Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/0051—Tabular grain emulsions
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
  • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

• 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.
• 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.
• pyrazoloazole couplers have been proposed in U.S. Patent 4,540,654, and European Patent 226849A.
• these couplers are disadvantageous in that their dispersions become unstable with time.
• 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").
• 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.
• 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.
• these emulsions are disadvantageous when used in combination with conventional magenta couplers, since they give a low sensitivity or poor color reproducibility.
• 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%.
• 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.
• 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.
• 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):
• 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).
• R 51 , R 52 and R 53 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,
• 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.
• polymers derived from vinyl monomers containing a portion represented by these general formulae are preferred.
• R 51 , R 52 , R 53 or V represents a vinyl group or connecting group.
• R 51 , R 52 and R 53 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-tetradecanamid
• 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., benzenes
• R 52 and R 53 may be connected to each other to form a 5- to 7-membered ring.
• R 51 , R 52 , R 53 or V is a divalent group to form a bis compound
• R 51 , R 52 and R 53 each preferably represents a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 O-CH 2 CH 2 -); a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, an -NHCO-R 54- CONH- group (in which R 54 represents a substituted or unsubstituted alkylene group or phenylene group) such as or an -S-R 55 -S- group (in which R 55 represents a substituted or unsubstituted alkylene group) such as -S-CH 2 CH 2 -S- and V represents a group obtained by removing a substituent, such as hydrogen, from previously mentioned monovalent group to form a divalent group.
• examples of the connecting group represented by R 51 , R S2 , R 53 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 -CH 2 CH 2 0CH 2 CH 2 -), 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-CH 2 CH 2 NHCO-, -CH 2 CH 2 O-CH 2 CH 2 -NH
• 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).
• 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.
• noncoloring ethylenic monomer which does not undergo a coupling reaction with an oxidation product of an aromatic primary amine developing agent examples include acrylic acid, a-chloroacrylic acid, ⁇ -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 bisacrylate
• 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.
• 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).
• R 51 preferably represents an alkyl group, aryl group, alkoxy group or aryloxy group
• R 52 preferably represents an alkyl group, aryl group, alkylthio group, arylthio group or heterocyclic thio group
• V preferably represents a halogen atom, aryloxy group, alkylthio group, arylthio group or heterocyclic group.
• R 52 is alkyl group.
• R 52 preferably is a group represented by formula (XV): -L 1 -R 56 (XV) wherein L 1 represents a straight chain or branched alkylene group (e.g., -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, and R 56 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, hexadecansul
• L 1 represents a straight chain
• 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.
• 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/m 2 , preferably 0.03 to 0.7 g/m 2 , more preferably 0.1 to 0.5 gim 2 .
• 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 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.
• 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.
• 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.
• 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.
• the X-ray diffractiometry also provides two diffraction peaks.
• the EPMA Electro Probe Micro Analyzer
• 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.
• 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.
• 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.
• 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.
• the logarithm of grain size and the iodine content show a positive relationship.
• 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.
• silver halide other than silver iodide may be silver bromochloride or silver bromide.
• 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.
• 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.
• the silver halide other than silver iodide may be silver chloride, silver bromochloride or silver bromide.
• the proportion of silver bromide is high.
• the outermost layer comprises silver bromoiodide or silver bromide containing 0.5 to 6 mol% of silver iodide.
• 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%.
• 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 ⁇ m, 0.1 to 1.5 ⁇ m, more preferably 0.2 to 1.3 u.m, particularly 0.3 to 1.0 u.m.
• 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).
• 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.
• grains having a (111) plane in a proportion of 50% or more are particularly preferred.
• 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.
• 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/m 2 , preferably 0.01 to 0.5 g/m 2 , more preferably 0.05 to 0.4 g/m 2 .
• a compound represented by formula (A) is preferably present in at least one layer:
• Q represents a heterocyclic group substituted with at least one moiety selected from the group consisting of -So 3 M 2 , -COOM 2 , -OH and -NR l R 2 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, M 1 and M 2 each quaternary ammonium or quaternary phosphonium; and R' and R 2 each represents hydrogen or a substituted or unsubstituted alkyl group.
• 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, M 1 and M 2
• 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 -SO 3 H, -COOH, -OH and -NH 2 in JP-B-58-9939 (the term "JP-B” as used herein means an "examined Japanese patent publication").
• heterocyclic group represented by Q in formula (A) examples 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):
• Y and Z which may be the same or different, each represents nitrogen or CR 4- (in which R 4 represents hydrogen, a substituted or unsubstituted alkyl group or substituted or unsubstituted aryl groups.
• R 3 represents an organic group, such as a C 1 - 20 alkyl group (e.g., methyl, ethyl, propyl, hexyl, dodecyl, octadecyl), and a C 6 - 20 aryl group (e.g., phenyl group, naphthyl group), substituted by at least one group selected from the group consisting of -SO 3 M 2 , -COOM 2 , -OH and -NR 1 R 2 , wherein M 2 , R' and R 2 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).
• a C 1 - 20 alkyl group e.g., methyl, ethyl, propyl, hexyl, dodecyl, octadecyl
• C 6 - 20 aryl group e.g.,
• 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 R 2 is an aryl group), aryl group (when R 2 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 sulfam
• R 3 is substituted by two or more substituents (-S)) 3 M, -COOM 2 , -OH and -NR l R 2 ), they may be the same or different.
