×10^-7 to 1×10^-4 mol/m², more preferably 1×10^-6 to 3x10-⁵ mol/m².
The color photographic light-sensitive material for photographing can have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. The number of silver halide emulsion layers and light-insensitive layers and the order of arrangement of these layers are not specifically limited. In a typical embodiment, the silver halide photographic material has at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity and different light sensitivities on a support. The light-sensitive layers are unit light-sensitive layers having a color sensitivity to any of blue light, green light and red light. In the multilayer silver halide color photographic material, these unit light-sensitive layers are normally arranged in the order of red-sensitive layer, green-sensitive layer and blue-sensitive layer viewed from the support. However, the order of arrangement can be optionally reversed depending on the purpose of application. Alternatively, two unit light-sensitive layers having the same color sensitivity can be arranged with a unit light-sensitive layer having a different color sensitivity interposed therebetween.
Light-insensitive layers such as various interlayers can be provided between these silver halide light-sensitive layers and on the uppermost layer and lowermost layer.
These interlayers can contain couplers, DIR compounds or the like as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037 and JP-A-61-20038. These interlayers can further contain a color mixing inhibitor as commonly used
The plurality of silver halide emulsion layers constituting each unit light-sensitive layer can be preferably in a two-layer structure, i.e., high sensitivity emulsion layer and low sensitivity emulsion layer, as described in West German Patent 1,121,470 and British Patent 923,045. In general, these layers are preferably arranged in such an order that the light sensitivity becomes lower towards the support. Furthermore, a light-insensitive layer can be provided between these silver halide emulsion layers. As described in JP-A-57-112751, JP-A-62-200350, JP-A-62206541, and JP-A-62-206543, a low sensitivity emulsion layer can be provided remote from the support while a high sensitivity emulsion layer can be provided nearer to the support.
In an embodiment of such an arrangement a low sensitivity blue-sensitive layer (BL), a high sensitivity blue-sensitive layer (BH), a high sensitivity green-sensitive layer (GH), a low sensitivity green-sensitive layer (GL), a high sensitivity red-sensitive layer (RH), and a low sensitivity red-sensitive layer (RL) can be arranged in this order from the uppermost layer to the support. In another embodiment, BH, BL, GL, GH, RH, and RL can be arranged in this order from the surface layer to the support. In a further embodiment, BH, BL, GH, GL, RL, and RH can be arranged in this order from the surface layer to the support.
As described in JP-B-55-34932, a blue-sensitive layer, GH, RH, GL, and RL can be arranged in this order from the surface layer to the support. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, a blue-sensitive layer, GL, RL, GH, and RH can be arranged in this order from the surface to the support.
As described in JP-B-49-15495, a layer arrangement can be used such that the uppermost layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lowermost layer is a silver halide emulsion layer having a lower sensitivity that that of the middle layer. In such a layer arrangement, the light sensitivity becomes lower towards the support. Even if the layer structure comprises three layers having different light sensitivities, a middle sensitivity emulsion layer, a high sensitivity emulsion layer and a low sensitivity emulsion layer can be arranged in this order from the surface to the support in a color-sensitive layer as described in JP-A-59-202464.
Alternatively, a high sensitivity emulsion layer, a low sensitivity emulsion layer and a middle sensitivity emulsion layer, or a low sensitivity emulsion layer, a middle sensitivity emulsion layer and a high sensitivity emulsion layer can be arranged in this order.
In the case where the layer structure has four or more layers, too, the order of arrangement of layers can be altered as described above.
In order to improve color reproducibility, a donor layer (CL) having an interlayer effect and a different spectral sensitivity distribution from the main light-sensitive layer such as BL, GL and RL is preferably provided adjacent or close to the main light-sensitive layer, as described in U.S. Patents 4,663,271, 4,705,744 and 4,707,436, and JP-A-62-160448, and JP-A-63-89580.
As described above, various layer structures and arrangements can be selected depending on the purpose of the light-sensitive material.
A suitable silver halide to be incorporated in the photographic emulsion layer in the present color light-sensitive material for photographing is silver bromoiodide, silver chloroiodide or silver bromochloroiodide containing silver iodide in an amount of about 30 mol% or less. Particularly suitable is silver bromoiodide or silver bromochloroiodide containing silver iodide in an amount of about 2 mol% to about 25 mol%.
Silver halide grains other than those previously disclosed which may be used in the photographic emulsions may be regular grains having a regular crystal form, such as cube, octahedron and tetradecahedron, or those having an irreggular crystal form such as a sphere and tabular form, those having a crystal defect such as a twinning plane, or those having a combination of these crystal forms.
The silver halide grains may be either fine grains of about 0.2 _Ilm or smaller in diameter or giant grains having a projected area diameter or up to about 10 _Ilm. The emulsion may be either a monodisperse emulsion or a polydisperse emulsion.
The preparation of the silver halide photographic emulsion which can be used in the present invention can be accomplished by any suitable method as described in Research Disclosure No. 17643 (December 1978), pp. 22-23, I. Emulsion Preparation and Types , and No. 18716 (November 1979), page 648, Glafkides, Chimie et Phisique Photographique , Paul Montel (1967), G.F. Duffin, Photographic Emulsion Chemistry , Focal Press (1966) and V.L. Zelikman et al, Making and Coating Photographic Emulsion , Focal Press (1964).
Furthermore, monodisperse emulsions as described in U.S. Patents 3,574,628 and 3,655,394 are preferably used in the present invention.
Tabular grains having an aspect ratio of about 5 or more can be used in the present invention. The preparation of such tabular grains can be easily accomplished by any suitable method as described in Gutoff, Photographic Science and Engineering , vol. 14, pp. 248-257, 1970, U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent 2,112,157.
The individual silver halide crystals may have either a homogeneous structure or a heterogeneous structure composed of a core and an outer shell differing in halogen composition, or may have a layered structure. Furthermore, the grains may have fused thereto a silver halide having a different halogen composition or a compound other than silver halide, e.g., silver thiocyanate, or lead oxide, by an epitaxial junction.
Mixtures of grains having various crystal forms may also be used.
The silver halide emulsion used in the present invention is normally subjected to physical ripening, chemical ripening and spectral sensitization. Additives to be used in these steps are described in Research Disclosure Nos. 17643 and 18716 as tabulated below.
Known photographic additives which can be used in the present invention are also described in these articles as shown in the table.
In order to inhibit deterioration in photographic properties due to formaldehyde gas, a compound capable of reacting with and solidifying formaldehyde as disclosed in U.S. Patents 4,411,987 and 4,435,503 can be incorporated in the light-sensitive material.
Various color couplers can be used in the present invention. Specific examples of the color couplers are described in the above cited Research Disclosure No. 17643, VII-C to G.
Preferred yellow couplers include those described in U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, 3,973,968, 4,314,023, and 4,511,649, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, and European Patent 249,473A.
Preferred magenta couplers other than the present magenta couplers include 5-pyrazolone compounds. Particularly preferred are those described in U.S. Patents 4,310,619, 4,351,897, 3,061,432, and 4,556,630, European Patent 73,636, JP-A-60-33552, JP-A-60-35730, JP-A-55-118034, and JP-A-60-185951, RD Nos. 24220 (June 1984), and WO(PCT)88/04795.
Cyan couplers include naphthol and phenol couplers. Preferred are those described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, 4,327,173, 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199, West German Patent Disclosure No. 3,329,729, European Patents 121,365A and 249,453A, and JP-A-61-42658. Particularly preferred are 1-naphthol couplers represented by formula [D] containing a substituted amino group in the 5-position:
wherein R₁ represents a halogen atom, aliphatic group, aromatic group, heterocyclic group, amidino group, guanidino group, -COR₄, -S0₂R₄, -SOR4,
-NHCOR₄, -NHSO₂R₄, -NHSOR₄ or
(R₄ and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an aliphatic oxy group or an aromatic oxy group; R₂ represents a group capable of substituting the naphthol ring; ℓ is 0 or an integer of 1 to 3; R₃ represents hydrogen or an organic substituent; and T represents hydrogen or a group capable of being separated upon coupling reaction with an oxidation product of an aromatic primary amine developing agent.
R₂ preferably represents a halogen atom, hydroxy group, carboxy group, sulfo group, amino group, cyano group, nitro group, aliphatic group, aromatic group, carbonamido group, sulfonamido group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic oxy carbonyl group, aromatic oxy carbonyl group, aliphatic oxy carbonylamino group, aromatic oxy carbonylamino group, sulfamoylamino group, heterocyclic group or imido group.
Organic substituent represented by R₃ includes R₆ U, wherein R₆ represents hydrogen, aliphatic group, aromatic group, heterocyclic group, -OR₇, -SR₇, -COR₈,
-PO(R₇)₂, -PO(-OR₇)₂,

