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
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
• • 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
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising

Definitions

• This invention relates to a light-sensitive silver halide photographic material (hereinafter called to "a light-sensitive material”), more particularly to a light-sensitive material which is improved in gradation fluctuation caused by variation of exposure illuminance and therefore can give high quality photographs excellent in color reproducibility easily and stably.
• a light-sensitive material a light-sensitive silver halide photographic material
• gradation fluctuation due to exposure illuminance (hereinafter called “illuminance dependency of gradation”) is remarkable, the above phenomenon becomes a fetal defect in quality of a light-sensitive material.
• Light-sensitive materials have different desired gradations depending on the purpose of use and are designed so as to control gradation, respectively. When these light-sensitive materials are exposed actually, exposure illuminance is changed as a matter of course due to exposure conditions such as brightness of a photographic object in a light-sensitive material for photography and difference in image density caused by excessive or insufficient exposure of an original film in a light-sensitive material for print.
• an actual gradation is outside an allowable range of designed target gradation due to the degree of exposure illuminance.
• An object of the present invention is to provide a light-sensitive material having extremely small exposure illuminance dependency of gradation by introducing a novel technique for improving reciprocity law failure property.
• Another object of the present invention is to provide a light-sensitive material having high sensitivity, excellent in gradation and color reproducibility and also excellent in reciprocity law property.
• a light-sensitive silver halide photographic material having at least one silver halide emulsion layer on a support, characterized in that at least one of the above silver halide emulsion layers contains a coupler represented by the following formula (M-I), a silver halide grain contained in said silver halide emulsion layer is a mixture of at least two kinds of silver halide emulsions different in sensitivity, and the illuminance dependency of sensitivity of the silver halide emulsion having lower sensitivity is smaller than the illuminance dependency of sensitivity of the silver halide emulsion having higher sensitivity
• Z represents a group of non-metallic atoms necessary for forming a nigrogen-containing heterocyclic ring and the ring formed by said Z may have a substituent
• X represents hydrogen atom or a eliminatable group by reaction with an oxidized product of a color developing agent
• R represents hydrogen atom or a substituent.
• magenta coupler represented by the formula (M-I) to be used in the present invention is described.
• the substituent represented by R is not particularly limited, but may specifically include each group of alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl.
• a halogen atom each group of cycloalkenyl, alkynyl, heterocyclic ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and heterocyclicthio; a spiro compound residue; and a bridged hydrocarbon compound residue.
• the alkyl group represented by R preferably have 1 to 32 carbon atoms, and may be straight or branched.
• the aryl group represented by R is preferably phenyl group.
• the acylamino group represented by R may include alkylcarbonylamino group and arylcarbonylamino group.
• the sulfonamide group represented by R may include alkylsulfonylamino group and arylsulfonylamino group.
• alkyl component or an aryl component in the alkylthio group or arylthio group represented by R there may be mentioned the alkyl group or aryl group represented by the above R.
• the alkenyl group represented by R preferably have 2 to 32 carbon atoms, and the cycloalkyl group preferably have 3 to 12, particularly preferably 5 to 7 carbon atoms.
• the alkenyl group may be straight or branched.
• the cycloalkenyl group represented by R preferably have 3 to 12, particularly preferably 5 to 7 carbon atoms.
• the sulfonyl group represented by R may include an alkylsulfonyl group and an arylsulfonyl group;
• the sulfinyl group may include an alkylsulfinyl group and an arylsulfinyl group;
• the phosphonyl group may include an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group and an arylphosphonyl group;
• the acyl group may include an alkylcarbonyl group and an arylcarbonyl group;
• the carbamoyl group may include an alkylcarbamoyl group and an arylcarbamoyl group;
• the sulfamoyl group may include an alkylsulfamoyl group and an arylsulfamoyl group;
• the acyloxy group may include an alkylcarbonyloxy group and an arylcarbon
• a halogen atom chlorine atom, bromine atom and fluorine atom
• nitrogen-containing heterocyclic ring formed by Z or Z′ there may be mentioned a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring, and as the substituent which may be possessed by said ring, there may be mentioned those as described for the above R.
• the coupler represented by the formula (M-I) is more specifically represented by, for example, the following formulae (M-II) to (M-VII).