• X represents sulfur, oxygen or R 5 represents hydrogen, a substituted or unsubstituted alkyl group or substituted or unsubstituted aryl group.
• L 2 represents -CONR 6 , -NR 6 CO-, -SO 2 NR 6 -, -NR 6 SO 2 -, -OCO-, -COO-, -S-, -NR 6- , -CO-, -SO-, -OCOO-, -NR 6 CONR 7 -, -NR 6 COO-, -OCONR 6 - or -NR 6 S0 2 NR 7- (in which R 6 and R 7 each represents hydrogen, a substituted or unsubstituted alkyl group or substituted or unsubstituted aryl group).
• R 3 , M 1 and M 2 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 R 4 , R S , R 6 and R 7 may be the same as those for R 3 .
• R 3 is particularly preferably -SO 3 M 2 or -COOM 2 .
• 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.
• 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/m 2 , preferably 5 ⁇ 10 -7 to 1 ⁇ 10 -4 mol/m 2 , more preferably 1 ⁇ 10 -6 to 3x10- 5 mol/m 2 .
• 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.
• 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.
• 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.
• 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.
• these layers are preferably arranged in such an order that the light sensitivity becomes lower towards the support.
• a light-insensitive layer can be provided between these silver halide emulsion layers.
• 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.
• 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.
• BH, BL, GL, GH, RH, and RL can be arranged in this order from the surface layer to the support.
• BH, BL, GH, GL, RL, and RH can be arranged in this order from the surface layer to the support.
• a blue-sensitive layer, GH, RH, GL, and RL can be arranged in this order from the surface layer to the support.
• a blue-sensitive layer, GL, RL, GH, and RH can be arranged in this order from the surface to the support.
• 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.
• the light sensitivity becomes lower towards the support.
• 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.
• 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.
• the order of arrangement of layers can be altered as described above.
• 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.
• 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 I lm or smaller in diameter or giant grains having a projected area diameter or up to about 10 I lm.
• 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).
• 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.
• 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.
• 1-naphthol couplers represented by formula [D] containing a substituted amino group in the 5-position: wherein R 1 represents a halogen atom, aliphatic group, aromatic group, heterocyclic group, amidino group, guanidino group, -COR 4 , -S0 2 R 4 , -SOR4, -NHCOR 4 , -NHSO 2 R 4 , -NHSOR 4 or (R 4 and R 5 each represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an aliphatic oxy group or an aromatic oxy group; R 2 represents a group capable of substituting the naphthol ring; l is 0 or an integer of 1 to 3; R 3 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.
• R 1 represents a halogen atom, aliphatic group, aromatic group, heterocycl
• 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.
• Z 2 may be a diffusible development inhibitor or a development inhibitor having a small diffusibility. If -TIME-Z 2 or -P-Z z is diffusible, A-TIME-Z 2 and A(or B)-P-Z 2 are diffusible DIR compounds.
• R 118 , R 119 and R 120 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.
• R 118 and R 119 , R 118 and G, R 119 and G , and R 120 and G may be connected to each other to form an aromatic group or nonaromatic group. At least one of R 118 , R 119 and R120 contains a C 10-20 nondiffusble ballasting group.
• Z is the same development inhibitor as described above.
• 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.
• 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)
• 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 total thickness of all hydrophilic colloidal layers on the emulsion side is preferably in the range of 28 ⁇ m 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.
• 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.
• 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.
• 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 m 2 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/m 2 or less by decreasing the bromide ion concentration in the replenisher.
• the area of the liquid surface in contact with air can be represented by the opening value defined as follows:
• 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 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.
• fixation i.e., blix
• bleach may be followed by blix.
• 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.
• the bleaching bath, blix bath or a prebath thereof can contain, if desired, a bleaching accelerator.
• a bleaching accelerator examples 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.
• Preferred among these compounds are compounds containing a mercapto group or disulfide group because of their great acceleratory effects.
• 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 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.
• 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 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).
• 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.
• 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.
• 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.
• a dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde-sulfurous acid adducts.
• 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.
• 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.
• a higher temperature range can be used to accelerate processing, reducing the processing time.
• a lower temperature range can be used to improve the picture quality or the stability of the processing solutions.
• 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.
• Emulsion 1 850 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 ⁇ m.
• 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.
• 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):
• 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):
• 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.
• the figures indicate the amount of each component (g) added per m 2 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.
• 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/m 2 , and 0.50 g/m 2 of surface active agents.
• 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 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.
• 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 ⁇ m 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:
• 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 m 2 of color light-sensitive material.
• the replenishment rate of the other processing solutions were each 800 ml per m 2 of color light-sensitive material.
• the amount of the processing solution came over to the washing step was 50 ml per m 2 of color light-sensitive material.
• 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.
• 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.
• a multilayer color light-sensitive material 301 was prepared by coating various layers having the following compositions on an undercoated cellulose triacetate support.
• the figures indicate the amount (g) of each component added per m 2 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
• 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
• 2-phenoxyethanol in an average amount of 1,000 ppm based on gelatin
• 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 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).
• the color development was effected at a temperature of 38 C as follows:
• composition of the various processing solutions are set forth below.
• 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.

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