-C0₂R₇, -SO₂R₇, -S0₂0R₇, or imido group, and U represents
or a single bond. (R₇ represents aliphatic group, aromatic group, or heterocyclic group, R₈ represents hydrogen, aliphatic group, aromatic group, or heterocyclic group, and R₉ and R₁₀ each represents hydrogen, aliphatic group, aromatic group, heterocyclic group, acyl group, aliphatic sulfonyl group or aromatic sulfonyl group).
If ℓ' is plural, the plurality of R₂'s may be the same or different or may be connected to each other to form a ring. R₂ and R₃, or R₃ and T may be connected to each other to form a ring. Any of 1, 2, 3 and T may be connected to each other via a group having a valency of two or more to form a dimer or higher polymer (oligomer or polymer).
Specific examples of couplers represented by formula [A] used in the present invention are described below, but the present invention is not to be construed as being limited thereto.
The synthesis of the cyan coupler represented by formula [A] can be easily accomplished by any suitable method as described in European Patent 161626A.
The cyan coupler represented by formula [A] is incorporated in a red-sensitive emulsion layer and/or its adjacent layers. The total amount of the present cyan coupler to be incorporated is in the range of 0.01 to 1.5 g/m², preferably 0.1 to 1.2 g/m², more preferably 0.2 to 1.0 g/m². In the present invention, the red-sensitive emulsion layer preferably consists of two or more layers having different sensitivities. Among the present cyan couplers, a four equivalent coupler wherein T is hydrogen is preferably incorporated in a low sensitivity layer. A two equivalent coupler wherein T is not hydrogen is preferably incorporated in a high sensitivity layer. The incorporation of the present cyan coupler in the light-sensitive material can be accomplished in accordance with the method for the incorporation of other couplers described below. The proportion of the high boiling organic solvent to be used as dispersing solvent to the cyan coupler is preferably in the range of 0 to 1.0, more preferably 0 to 0.5, particularly 0 to 0.3 by weight.
In order to improve the finish in various automatic printers commonly used in a cyan coupler represented by the following formula (III) can be used in combination with the cyan coupler represented by the general formula [D]. The cyan coupler of the general formula (III) is normally used in an amount of 0.01 to 0.5 mol, preferably 0.05 to 0.30 mol per mol of coupler of the general formula [D].
wherein Bal represents a nondiffusion ballasting coupler; R₃₀ represents hydrogen or a halogen atom; R₄₀ represents an alkyl group; and X₁₀ represents hydrogen or a coupling-off group.
The compound represented by formula (III) is synthesized by any suitable method as described in U.S. Patents 4,124,396, 4,304,844, 4,299,914, 4,362,810, 4,368,257, 4,341,864, 4,342,825, 4,463,086, 4,532,202, 4,557,999, 4,500,635, etc.
Specific examples of the compound represented by formula (III) are set forth below, but the present invention is not to be construed as being limited thereto.
In order to improve color reproducibility and sharpness, a compound represented by any of formula (VI) to (IX) which releases a diffusible development inhibitor preferably be used in combination with these compounds.

wherein A represents a coupling component capable of reacting with an oxidation product of a color developing agent to release a -TIME-Z₂ group or -P-Z₂ group; B represents a redox component which undergoes an oxidation reduction reaction with an oxidation product of a color developing agent and then undergoes hydrolysis with an alkali to release Zi; TIME represents a timing group; Z₁ represents a diffusible development inhibitor; and -P-Z₂ represents a group which undergoes reaction with an oxidation product of a developing agent after cleavage from A or B to release a development inhibitor.
Z₂ may be a diffusible development inhibitor or a development inhibitor having a small diffusibility. If -TIME-Z₂ or -P-Z_z is diffusible, A-TIME-Z₂ and A(or B)-P-Z₂ are diffusible DIR compounds.
Examples of development inhibitors represented by Z₁ or Z₂ include those described in Research Disclosure , vol. 176, No. 17643, December 1978. Preferred examples of development inhibitors represented by Z₁ or Z₂ include mercaptotetrazole, selenotetrazole, mercaptobenzothiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole, mercaptobenzimidazole, selenobenzimidazole, benzotriazole mercaptotriazole, mercaptooxadiazole, mercaptothiadiazole, and derivatives thereof.
The development inhibitor is used in an amount of 0.001 g/m² to 0.50 g/m², preferably 0.01 g/m² to 0.30 g/m² and more preferably 0.020 g/m² to 0.15 g/m² in a photosensitive material.
Preferred examples of diffusible development inhibitors represented by Z₁ or Z₂ include those represented by the following formulae:
In formulae (Z-1) and (Z-2), R₁₁₁ and R₁₁₂ each represents an alkyl group, alkoxy group, acylamino group, halogen atom, alkoxycarbonyl group, thiazolilideneamino group, aryloxycarbonyl group, acyloxy group, carbamoyl group, N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, sulfonamido group, N-alkylcarbamoyloxy group, ureido group, hydroxy group, alkoxycarbonylamino group, aryloxy group, alkylthio group, arylthio group, anilino group, aryl group, imido group, heterocyclic group, alkylsulfonyl group or aryloxycarbonylamino group.
The value of t is 1 or 2. If t is 2, the two R₁₁₁'s or R₁₁₂'s may be the same or different. The total number of carbon atoms contained in these R₁₁₁'s or R₁₁₂'s is in the range of 0 to 20.
In formulae (Z-3), (Z-4), (Z-5), and (Z-6), R₁₁₃, R₁₁₄, R₁₁₅, R₁₁₆ and R₁₁₇ each represents an alkyl group, aryl group or heterocyclic group.
When R₁₁₁ to R₁₁₇ each represents an alkyl group, the alkyl group may be substituted or unsubstituted, chain or cyclic. Examples of substituents contained in such substituted alkyl groups represented 'by R₁₁₁ to R₁₁₇ include a halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, carbamoyl group, hydroxyl group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, and arylthio group.
When R₁₁₁ to R₁₁₁₇ each represents an aryl group, the aryl group may be substituted. Examples of substituents contained in such substituted aryl groups represented by R₁₁₁ to R₁₁₇ include an alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, halogen atom, nitro group, amino group, sulfamoyl group, hydroxyl group, carbamoyl group, aryloxycarbonylamino group, alkoxycarbonylamino group, acylamino group, cyano group, and ureido group.
When R111 to R₁₁₇ each represents a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic or condensed ring containing as hetero atoms, nitrogen, oxygen or sulfur. Such a heterocyclic group can be selected from a pyridyl group, quinolyl group, furyl group, benzothiazolyl group, oxazolyl group, imidazolyl group, thiazolyl group, triazolyl group, benzotriazolyl group, imideo group, and oxazine group. These groups may be substituted by substituents described for the aryl group represented by R₁₁₁ to R_117.
In formulae (Z-1) and (Z-2), the number of carbon atoms contained in R₁₁₁ and R₁₁₂ is preferably in the range of 1 to 20, and more preferably 7 to 20.
In formulae (Z-3), (Z-4), (Z-5), and (Z-6), the total number of carbon atoms contained in R₁₁₃ to Rii7 is in the range of 1 to 20, preferably 4 to 20.
A development inhibitor which is preferably used in the present invention is a compound which undergoes reaction with an oxidation product of a developing agent to release a development inhibitor which diffuses from the layer in which it has been held to other layers upon development to exhibit an effect of inhibiting development.
Examples of the coupler component represented by A include dye-forming couplers such as ac- ylacetanilide, malondiester, malondiamide, benzoylmethane, pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, indazolone, phenol and naphthol, and coupler components which do not substantially form a dye, such as acetophenone, indanone, and oxazolone.
Preferred examples of coupler components represented by (A) include those represented by formulae (X) to (XIII):