• R1 to R8 and X each have the same meanings as those of the above R and X.
• couplers represented by the formula (M-I) a coupler represented by the following formula (M-VIII) is preferred. wherein R1, X and Z1 each have the same meanings as those of R, X and Z in the formula (M-I).
• magenta couplers represented by the formulae (M-II) to (M-VII) are particularly preferred.
• R9 and R10 may be bonded to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene and heterocyclic ring), and also R11 may be bonded to said ring to constitute a bridged hydrocarbon compound residue.
• a saturated or unsaturated ring e.g. cycloalkane, cycloalkene and heterocyclic ring
• R11 may be bonded to said ring to constitute a bridged hydrocarbon compound residue.
• R9 to R11 are alkyl groups and R11i) a case where one of R9 to R11, for example, R11 is hydrogen atom and the other two of R9 and R10 are bonded to form cycloalkyl together with a root carbon atom.
• the alkylene group represented by R1 preferably have 2 or more, more preferably 3 to 6 carbon atoms in a straight portion, and may be either straight or branched.
• the cycloalkyl group represented by R2 is preferbly 5- to 6-membered.
• the coupler represented by the formula (M-I) may be used generally in an amount of 1 x 10 ⁇ 3 mole to 1 mole, preferably in the range of 1 x 10 ⁇ 2 mole to 8 x 10 ⁇ 1 mole per mole of silver halide. Further, said coupler may be used in combination with other kinds of magenta couplers
• the silver halide grain to be contained in the silver halide emulsion layer containing the pyrazoloazole type magenta coupler represented by the formula (M-I) is a mixture of at least two kinds of silver halide emulsions having substantially the same color sensitivity (preferably green sensitivity) and also different in sensitivity.
• the illuminance dependency of sensitivity of the silver halide emulsion having lower sensitivity is smaller than the illuminance dependency of sensitivity of the silver halide emulsion having higher sensitivity should be satisfied.
• the illuminance dependency of sensitivity is represented by variation width of sensitivity when exposure time is changed from 0.02 second to 10 seconds.
• the above sensitivity is represented by a reciprocal of exposure dose necessary for obtaining a reflection density of 0.8, and evaluated with its relative value.
• the illuminance dependency is examined by an illuminance dependency of sensitivity ( ⁇ S) after the respective samples are subjected to wedge exposure for an exposure time of 0.02 second (high illuminance condition) and for an exposure time of 10 seconds (low illuminance condition) so that the same exposure dose is irradiated, respectively.
• the ⁇ S is a ratio of sensitivity obtained by exposure under high illuminance condition to sensitivity obtained by exposure under low illuminance condition, and represented by the following formula. As the ⁇ S value is smaller, a silver halide photographic material has smaller illuminance dependency of sensitivity.
• Illuminance dependency of sensitivity ( ⁇ S) Sensitivity obtained by exposure under high illuminance condition Sensitivity obtained by exposure under low illuminance condition
• a method for making the illuminance dependency of sensitivity of the silver halide emulsion having lower sensitivity smaller than the illuminance dependency of sensitivity of the silver halide emulsion having higher sensitivity is not particularly limited.
• the amount to be added may be changed.
• At least a part of means for controlling illuminance dependency of sensitivity is preferably carried out by controlling the amount of a water-soluble iridium compound added to at the time of forming or growing a silver halide grain.
• the amount of the water-soluble iridium compound to be added is represented by an average amount added per grain of silver halide, and it is preferred that the average amount of the water-soluble iridium compound added per grain of the silver halide emulsion having lower sensitivity is larger than that of the silver halide emulsion having higher sensitivity.
• the average amount added per grain of silver halide (Ir) av is represented by the following formula.
• the water-soluble iridium compound may be used or may not be used in the silver halide emulsion having higher sensitivity, but the average amount added per grain of silver halide is preferably smaller than that of the emulsion having lower sensitivity.
• the water-soluble iridium compound may be added in an amount within the range satisfying the above relationship.