wherein R₁₃₀ represents an aliphatic group, aromatic group, alkoxy group or heterocyclic group; and R₁₃₁ and Ri32 each represents an aromatic group or heterocyclic group.
The aliphatic group represented by R₁₃₀ preferably contains 1 to 20 carbon atoms and may be substituted or unsubstituted, chain or cyclic. Preferred examples of substituents for the alkyl group include alkoxy, aryloxy, and acylamino.
If R₁₃₀, R₁₃₁ or Ri32 is an aromatic group, the aromatic group is a phenyl group, naphthyl group or the like, and particularly phenyl group. The phenyl group may contain substituents. Examples of such substituents include an alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, and alkylamido group, which contain 30 or less carbon atoms. The phenyl group represented by R₁₃₀, R₁₃₁ and R₁₃₂ may be substituted by an alkyl group, alkoxy group, cyano group or halogen atom.
R₁₃₃ represents hydrogen, an alkyl group, halogen atom, Carbonamido group or sulfonamido group. j is an integer of 1 to 5; and R134. and R₁₃₅ each represents hydrogen, an alkyl group or aryl group. The aryl group represented by R₁₃₄. or R₁₃₅ is preferably a phenyl group. The alkyl group and aryl group represented by R₁₃₄. or R₁₃₅ may contain substituents. Examples of such substituents include a halogen atom, alkoxy group, aryloxy group, and carboxyl group. R₁₃₄. and R₁₃₅ may be the same or different.
The compound represented by formula (VIII) is a compound which undergoes an oxidation-reduction reaction with an oxidation product of an aromatic primary amine developing agent and then undergoes hydrolysis with an alkali to release a development inhibitor or a precursor thereof (hereinafter referred to as "DIR redox compound"). B represents a redox portion. More particularly, B is represented by formula (XIV):
In formula (XIV), G and G each represents hydrogen or a protective group for phenolic hydroxyl group capable of being deprotected during photographic processing. Typical examples of such a protective group include hydrogen, an acyl group, sulfonyl group, alkoxycarbonyl group, carbamoyl group, and oxalyl group.
R₁₁₈, R₁₁₉ and R₁₂₀ may be the same or different and each represents hydrogen, a halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, cyano group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxyl group, sulfo group, sulfonyl group, acyl group, carbonamido group, sulfonamido group or heterocyclic group.
R₁₁₈ and R₁₁₉, R₁₁₈ and G, R₁₁₉ and G , and R₁₂₀ and G may be connected to each other to form an aromatic group or nonaromatic group. At least one of R₁₁₈, R₁₁₉ and R120 contains a C_10-20 nondiffusble ballasting group.
Z is the same development inhibitor as described above.
A preferred example of the development inhibitor used in the present invention is a compound wherein P becomes a redox group or coupler after cleavage from A or B.
Such a development inhibitor include a compound which undergoes a reaction with an oxidation product of a developing agent to release a development inhibitor which diffuses from the layer in which it has been contained to other layers to inhibit development.
These compounds according to the present invention can easily be synthesized by any suitable method as described in U.S. Patents 3,227,554, 3,617,291, 3,933,500, 3,958,993, 4,149,886, 4,234,678, and 4,248,962, JP-A-51-13239, JP-A-57-56837, JP-A-56-114946, JP-A-57-154234, JP-A-58-98728, JP-A-58-209736, JP-A-58-209737, JP-A-58-209738, JP-A-58-209740, JP-A-61-255342, JP-A-52-90932 and JP-A-62-24252, British Patents 2,070,266, and 2,072,363, Research Disclosure No. 21228 (December 1981), JP-B-58-9942, and JP-B-51-16141, and Japanese Patent Application No. 59-278,853.
Specific examples of typical diffusible development inhibitor-releasing compounds will be set forth below, but the present invention should not be construed as being limited thereto.
Colored couplers for correction of undesired absorptions of the developed color preferably include those described in Research Disclosure No. 17643, VII-G, U.S. Patents 4,163,670, 4,004,929, and 4,138,258, JP-B-57-39413, and British Patent 1,146,368. Furthermore, couplers for correction of unnecessay absorptions of the developed color by a fluorescent dye released upon coupling as described in U.S. Patent 4,774,181 and couplers containing as a separatable group a dye precursor group capable of reacting with a developing agent to form a dye as described in U.S. Patent 4,777,120 are preferably used.
Couplers which form a dye having moderate diffusibility preferably include those described in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent Publication No. 3,234,533.
Typical examples of polymerized dye-forming couplers are described in U.S. Patents 3,451,820, 4,080,211, 4,367,282, 4,409,320, and 4,576,910, and British Patent 2,102,173.
Couplers capable of releasing a photographically useful residue upon coupling can also be used in the present invention. Preferred examples of DIR couplers which release a developing inhibitor are described in the patents cited in RD 17643 VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37350 and JP-A-63-37346, and U.S. Patents 4,248,962, and 4,782,012.
Couplers capable of imagewise releasing a nucleating agent or a developing accelerator at the time of development preferably include those described in British Patents 2,097,140 and 2,131,188, and JP-A-59-157638 and JP-A-59-170840.
In addition to the foregoing couplers, the photographic material according to the present invention can further contain competing couplers as described in U.S. Patent 4,130,427, polyequivalent couplers as described in U.S. Patents 4,283,472, 4,338,393, and 4,310,618, DIR redox compound releasing coupler, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds as described in JP-A-60-185950 and JP-A-62-24252, couplers capable of releasing a dye which returns to its original color after release as described in European Patents 173,302A and 313,308A, couplers capable of releasing a bleach accelerator as described in R.D. No. 11449, R.D. No. 24241 and JP-A-61-201247, couplers capable of releasing a ligand as described in U.S. Patent 4,553,477, couplers capable of releasing a leuco dye as described in JP-A-63-75747, and couplers capable of releasing a fluorescent dye as described in U.S. Patent 4,774,181.
In the present invention, the light-insensitive layer provided interposed between the two light-sensitive layers having different color sensitivities can contain a compound represented by formula (E) to inhibit color contamination, further improving color reproducibility and preservability.
wherein Ra and Rb each represents hydrogen, a halogen atom, sulfo group, carboxyl group, alkyl group, acylamino group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfonyl group, acyl group or carbamoyl group, sulfamoyl group; Ra and Rb may together form a carbon ring; X represents -CO- or SOz-; and Rc represents an alkyl group, aryl group, heterocyclic group, cycloalkyl group, alkoxy group, aryloxy group or amino group. The total number of carbon atoms contained in Ra, Rb and Rc is 10 or more. The compound represented by formula (E) is substantially colorless and does not form a dye image upon a coupling reaction with a developing agent.
Specific examples of the compound represented by formula (E) and its precursor, which is unstable to alkali, are set forth below, but the present invention is not to be construed as being limited thereto.

Compound No.

In the present invention, the compound represented by formula (E) and the coupler represented by formula (I) are preferably incorporated in the light-sensitive material at the same time. More preferably, the compound represented by formula (E) is incorporated in the same layer as the coupler represented by formula (I) and/or adjacent layers, particularly in a light-insensitive layer adjacent to the light-sensitive silver halide emulsion layer in which the coupler represented by formula (I) is incorporated.
The compound represented by formula (E) and/or its precursor unstable to alkali can be incorporated in the light-sensitive material by the same method as the method described below for the dispersion and incorporation of coupler.
The total amount of the compound represented by formula (E) to be incorporated is in the range of 0.003 to 2.0 g/m², preferably 0.01 to 1.0 g/m², more preferably 0.05 to 0.3 g/m².
The incorporation of these couplers in the light-sensitive material can be accomplished by any suitable known dispersion method.
Examples of high boiling solvents to be used in the oil-in-water dispersion process are described in U.S. Patent 2,322,027.
Specific examples of high boiling organic solvents having a boiling point of 175" C or higher at normal pressure which can be used in the oil-in-water dispersion process include phthalic esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl)-phthalate, bis(2,4-di-t-amylphenyl)isophthalate, bis(1,1-diethylpropyl)phthalate), phosphoric or phosphonic esters (e.g., triphenylphosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxy ethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate), benzoic esters (e.g., 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxy benzoate), amides (e.g., N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (e.g., isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic esters (e.g., bis(2-ethylhexyl)sebacate, dioctyl azerate, glycerol tributylate, isostearyl lactate, trioctyl citrate), aniline derivatives (N,N-dibutyl-2-butoxy-5-tert-octylaniline), and hydrocarbons (e.g., paraffin, dodecylbenzene, diisopropyl naphthalene). As an auxiliary solvent there can be used an organic solvent having a boiling point of about 30° C or higher, preferably 50° C to about 160° C. Typical examples of such an organic solvent include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.
The process and effects of latex dispersion method and specific examples of latexes to be used in dipping are described in U.S. Patent 4,199,363, West German Patent Application (OLS) 2,541,274, and 2,541,230.
Various preservatives or antimolds such as 1,2-benzisothiazoline-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)benzimidazole as described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941 may be preferably incorporated in the present color light-sensitive material.
The present invention is applicable to various types of color light-sensitive materials, particularly preferably to color negative films for common use or motion picture, color reversal films for slide or television, color papers, color positive films and color reversal papers.
Suitable supports which can be used in the present invention are described in the above cited RD 17643 (page 28) and 18716 (right column on page 647 to left column on page 648).
In the present light-sensitive material, the total thickness of all hydrophilic colloidal layers on the emulsion side is preferably in the range of 28 µm or less, more preferably 23 u.m or less, particularly 20 u.m or less. The film swelling rate T_1/2 is preferably in the range of 30 seconds or less, more preferably 20 seconds or less. In the present invention, the film thickness is determined after being stored at a temperature of 25° C and a relative humidity of 55% over 2 days. The film swelling rate T_1/2 can be determined by a method known in the art, e.g., by means of a swellometer of the type as described in A. Green et al, Photographic Science Engineering , vol. 19, No. 2, pp. 124-129. T_1/2 is defined as the time taken until half the saturated film thickness is reached wherein the saturated film thickness is 90% of the maximum swollen film thickness reached when the light-sensitive material is processed with a color developer at a temperature of 30° C over 195 seconds.
The film swelling rate T,_;2 can be adjusted by adding a film hardener to gelatin as binder or altering the aging condition after coating. The percentage swelling of the light-sensitive material is preferably in the range of 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness determined as described above in accordance with the equation: (maximum swollen film thickness film thickness)/film thickness.
The color photographic light-sensitive material according to the present invention can be developed in accordance with an ordinary method as described in RD Nos. 17643 (pp.28-29) and 18716 (left column to right column on page 615).
The color developer to be used in the development of the present light-sensitive material is preferably an alkaline aqueous solution containing as a main component an aromatic primary amine color developing agent. As such a color developing agent there can be effectively used an aminophenolic compound. In particular, p-phenylenediamine compounds are preferably used. Typical examples of such p-phenylenediamine compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-a-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and sulfates, hydrochlorides and p-toluenesulfonates thereof. Particularly preferred among these compounds is 3-methyl-4-amino-N-ethyl-N-(3-hydroxyethyl aniline sulfate. These compounds can be used in combination of two or more thereof depending on the purpose of application.
The color developer normally contains a pH buffer such as carbonate and phosphate of alkaline metal or a development inhibitor or fog inhibitor such as chlorides, bromides, iodides, benzimidazoles, ben- zothiazoles and mercapto compounds. If desired, the color developer may further contain various preservatives, e.g., hydroxylamine, diethylhydroxylamine, sulfites, hydrazines (e.g., N,N-biscarboxymethyl hydrazine), phenylsemicarbazides, triethanolamine, and catecholsulfonic acids; organic solvents, e.g., ethylene glycol and diethylene glycol; development accelerators, e.g., benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines; color-forming couplers; competing couplers; auxiliary developing agents, e.g., 1-phenyl-3-pyrazolidone; viscosity-imparting agents; various chelating agents exemplified by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminoacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephos phonic acid, ethyienediamine-N,N,N ,N -tetramethyienephosphonic acid, and ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof.
Reversal processing is usually carried out by black-and-white development followed by color development. Black-and-white developers to be used can contain one or more of known black-and-white developing agents, such as dihydroxybenzenes, e.g., hydroquinone, 3-pyrazolidones, e.g., 1-phenyl-3-pyrazolidone, and aminophenols, e.g., N-methyl-p-aminophenol.
The color developer or black-and-white developer usually has a pH of from 9 to 12. The replenishment rate of the developer is usually 3 1 or less per m² of the light-sensitive material, though depending on the type of the color photographic material to be processed. The replenishment rate may be reduced to 500 ml/m² or less by decreasing the bromide ion concentration in the replenisher. When the replenishment rate is reduced, it is preferable to reduce the area of the liquid surface in contact with air in the processing tank to thereby prevent evaporation and air-oxidation of the liquid.
The area of the liquid surface in contact with air can be represented by the opening value defined as follows:

Opening value = Area of liquid surface incontact with air (cm²)/volume of liquid (cm³)

The opening value is preferably in the range of 0.1 or less, more preferably 0.001 to 0.05. The reduction of the opening value can be accomplished by providing a cover such as floating cover on the surface of a photographic processing solution in the processing tank, or by a process which comprises the use of a mobile cover as described in JP-A-1-82033, or a slit development process as described in JP-A-63-216050. The reduction of the opening value can be applied not only to both the color development and black-and-white development but also to the subsequent steps such as bleach, blix, fixing, rinse and stabilization. The replenishment rate can also be reduced by a means for suppressing accumulation of the bromide ion in the developing solution.
The color development time is normally selected between 2 and 5 minutes. The color development time can be further reduced by carrying out color development at an elevated temperature and a high pH value with a color developing solution containing a color developing agent in a high concentration.
The photographic emulsion layer which has been color-developed is normally subjected to bleach. Bleach may be effected simultaneously with fixation (i.e., blix), or these two steps may be carried out separately. For speeding up of processing, bleach may be followed by blix. Further, any of an embodiment wherein two blix baths connected in series are used, an embodiment wherein blix is preceded by fixation, and an embodiment wherein blix is followed by bleach may be selected as desired. Bleaching agents include compounds of polyvalent metals, e.g., iron(III), peroxides, quinones, and nitro compounds. Typical examples of these bleaching agents are organic complex salts of iron(III) with aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid, or citric acid, tartaric acid, and malic acid. Of these, aminopolycarboxylic acid-iron(III) complex salts such as (ethylenediaminetetraacetato)iron(III) complex salts are preferred in view of speeding up of processing and conservation of the environment. In particular, aminopolycarboxylic acid-iron(III) complex salts are useful in both a bleaching solution and a blix solution. The bleaching or blix solution containing such an aminopolycarboxylic acid-iron(ill) complex salt normally has a pH value of 4.0 to 8.0. For speeding up of processing, it is possible to adopt a lower pH value.
The bleaching bath, blix bath or a prebath thereof can contain, if desired, a bleaching accelerator. Examples of useful bleaching accelerators include compounds containing a mercapto group or a disulfide group as described in U.S. Patent 3,893,858, West German Patent 1,290,812, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, and JP-A-53-28426, and Research Disclosure No. 17129 (July 1978), thiazolidine derivatives as described in JP-A-50-140129, thiourea derivatives as described in U.S. Patent 3,706,561, iodides as described in West German Patent 1,127,715 and JP-A-58-16235, polyoxyethylene compounds as described in West German Patents 966,410 and 2,748,430 polyamine compounds as described in JP-B-45-8836, compounds as described in JP-A-49-42434, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506, and JP-A-58-163940, and bromine ions. Preferred among these compounds are compounds containing a mercapto group or disulfide group because of their great acceleratory effects. In particular, the compounds disclosed in U.S. Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are preferred. The compounds disclosed in U.S. Patent 4,552,834 are also preferred. These bleaching accelerators may be incorporated into the light-sensitive material. These bleaching accelerators are particularly effective for blix of color light-sensitive materials for photographing.
The bleaching solution or blix solution used in the present invention preferably contains an organic acid besides the above-mentioned compounds for the purpose of inhibiting bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5. Specific examples of such an organic acid include acetic acid and propionic acid.
Fixing agents to be used for fixation include thiosulfates, thiocyanates, thioethers, thioureas, and a large amount of iodides. The thiosulfates are normally used, with ammonium thiosulfate being applicable most broadly. These thiosulfates may be preferably used in combination with thiocyanates, thioether compounds, thiourea or the like. As preservatives of the fixing bath or blix bath there can be preferably used sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds as described in European Patent 294769A. Further, various aminopolycarboxylic acids or organic phosphonic acids can be added to the fixing bath or blix bath for the purpose of stabilizing the solution. The total desilvering time is preferably short, provided that no misdesilvering takes place. The total desilvering time is preferably in the range of 1 to 3 minutes, more preferably 1 to 2 minutes. The desilvering temperature is in the range of 25 to 50 C, preferably 35 to 45 C. In this preferred temperature range, the desilvering rate can be improved, and the occurrence of stain after processing can be effectively inhibited.
In the desilvering step, the agitation is preferably intensified as much as possible. In particular, the agitation can be intensified by various methods. For example, the processing solution may be jetted to the surface of the emulsion layer in the light-sensitive material as described in JP-A-62-183460 and JP-A-62-183461. The agitating effect can be improved by a rotary means as described in JP-A-62-183461. Furthermore, the agitating effect can be improved by moving the light-sensitive material with the emulsion surface in contact with a wiper blade provided in the bath so that a turbulence occurs on the emulsion surface. Moreover, the agitation can be intensified by increasing the total circulated amount of processing solution. Such an agitation improving method can be effectively applied to the bleaching bath, blix bath or fixing bath. The improvement in agitation effect increases the supply of a bleaching agent, fixing agent or the like into the emulsion film, resulting in an improvement in desilvering rate. The above-mentioned agitation improving method is more effective when a bleach accelerator is used. In this case, the agitation improving method can remarkably enhance the bleach accelerating effect or eliminate the effect of inhibiting fixation by the bleach accelerator.
The automatic developing machine to be used in the present invention is preferably equipped with a light-sensitive material conveying means as described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. As described in the above cited JP-A-60-191257, such a conveying means can remarkably reduce the amount of the processing solution carried over from a bath to the succeeding bath, thus inhibiting the deterioration of properties of the processing solution. This is particularly effective for the reduction of processing time at each step or the replenishment rate of the processing solution.
It is usual that the desilvered silver halide color photographic materials of the invention are subjected to washing and/or stabilization. The quantity of water to be used in the washing can be selected from a broad range depending on the characteristics of the light-sensitive material (for example, the kind of couplers, etc.), the end use of the light-sensitive material, the temperature of washing water, the number of washing tanks (number of stages), the replenishment system (e.g., counter-flow system or direct-flow system), and other various factors. Of these factors, the relationship between the number of washing tanks and the quantity of water in a multistage counter-flow system can be obtained according to the method described in Journal of the Society of Motion Picture and Television Engineers , vol. 64, pp-248-253 (May 1955).
According to the multi-stage counter-flow system described in the above reference, although the requisite amount of water can be greatly reduced, bacteria would grow due to an increase of the retention time of water in the tank, and floating masses of bacteria might stick to the light-sensitive material. In the present invention, in order to cope with this problem, the method of reducing calcium and magnesium ion concentrations described in JP-A-62-288838 can be used very effectively. Further, it is also effective to use isothiazolone compounds or thiabendazoles as described in JP-A-57-8542, chlorine type bactericides, e.g., chlorinated sodium isocyanurate, benzotriazole, and bactericides described in Hiroshi Horiguchi, Bokin- bobaizai no Kagaku , Eisei gijutsu Gakkai (ed.), Biseibutsu no Mekkin, Sakkin, Bobigijutsu , and Nippon Bokin Bobi Gakkai (ed.), Bokin Bobizai Jiten .
The washing water has a pH value of from 4 to 9, preferably from 5 to 8. The temperature of the water and the washing time can be selected from broad ranges depending on the characteristics and enduse of the light-sensitive material, but usually ranges from 15 to 45 C in temperature and from 20 seconds to 10 minutes in time, preferably from 25 to 40 C in temperature and from 30 seconds to 5 minutes in time. The light-sensitive material of the invention may be directly processed with a stabilizer in place of the washing step. For the stabilization, any of the known techniques as described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used.
The washing step may be followed by stabilization in some cases. For example, a stabilizing bath containing a dye stabilizer and a surface active agent as is used as a final bath for color light-sensitive materials for photographing. Examples of such a dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde-sulfurous acid adducts.
This stabilizing bath may also contain various chelating agents or bactericides.
The overflow accompanying replenishment of the washing bath and/or stabilizing bath can be reused in other steps such as desilvering.
In the processing using an automatic developing machine, if these processing solutions are concentrated due to evaporation, water may be preferably supplied to the system to make up for the concentration.
The present silver halide color light-sensitive material may contain a color developing agent for the purpose of simplifying and expediting processing. Such a color developing agent is preferably used in the form of various precursors. Examples of such precursors include indoaniline compounds as described in U.S. Patent 3,342,597, Schiff's base type compounds as described in U.S. Patent 3,342,599, and Research Disclosure Nos. 14,850 and 15,159, and aldol compounds as described in Research Disclosure No. 13,924, metal complexes as described in U.S. Patent 3,719,492, and urethane compounds as described in JP-A-53-135628.
The present silver halide color light-sensitive material may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical examples of such compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
In the present invention, the various processing solutions are used at a temperature of 10°C to 50°C. The standard temperature range is normally from 33 C to 38 C. However, a higher temperature range can be used to accelerate processing, reducing the processing time. On the contrary, a lower temperature range can be used to improve the picture quality or the stability of the processing solutions. In order to save silver, a processing using cobalt intensification or hydrogen peroxide intensification as described in West German Patent 2,226,770 and U.S. Patent 3,674,499 can be effected.
The present silver halide photographic material includes a heat-developable light-sensitive material as described in U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, and JP-A-61-238056, and European Patent 210,660A2.
The present invention is now described in greater detail with reference to the following examples, but the present invention is not to be construed as being limited thereto. Unless otherwise indicated, all parts percents and ratios are by weight.