• the amount is preferably in the range of 2 x 10 ⁇ 23 to 5 x 10 ⁇ 16 mole/grain in the emulsion having lower sensitivity and 2 x 10 ⁇ 24 to 2 x 10 ⁇ 18 mole/grain in the emulsion having higher sensitivity, more preferably in the range of 2 x 10 ⁇ 23 to 5 x 10 ⁇ 18 mole/grain in the emulsion having lower sensitivity and 2 x 10 ⁇ 24 to 2 x 10 ⁇ 20 mole/grain in the emulsion having higher sensitivity.
• the water-soluble iridium compound to be used in the present invention is not particularly limited, but as the compound which can be preferably used industrially from the standpoints of stability, safety and economy thereof, there may be mentioned an iridium (III) halide compound, an iridium (IV) halide compound and an iridium complex salt having halogen, amines or oxalate as a ligand.
• any desired one may be selected from these compounds, and these compounds may be used in combination, if necessary.
• iridium compounds are used by dissolving them in water or a solvent which is miscible with water.
• a method frequently used for stabilizing a solution of an iridium compound that is, a method in which a hydrogen halide (e.g. hydrochloric acid and bromic acid) or an alkali halide (e.g. potassium chloride, sodium chloride and potassium bromide) is added.
• a hydrogen halide e.g. hydrochloric acid and bromic acid
• an alkali halide e.g. potassium chloride, sodium chloride and potassium bromide
• the method of adding the water-soluble iridium compound is not particularly limited, but there may be mentioned, for example, a method in which the iridium compound is previously added in a mother liquor before formation of a nucleus, a method in which the compound is added instantaneously during growth of silver halide, a method in which the compound is added to a halide solution and a method in which the compound is added after completion of growth and immediately after physical ripening.
• the method in which the compound is added to a halide solution is preferred.
• the iridium compound may be added dividedly at different stages.
• the iridium compound to be added may be a solution of a mixture of two or more different iridium compounds. Also, solutions of two or more different iridium compounds may be added at different stages, respectively.
• the halide composition of the silver halide grain to be used in the silver halide emulsion layer according to the present invention is preferably silver chloride or silver chlorobromide substantially containing no silver iodide.
• substantially containing no silver iodide means an amount of silver iodide contained being 0.1 mole % or less
• the composition is preferably silver chloride or silver chlorobromide comprising 90 mole % or more of silver chloride composition, more preferably silver chloride or silver chlorobromide comprising 95 mole % or more of silver chloride composition.
• the silver halide grain in the silver halide emulsion layer according to the present invention may have any desired shape.
• One preferred example is a cube having a (100) face as a crystal surface.
• a grain having a twin or a grain having an irregular shape may be also used.
• the grain size of the silver halide grain to be used in the silver halide emulsion layer according to the present invention is not particularly limited, but the average grain size of the silver halide grain (hereinafter called "Grain A") contained in the silver halide emulsion having lower sensitivity (silver halide emulsion having the lowest sensitivity when three or more kinds of silver halide emulsions having different sensitivities are mixed) is suitably in the range of 0.2 to 1.6 ⁇ m.
• the average grain size of the silver halide grain (hereinafter called "Grain B") contained in the silver halide emulsion having higher sensitivity is suitably in the range of 0.3 to 1.7 ⁇ m.
• the above grain size is represented by a diameter of the grain when the silver halide grain is spherical or has a shape similar to a sphere, or by a diameter of a circle obtained by converting a projected area to a circle having the same area when the silver halide grain has a shape other than the shapes described above.
• the difference in grain size between Grain A and Grain B is not particularly limited, but said difference in grain size is preferably smaller, and no difference in grain size is most preferred.
• the grain size distribution of the silver halide grain contained in the silver halide emulsion before mixing to be used in the silver halide emulsion layer according to the present invention may be polydispersed, but preferably monodispersed .
• a monodispersed silver halide grain having the variation coefficient of the grain size distribution of the silver halide grain of 0.22 or less, more preferably 0.15 or less.
• Said variation coefficient is a coefficient showing a width of the grain size distribution, and represented by (standard deviation of grain size distribution/average grain size).
• the silver halide emulsion according to the present invention may be subjected to gold sulfur sensitization, and it may be also subjected to chemical sensitization by at least one selected from sulfur sensitization, selenium sensitization, noble metal sensitization and reducing sensitization.
• the silver halide emulsions to be mixed are preferably chemically sensitized, separately.
• a yellow dye-forming coupler in a blue-sensitive emulsion layer there may be generally used a magenta dye-forming coupler in a green-sensitive emulsion layer and a cyan dye-forming coupler in a red-sensitive emulsion layer.
• a light-sensitive silver halide color photographic material may be prepared by using a different combination from the above.
• these dye-forming couplers have, in their molecules, a so-called ballast group having 8 or more carbon atoms, which can made a coupler nondiffusible. Further, these dye-forming couplers may be either a four equivalent coupler in which four molecules of silver ions are required to be reduced for forming one molacule of a dye, or a two equivalent coupler in which only two molecules of silver ions are required to be reduced.
• the yellow dye-forming coupler there may be preferably used various acylacetanilide type couplers.
• benzoyl acetanilide type and pivaloyl acetanilide type compounds are advantegeous.
• cyan dye-forming coupler there may be preferably used a naphthol type coupler and a phenol type coupler.
• the compounds such as the dye-forming couplers of the light-sensitive material of the present invention are generally dissolved by using a high boiling point organic solvent having a boiling point of about 150 °C or higher or a water-insoluble polymer, and if necessary, in combination with a low boiling point and/or water-soluble organic solvent, emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution by using a surfactant, and then added to a desired hydrophilic colloid layer.
• a step of removing a dispersing medium or a low boiling point organic solvent similtaneously with dispersion may be added.
• the high boiling point organic solvent is preferably a compound having a dielectric constant of 6.5 or less, for example, esters such as phthalate and phosphate, organic acid amides, ketones and hydrocarbon compounds each having a dielectric constant of 6.5 or less.
• a high boiling point organic solvent having a dielectric constant of 1.9 to 6.5 and a vapor pressure at 100 °C of 0.5 mmHg or lower.
• phthalates and phosphates are more preferred.
• dialkyl phthalate having an alkyl group with 9 or more carbon atoms.
• the high boiling point organic solvent may be a mixture of two or more solvents.
• the dielectric constant means a dielectric constant at 30 °C.
• These high boiling point organic solvents are generally used in an amount of 0 to 400 % by weight based on a coupler, preferably 10 to 100 % by weight based on a coupler.
• the light-sensitive material of the present invention may be, for example, negative films for a color negative, positive films and a color printing paper. Particularly when a color printing paper provided for direct observation is used, the effect of the present invention can be exhibited efficiently.
• the light-sensitive material of the present invention including this color printing paper may be for monochrome or for multicolor.
• the silver halide emulsion to be used in the present invention may be optically sensitized to a desired wavelength by using a dye known as a sensitizing dye in the photographic field.
• gelatin is preferably used as a binder to be used in the light-sensitive silver halide photographic material of the present invention.
• the gelatin generally used in the photographic industry may include alkali-treated gelatin treated with lime and acid-treated gelatin treated with hydrochloric acid during preparation from collagen, and may be generally prepared by using a cattle bone, oxhide and pigskin as a starting material.
• the gelatin to be used in the light-sensitive material of the present invention may be either lime-treated gelatin or acid-treated gelatin prepared by using any of a cattle bone, oxhide and pigskin as a starting material, preferably lime-treated gelatin prepared by using a cattle bone as a starting material.
• the photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention can be hardened by crosslinking binder (or protective colloid) molecules using a hardener for increasing film strength singly or in combination.
• the hardener is preferably added to such an amount that the light-sensitive material can be hardened without necessity of adding a hardener to a processing solution, but the hardener may be also added to a processing solution.
• a UV absorber may be contained for preventing fog due to discharge caused by charging of the light-sensitive material with friction and preventing deterioration of images by UV ray.
• auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer may be provided.
• a dye which flows out from the light-sensitive color material during development processing or bleached may be contained.
• a matting agent may be added for the purposes of reducing gloss, enhancing writability and preventing mutual adhesion of the light-sensitive material.
• a lubricant may be added for reducing sliding friction.
• an antistatic agent may be added for the purpose of preventing static charge.
• the antistatic agent may be used in an antistatic layer at the side of the support on which emulsion layers are not laminated, or may be used in emulsion layers and/or a protective colloid layer other than the emulsion layers at the side of the support on which emulsion layers are laminated.