EXAMPLE 1

Preparation of emulsion

1500 cc of an aqueous solution of 5.0 g of silver nitrate was instantaneously added to an aqueous solution of 20 g of inert gelatin, 2.4 g of potassium bromide and 2.05 g of potassium iodide in 800 ml of distilled water at a temperature of 58° C with stirring. Excess potassium bromide (4.0 g) was added to the material. The material was then subjected to physical ripening over 20 minutes. 0.2 mollt, 0.67 mol/t and 2 mol/i of aqueous solutions of silver nitrate and an aqueous solution of potassium halide (mixture of 58 mol% of potassium bromide with 42 mol% of potassium iodide) were added to the material at a flow rate of 10 cc/min, respectively, in accordance with the method described in U.S. Patent 4,242,445 to allow 42 mol% of silver bromoiodide grains to grow. The emulsion was then washed with water so that it was desilvered to obtain Emulsion a. The yield of Emulsion a was 900 g. The size of the emulsion grains was 0.61 µm. Emulsions of 32 mol% of silver bromoiodide grains having a size of 0.71 µm, 30 mol% of silver bromoiodide grains having a size of 0.65 µm, 42 mol% of silver bromoiodide grains having a size of 0.15 µm, 16 mol% of silver bromoiodide grains having a size of 0.83 µm, and 42 mol% of silver bromoiodide grains having a size of 0.56 u.m were prepared in the same manner as in Emulsion a to obtain Emulsions b, c, d, e and f, respectively.
850 cc of distilled water and 30 cc of 10% potassium bromide were added to 300 g of Emulsion a. The mixture was stirred at a temperature of 70 C. 300 cc of an aqueous solution of 33 g of silver nitrate and 320 cc of an aqueous solution of 25 g of potassium bromide were simultaneously added to the material in 30 minutes. 800 cc of an aqueous solution of 100 g of silver nitrate and 860 cc of an aqueous solution of 75 g of potassium bromide were simultaneously added to the material in 60 minutes to obtain Emulsion 1 containing silver bromoiodide grains having a silver iodide content of 14 mol% and a size of 0.90 µm. Emulsion 1 contained twin grains having an aspect ratio of 1.9 wherein the proportion of (111) plane was 85%. Emulsion 2 having a silver iodide content of 16 mol% was prepared from 450 g of Emulsion b in the same manner as in Emulsion 1 so that the grains were covered with a shell of a total amount of 100 g in terms of silver nitrate.
850 cc of distilled water and 3 cc of 1% potassium bromide were added to 450 g of Emulsion b. The material was then heated to a temperature of 75 cc. A compound of the structural formula (1) shown below was then adsorbed by the material. 250 g of an aqueous solution of 25 g of silver nitrate and 270 cc of an aqueous solution of 17.5 g of potassium bromide were simultaneously added to the material. 600 cc of an aqueous solution of 75 g of silver nitrate and 650 cc of an aqueous solution of 52.5 g of potassium bromide were simultaneously added to the material to obtain a silver bromoiodide emulsion 3 having a silver iodide content of 16 mol%.

Compound (1)

A silver bromoidide emulsion 4 was prepared from 360 g of Emulsion c in the same manner as in Emulsion 3 so that the grains were covered with a shell of a total amount of 120 g in terms of silver nitrate except that Compound (1) was replaced by a compound of the structural formula (2):

Compound (2)

Emulsion 5 was prepared by covering Emulsion d with a shell of silver bromide. Emulsion 6 was prepared in the same manner as in Emulsion 4 except that Compound (2) was replaced by a compound of the structural formula (3):

Compound (3)

Emulsions 7 and 8 were prepared from Emulsions e and f, respectively, in the same manner as in Emulsion 1.
Emulsion 9 was prepared in the same manner as in Example 1 of JP-A-63-296046.
The structures from Emulsion 1 are set forth in Table 1. The definite stratiform structure was a structure wherein the presence of a silver bromoiodide layer containing 15 to 45 mol% of silver iodide as defined herein Was confirmed by X-ray diffractometry.
A multilayer color light-sensitive material 101 was prepared by coating various layers having the following compositions on an undercoated cellulose triacetate support.

Composition of light-sensitive layer

The figures indicate the amount of each component (g) added per m² of light-sensitive material. The amount of silver halide and coupler is calculated in terms of silver. The amount of sensitizing dye is represented as a molar amount calculated in terms of the coated amount based on the amount of silver halide contained in the same layer.

Specimen 101

To each layer were added benzoisothiazolone (in an average amount of 400 ppm based on gelatin), phenoxyethanol (in an average amount of 4,000 rpm), a gelatin hardener H-1 in a total amount of 0.40 g/m², and 0.50 g/m² of surface active agents.

Specimens 102 to 127

Specimens 102 to 127 were prepared in the same manner as in Specimen 101 except that Emulsion 1 incorporated in the 9th layer was replaced by Emulsions 2 to 9 and/or Coupler ExM-7 was replaced by the present invention couplers A-2 to A-9 in molar amounts of 0.45 times the amount of coupler ExM-7, respectively.

Specimens 128 to 131

Specimens 128 to 131 were prepared in the same manner as in Specimens 119 to 122, respectively, except that the present invention compound (11) incorporated in the 10th layer was not used. The coating solutions thus prepared were coated on a support within 30 minutes after preparation.
These specimens were then imagewise exposed to green light, and then subjected to the following color development. These specimens were then examined to determine the relative sensitivity of the green-sensitive layer. After imagewise exposure to green light, another batch of these specimens were allowed to stand at a temperature of 50 ^*C and a relative humidity of 30% over 7 days, and then subjected to color development. These specimens were then examined for relative sensitivity. The relative sensitivity is represented as the logarithm of the reciprocal of the exposure giving a density of fog +0.2 for magenta density relative to that of Specimen 101 as 0.
A further batch of these specimens were exposed to light through a wedge for measurement of RMS granularity. The RMS value of the diameter of points exposed through an aperture with a diameter of 48 µm was determined at densities of fog + 0.3 and +0.7 for magenta density.
The color contamination was determined by subtracting the yellow density in the unexposed portion from that at a density of fog + 0.7 for magenta density. The results are set forth in Table 2.
The color development was effected at a temperature of 38 C as follows:
In the above mentioned process, the washing step was effected in a countercurrent process wherein the overflow washing water from step 2 was fed to the both in washing step 1. The composition of the various processing solutions are set forth below.
The replenishment rate of the color developer was 1,200 ml per m² of color light-sensitive material. The replenishment rate of the other processing solutions were each 800 ml per m² of color light-sensitive material. The amount of the processing solution came over to the washing step was 50 ml per m² of color light-sensitive material.

Bleaching solution

Washing water

Tap water containing 32 mg/ℓ of calcium ion and 7.3 mg/t of magnesium ion was passed through a column filled with an H-type strongly acidic cationic exchanging resin and an OH-type strongly basic anionic exchanging resin so that the calcium ion concentration and the magnesium ion concentration reached 1.2 mg/t and 0.4 mg/t, respectively. Sodium dichlorinated isocya nurate was then added to the solution in an amount of 20 mg per t.

Drying

The drying temperature was 50° C.
Table 1 shows that the specimens according to the present invention exhibited a higher sensitivity and/or better graininess and provided a higher sensitivity under extreme conditions after exposure than the comparative specimens containing the inveniton couplers and emulsions outside the scope of the present invention, and also exhibited a higher sensitivity, better graininess in the high density range, and less color contamination than the comparative specimens containing couplers outside the scope of the present invention.

EXAMPLE 2

Specimens 201 to 209 were prepared in the same manner as in Specimens 119 to 127, respectively, except that the coating solutions for the various layers were allowed to stand at a temperature of 42° C ±2°C over 5 hours before being coated. These specimens were then processed in the same manner as in Example 1. These specimens were then examined for relative sensitivity and granularity. The results are set forth in Table 3.
Table 3 shows that the present invention specimens exhibited no change in photographic properties, high sensitivity and excellent graininess even if the coating solutions were allowed to stand over an extended period of time.
The values in the parentheses indicate the difference from the data of Specimens 119 to 127, wherein the coating solutions were coated within 30 minutes after preparation.

EXAMPLE 3

A multilayer color light-sensitive material 301 was prepared by coating various layers having the following compositions on an undercoated cellulose triacetate support.

Composition of light-sensitive layer

The figures indicate the amount (g) of each component added per m² of light-sensitive material. The amount of silver halide and coupler is calculated in terms of silver. The amount of sensitizing dye is represented as a molar amount calculated in terms of the coated amount based on the amount of silver halide contained in the same layer.

3rd Layer: lst red-sensitive emulsion layer

7th Layer: lst green-sensitive emulsion layer

13th Layer: 1st blue-sensitive emulsion layer

14th Layer: 2nd blue-sensitive emulsion layer

16th Layer: 3rd blue-sensitive emulsion layer

To each layer were added benzoisothiazolone (in an average amount of 600 ppm based on gelatin), n-butyl-p-hydroxybenzoate (in an average amount of 1,000 ppm based on gelatin), and 2-phenoxyethanol (in an average amount of 1,000 ppm based on gelatin).

Specimens 302 to 316

Specimens 302 to 304 were prepared in the same manner as Specimen 301 except that Emulsion 10 incorporated in the 10th layer was replaced by Emulsions 11 to 13, respectively. Specimens 305 to 316 were prepared in the same manner as Specimens 301 to 304 except that EXM-4 incorporated in the 10th layer was replaced by the present invention coupler A-2, A-18 and A-19, respectively in the same molar amount.

Specimen 317

Specimen 317 was prepared in the same manner as in Specimen 313 except that 50 mol% of EXC incorporated in the 3rd and 4th layers was replaced by the present invention preferred cyan coupler (111-12).
Emulsions 10 to 13 were prepared in the same manner as in Example 1 (the composition of Emulsion 13 was the same as used in JP-A-1-102558).
These specimens were then exposed to light for sensitometry, subjected to the following color development, and measured for density (density D_A). Another batch of these specimens were subjected to the same processing except that the color development was omitted, and then measured for density (density D_B). The difference (D_A-D_B) was evaluated as fog. The relative sensitivity was evaluated by the logarithm of the reciprocal of the exposure giving a density of fog +0.3. RMS granularity and color contamination at (fog +0.7) were measured in the same manner as in Example 1.
Another batch of these specimens were subjected to development over 3 minutes and 45 seconds, and then measured for fog and relative sensitivity. The results are set forth in Table 4.
The color development was effected at a temperature of 38 C as follows:
The composition of the various processing solutions are set forth below.
With Fuji Photo film Co., Ltd.'s HG 400 as color paper and Fuji Photo Film Co., Ltd.'s FAP 3500 Printer, GRETAG's 3141 Printer and EASTMAN KODAK's 3510 Printer as printer, these specimens were then subjected to printing in such a manner that the print was best finished. As a result, a better print finish was obtained from Specimen 317 than from Specimen 313.
Table 4 shows that the present specimens exhibited little change in relative sensitivity with color development time, high sensitivity, excellent graininess as represented by RMS value, low color contamination, and excellent color reproducibility.
Specimen and specimen 317 wee loaded into 24-frame rolls and packed into a 135 size patrone. These specimens and Fuji Photo Film Co., Ltd.'s Super HG 400 were used to photograph outdoor scenery using Minolta Cameta Co., Ltd.'s Minolta a-7700i, with ISO sensitivity set to 6400, 1600 and 400.
(a mixture of 5-position substituted and 6-position substituted compounds)
(a mixture of 5-position substituted and 6-position substituted compounds)
(a mixture of 5-position substituted and 6-position substituted compounds)
(a mixture of 5-position substituted and 6-position substituted compounds)
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 departing from the spirit and scope thereof.