• various surfactants may be used for the purposes of improving coatability, preventing static charge, improving sliding property, improving emulsification and dispersion, preventing adhesion and improving photographic characteristics (such as acceleration of development, hardening and sensitization).
• the photographic emulsion layer and other layers of the light-sensitive material of the present invention may be coated on a baryta paper, a paper laminated with an ⁇ -olefin polymer and a paper support in which a paper support and an ⁇ -olefin polymer can be easily peeled off; a flexible reflective support such as a synthetic paper; a reflective support coated with a film comprising a semisynthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, and a white pigment; and a rigid body such as a glass, metal and ceramic.
• a thin reflective support having a thickness of 120 to 160 ⁇ m may be also used.
• the support to be used in the light-sensitive material of the present invention may be either a reflective support or a transparent support.
• a white pigment may be contained in the support, or a hydrophilic colloid layer containing a white pigment may be coated on the support.
• inorganic and/or organic white pigments may be used, and preferred is an inorganic white pigment.
• a pigment there may be mentioned sulfate of an alkaline earth metal such as barium sulfate, carbonate of an alkaline earth metal such as calcium carbonate, silicas such as fine powder of silicic acid and synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc and clay.
• the white pigment is preferably barium sulfate and titanium oxide.
• the light-sensitive material of the present invention may be coated directly or by using a substrate (at least one substrate for improving adhesion property of a support surface, antistatic property, dimensional stability, friction resistance, hardeness, antihalation property, friction characteristic and/or other characteristics) after the support surface is subjected to corona discharging, irradiation of UV ray and flame treatment, if necessary.
• a substrate at least one substrate for improving adhesion property of a support surface, antistatic property, dimensional stability, friction resistance, hardeness, antihalation property, friction characteristic and/or other characteristics
• a thickener may be used for increasing coatability.
• the coating method there may be particularly useful extrusion coating and curtain coating by which two or more layers can be coated at the same time.
• a color developing agent to be used in a color developing solution may include known agents widely used in various color photographic processes.
• These developers may include aminophenol type and p-phenylenediamine type derivatives.
• These compounds are generally used in the form of a salt, for example, in the form of a hydrochloride or a sulfate since they are more stable as compared with those under free state.
• These compounds are generally preferably used at a concentration of 0.1 to 30 g per liter of a color developing solution, more preferably at a concentration of about 1 g to about 15 g per liter of a color developing solution.
• aminophenol type developer there may be included, for example, o-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene and 2-oxy-3-amino-1,4-dimethylbenzene.
• the particularly useful primary aromatic amine type color developer is N,N-dialkyl-p-phenylenediamine type compounds, and the alkyl group and phenyl group may be substituted by a desired substituent.
• examples of the particularly useful compound may include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)toluene, N-ethyl-N- ⁇ -methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N- ⁇ -hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline and 4-amino-N-(2-methoxyethyl)-
• a known developing solution component compound may be added.
• an alkali agent such as sodium hydroxide, sodium carbonate and potassium carbonate, alkali metal sulfite, alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol, a water softener and a thickening agent may be contained as desired.
• the pH value of the color developing solution is generally 7 or more, most generally about 10 to 13.
• the color development temperature is generally 15 °C or higher, usually in the range of 20 °C to 50 °C.
• color development is preferably carried out at 30 °C or higher.
• the color development time is generally preferably in the range of 20 seconds to 60 seconds, more preferably in the range of 30 seconds to 50 seconds.
• the light-sensitive material of the present invention contains the color developing agent in a hydrophilic colloid layer as such or as a precursor thereof, and may be treated by an alkaline activating bath.
• the precursor of the color developing agent is a compound which can form a color developing agent under alkali conditions, and may include a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalimide derivative precursor, a phosphoric acid amide derivative precursor, a sugar amine reaction product precursor and an urethane type precursor.
• These precursors of the aromatic primary amine color developing agents are disclosed in U.S. Patents No. 3,342,599, No. 2,507,114, No. 2,695,234 and No.
• these color developing agents and precursors thereof may be added by dissolving them in a suitable solvent such as water, methanol, ethanol and acetone, or may be added by preparing an emulsified dispersion by using a high boiling point organic solvent such as dibutyl phthalate, dioctyl phthalate and tricresyl phosphate, or else may be added by impregnating a latex polymer therewith as described in Research Disclosure No. 14850.
• a suitable solvent such as water, methanol, ethanol and acetone
• a high boiling point organic solvent such as dibutyl phthalate, dioctyl phthalate and tricresyl phosphate
• the light-sensitive material of the present invention is subjected to bleaching processing and fixing processing after color development.
• Bleaching processing may be carried out simultaneously with fixing processing.
• polyvalent metal compounds such as iron (III), cobalt (III) and copper (II), particularly complex salts of these polyvalent metal cations with an organic acid, for example, an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, nitrilotriacetic acid and N-hydroxyethylethylenediaminediacetic acid, a metal complex salt of an acid such as malonic acid, tartaic acid, malic acid, diglycolic acid and dithioglycolic acid, ferricyanates and bichromic acid singly or in a suitable combination.
• an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, nitrilotriacetic acid and N-hydroxyethylethylenediaminediacetic acid
• a metal complex salt of an acid such as malonic acid, tartaic acid, malic acid, diglycolic acid and dithioglycolic acid
• ferricyanates and bichromic acid singly or
• a fixing agent there may be used a soluble complexing agent with which silver halide is made a complex salt to become soluble.
• a soluble complexing agent there may be mentioned, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea and thioether.
• washing processing is generally carried out.
• stabilizing processing may be carried out, or both processings may be also carried out in combination.
• a stabilizing solution to be used in the stabilizing processing a pH controlling agent, a chelating agent and an antifungal agent may be contained.
• Japanese Provisional Patent Publication No. 134636/1983 may be referred to about these specific conditions.
• a yellow coupler (Y-1), 10.0 g of a dye image stabilizer (ST-1), 6.67 g of (ST-2), 0.67 g of an additive (HQ-1) and 6.67 g of a high boiling point organic solvent (DNP) was added 60 ml of ethyl acetate and the mixture was dissolved, and the solution was dispersed by emulsification in 220 ml of a 10 % aqueous gelatin solution containing 7 ml of a 20 % surfactant (SU-1) by means of an ultrasonic homogenizer to prepare a yellow coupler dispersion.
• the dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.
• the second layer to the seventh layer coating solutions were prepared in the same manner as in the above first layer coating solution.
• (H-1) was added in the second and the fourth layer, and (H-2) was added in the seventh layer.
• surfactants (SU-2) and (SU-3) were added in order to control surface tension.
• the constitutions of the first layer to the seventh layer are shown in the following Table 1.
• the amount of the silver halide emulsion added are shown by calculating on silver.
• the emulsion EMP-2 was chemically ripened at 60 °C for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-R).
• the amount of an additive used at the time of preparing an emulsion is an amount per mole of silver halide unless otherwise indicated.
• a silver nitrate solution and a sodium chloride solution were added to an inactive aqueous gelatin solution over 120 minutes by a double jet method.
• the temperature and pAg were maintained at 40 °C and 7.3, respectively, and 9.3 x 10 ⁇ 9 mole/mole of AgX of K2IrCl6 was added during formation of silver halide grains.
• Em-1 comprising a cubic silver chloride grain having an average grain size of 0.50 ⁇ m and a variation coefficient of grain size distribution of 0.09.
• the amount of K2IrCl6 added to this emulsion was 4.5 x 10 ⁇ 23 mole/grain.
• Em-2 comprising a cubic silver chloride grain having an average grain size of 0.50 ⁇ m and a variation coefficient of grain size distribution of 0.08.
• the amount of K2IrCl6 added to this emulsion was 1.2 x 10 ⁇ 22 mole/grain.
• Em-1 The procedures were carried out in the same as in Em-1 except for adding 1.2 x 10 ⁇ 8 mole/mole of AgX of K2IrCl6 during formation of silver halide grains and changing the addition time to be shorter by 20 minutes than the addition time in the case of Em-1 to obtain Em-3 comprising a cubic silver chloride grain having an average grain size of 0.45 ⁇ m and a variation coefficient of grain size distribution of 0.08.