Claims

1. A silver halide color photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer comprising the combination of (1) at least one pyrazoloazole coupler and (2) a light-sensitive silver halide emulsion comprising chemically sensitized silver halide grains which have a distinct stratiform structure comprising silver bromoiodide containing 15 to 45 mol% of silver iodide with a total silver iodide content of more than 10 mol%.

2. The silver halide color photographic material as claimed in claim 1, wherein said pyrazoloazole coupler is represented by formula (I):

wherein Ro represents hydrogen, or a substituent; V represents hydrogen or a coupling-off group; and Za, Zb and Zc each represents a methine group, a substituted methine group, = N- or -NH-, provided that one of said Za-Zb bond and said Zb-Zc bond is a double bond and the other is a single bond.

3. The silver halide color photographic material as claimed in claim 2, wherein said pyrazoloazole coupler represented by formula (I) is represented by formula (I-a), (I-b), (I-c), (I-d), (I-e), (I-f) or (I-g):

wherein R⁵¹, R⁵² and R⁵³ each represents hydrogen, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group or an aryloxycarbonyl group; and V represents hydrogen, a halogen atom, a carboxyl group or a coupling-off group connected to the carbon atom in the coupling position via oxygen, nitrogen, or sulfur.

4. The silver halide color photographic material as claimed in claim 3, wherein said pyrazoloazole coupler is represented by formula (I-a), (I-d) or (i-e).

5. The silver halide color photographic material as claimed in claim 3, wherein said pyrazoloazole coupler is represented by formula (I-d).

6. The silver halide color photographic material as claimed in claim 3, wherein said pyrazoloazole coupler is represented by formula (I-e).

7. The silver halide color photographic material as claimed in claim 3, wherein said pyrazoloazole coupleris a polymeric coupler comprising a repeating coupler monomer comprising said pyrazoloazole couler moiety represented by formulae (I-a), (I-b), (I-c), (I-d), (I-e), (I-f) or (I-g), wherein at least one of R⁵¹, R⁵², R⁵³ and V comprises a polymerizable vinyl group.

8. The silver halide color photographic material as claimed in claim 3, wherein said pyrazoloazole coupler is a bis compound, wherein one of R⁵¹, R⁵², R⁵³ and V is a divalent group linking two coupler moieties represented by formulae (I-a), (I-b), (I-c), (I-d), (I-e), (I-f) or (I-g).

9. The silver halide color photographic material as claimed in claim 7, wherein said pyrazoloazole coupler moiety is linked to said vinyl group by a linking group selected from an alkylene group, a phenylene group and an aralkylene group.

10. The silver halide color photographic material as claimed in claim 7, wherein said polymer is a copolymer of said coupler monomer and at least one ethylenically unsaturated monomer which is incapable of coupling with an oxidation product of an aromatic primary amine developing agent.

11. The silver halide color photographic material as claimed in claim 4, wherein in formulae (I-d) and (I-e), R⁵¹ represents an alkyl group, an aryl group, an alkoxy group or an aryloxy group; R⁵² represents an alkyl group, an aryl group, an alkylthio group, an arylthio group or a heterocyclic thio group; and V represents a halogen atom, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group.

12. The silver halide color photographic material as claimed in claim 11, wherein R⁵² represents a group represented by formula (XV):

wherein L₁ represents a straight chain or branched chain alkylene group and R⁵⁶ represents a substituted or unsubstituted aryl group, a substituted or unsubstituted sulfonamido group, a substituted or unsubstituted carbonamido group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted alkylsulfonyl group.

13. The silver halide color photographic material as claimed in claim 2, wherein the amount of said pyrazoloazole coupler in said light-sensitive silver halide emulsion layer is from 0.001 to 1.0 g/m².

14. The silver halide color photographic material as claimed in claim 1, wherein said silver bromoiodide grains comprise a core containing 25 to 45 mol% of silver iodide and an outermost shell comprising at most 8 mol% of silver iodide.

15. The silver halide color photographic material as claimed in claim 14, wherein said core contains from 30 to 45 mol% silver iodide and said outermost shell contains from 0.5 to 6 mol% of silver iodide.

16. The silver halide color photographic material as claim 15, wherein the total silver iodide content of said bromoiodide grains is from 10.5 to 25 mol%.

17. The silver halide color photographic material as claimed in claim 16, wherein the total silver iodide content of said bromoiodide grains is from 12 to 20 mol%.

18. The silver halide color photographic material as claimed in claim 14, wherein said silver bromoiodide grains have an average grain size of 0.3 to 1.0 µm.

19. The silver halide color photographic material as claimed in claim 18, wherein said silver bromoiodide grains comprise tabular twin grains having an aspect ratio of 1.2 to 8.

20. The silver halide color photographic material as claimed in claim 19, wherein said pyrazoloazole coupler is a magenta dye-forming coupler and said light-sensitive silver halide emulsion comprising said silver bromoiodide grains is chemically sensitized to green light.

21. The silver halide color photographic material as climed in claim 1, wherein a compound represented by formula (A) is further present in at least one layer: Q-SM^I (A) wherein Q represents a heterocyclic group substituted with at least one moiety selected from the group consisting of -SO₃M², -COOM², -OH and -NR^lR² directly or via a connecting group, M¹ and M² each represents hydrogen, an alkaline metal, quaternary ammonium or quaternary phosphonium and R' and R² each represents hydrogen atom or a substituted or unsubstituted alkyl group.

22. The silver halide color photographic material as claimed in claim 1, wherein a 1-naphthol coupler represented by formula (D) is used in at least one layer:

wherein R₁ represents a halogen atom, aliphatic group, aromatic group, heterocyclic group, amidino group, guanidino group, -COR₄, -S02R4., -SOR4,

-NHCOR₄, -NHSO₂R₄, -NHSOR₄. or

(R4 and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an aliphatic oxy group or aromatic oxy group; R₂ represents a group capable of substituting the naphthol ring; ℓ is 0 or an integer of 1 to 3; R₃ represents hydrogen or an organic substituent; and T represents hydrogen or a group capable of being separated upon coupling reaction with an oxidation product of an aromatic primary amine developing agent.