• the amount of K2IrCl6 added to this emulsion was 4.2 x 10 ⁇ 23 mole/grain.
• Samples No. 101 to No. 107 were prepared by combining magenta couplers and the above green-sensitive silver chloride emulsions as shown in Table 2 in the third layer (green-sensitive layer) in Table 1.
• Samples No. 101 to No. 103 in which one emulsion was used were prepared for evaluating samples before mixing two kinds of silver halide emulsions, and the illuminance dependency of sensitivity of the samples in which one emulsion was used and that of the sample of the present invention were measured at the same time.
• the sensitivity (S) was represented by a reciprocal of exposure dose necessary for obtaining a reflection density of 0.8, and evaluated with its relative value.
• the gradation ( ⁇ ) was represented by a slope of a reflection density from 0.8 to 1.8.
• the ⁇ S is a ratio of sensitivity obtained by exposure under high illuminance condition to sensitivity obtained by exposure under low illuminance condition, and as this value is smaller, the light-sensitive silver halide photographic material has smaller illuminance dependency of sensitivity.
• the ⁇ is a difference between ⁇ obtained by exposure under low illuminance condition and ⁇ obtained by exposure under high illuminance condition, and as an absolute value of this value is smaller, the light-sensitive silver halide photographic material is an excellent material having smaller illuminance dependency of gradation.
• Spectral reflection spectra of the magenta color-developed samples were measured by using a color analyzer Model 607 (trade name, manufactured by Hitachi Ltd.). At this time, measurement was carried out by standardizing the maximum density of an absorption spectrum at a visible portion of each sample to be 1.0.
• the absorbance at 440 nm at a visible portion (magenta) of each sample was read, and this value was regarded as a standard of unnecessary absorption at a yellow portion and defined as secondary absorption.
• the light-sensitive material having small secondary absorption can be said to be a light-sensitive silver halide photographic material excellent in color reproducibility.
• the respective layers having the constitutions shown in Table 5 were provided by coating to prepare multilayer light-sensitive silver halide color photographic material samples.
• the coating solutions were prepared as described below.
• a yellow coupler (Y-2), 10.0 g of a dye image stabilizer (ST-1), 0.46 g of an additive (HQ-1) and 10 g of a high boiling point organic solvent (DNP) was added 60 ml of ethyl acetate and the mixture was dissolved, and the solution was dispersed by emulsification in 220 ml of a 10 % aqueous gelatin solution containing 7 ml of a 20 % surfactant (SU-1) by means of an ultrasonic homogenizer to prepare a yellow coupler dispersion.
• the dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.
• the second layer to the seventh layer coating solutions were prepared in the same manner as in the above first layer coating solution.
• SU-4 and SU-5 were used, and as a hardener, H-1 and H-2 were used.
• a silver chlorobromide emulsion having an average grain size of 0.7 ⁇ m and a silver bromide content of 90 mole % was optimumly sensitized at 57 °C by using sodium thiosulfate and a sensitizing dye (BS-2), and Z-1 was added as a stabilizer.
• BS-2 sodium thiosulfate and a sensitizing dye
• a silver chlorobromide emulsion having an average grain size of 0.4 ⁇ m and a silver bromide content of 60 mole % was optimumly sensitized at 60 °C by using sodium thiosulfate, a sensitizing dye (RS-2) and a phenol resin, and Z-1 was added as a stabilizer.
• a silver nitrate solution and a solution mixture of potassium bromide and sodium chloride were added to an inactive aqueous gelatin solution over 140 minutes by a double jet method.
• the temperature and pAg were maintained at 50 °C and 7.5, respectively, and 6.1 x 10 ⁇ 9 mole/mole of AgX of K2IrCl6 was added during formation of grains.
• Em-4 comprises a tetradecahedral silver chlorobromide grain having an average grain size of 0.52 ⁇ m, a silver bromide content of 70 mole % and a variation coefficient of grain size distribution of 0.10.
• the amount of K2IrCl6 added to this emulsion was 3.3 x 10 ⁇ 23 mole/grain.
• aqueous silver nitrate solution and an aqueous halide solution were added to an inactive gelatin aqueous solution over 120 minutes by a double jet method.
• the temperature and pAg were maintained at 60 °C and 9.0, respectively, and 9.3 x 10 ⁇ 9 mole/mole of AgX of K2IrCl6 was added during formation of grains.
• Em-9 was an emulsion comprising a silver iodobromide grain having an average grain size of 0.5 ⁇ m, a silver iodide content of 2 mole % and a variation coefficient of grain size distribution of 0.13, and K2IrCl6 added to this emulsion was 4.5 x 10 ⁇ 23 mole/grain.
• aqueous silver nitrate solution and an aqueous halide solution were added to an inactive gelatin aqueous solution over 120 minutes by a double jet method.
• the temperature and pAg were maintained at 60 °C and 9.0, respectively, and 2.5 x 10 ⁇ 8 mole/mole of AgX of K2IrCl6 was added during formation of grains.
• Em-10 was an emulsion comprising a silver iodobromide grain having an average grain size of 0.50 ⁇ m, a silver iodide content of 2.5 mole % and a variation coefficient of grain size distribution of 0.14, and K2IrCl6 added to this emulsion was 1.2 x 10 ⁇ 22 mole/grain.
• Samples No. 201 to No. 218 were prepared by combining magenta couplers and the above green-sensitive silver chloride emulsions as shown in Table 7 in the third layer (green-sensitive layer) in Table 5.
• Samples No. 201 to No. 207 in which one emulsion was used were samples before mixing two kinds of silver halide emulsions, and the illuminance dependency of sensitivity of the samples in which one emulsion was used and that of the samples of the present invention were measured at the same time.
• the silver halide grain of the present invention is silver iodobromide
• the illuminance dependency of gradation is improved.
• the sensitivity is relatively lower as compared with that of silver chloride or silver chlorobromide, and even when the same coupler is used, the absorption becomes high at around 440 nm, and the color reproducibility is slightly inferior.
• the silver halide grain to be contained in the silver halide emulsion of the present invention contains substantially no silver iodide.
• aqueous silver nitrate solution and an aqueous halide solution were added to an inactive gelatin aqueous solution over 100 minutes by a double jet method.
• the temperature and pAg were maintained at 50 °C and 7.8, respectively, and 1.3 x 10 ⁇ 8 mole/mole of AgX of K2IrCl6 was added during formation of grains.
• Em-a was a monodispersed emulsion comprising a cubic silver chlorobromide grain having an average grain size of 0.40 ⁇ m, a silver bromide content of 0.10 mole % and a variation coefficient of grain size distribution of 0.12.
• the amount of K2IrCl6 added to this emulsion was 3.3 x 10 ⁇ 23 mole/grain.
• aqueous silver nitrate solution and an aqueous halide solution were added to an inactive gelatin aqueous solution over 100 minutes by a double jet method.
• the temperature and pAg were maintained at 50 °C and 7.8, respectively, and 3.3 x 10 ⁇ 8 mole/mole of AgX of K2IrCl6 was added during formation of grains.
• Em-b was a monodispersed emulsion comprising a cubic silver chlorobromide grain having an average grain size of 0.40 ⁇ m, a silver bromide content of 0.10 mole % and a variation coefficient of grain size distribution of 0.11.
• the amount of K2IrCl6 added to this emulsion was 8.3 x 10 ⁇ 23 mole/grain.
• aqueous silver nitrate solution and an aqueous halide solution were added to an inactive gelatin aqueous solution over 90 minutes by a double jet method.
• the temperature and pAg were maintained at 50 °C and 7.8, respectively, and 6.6 x 10 ⁇ 9 mole/mole of AgX of K2IrCl6 was added during formation of grains.
• Em-c was a monodispersed emulsion comprising a cubic silver chlorobromide grain having an average grain size of 0.50 ⁇ m, a silver bromide content of 0.10 mole % and a variation coefficient of grain size distribution of 0.11.
• the amount of K2IrCl6 added to this emulsion was 3.2 x 10 ⁇ 23 mole/grain.
• Example 11 there were prepared multilayer light-sensitive silver halide color photographic materials (Samples No. 301 to No. 311) in which the magenta coupler of the present invention and the respective monodispersed silver chlorobromide emulsions were combined as shown in Table 11.
• Samples No. 301 to No. 306 in which one emulsion was used were samples before mixing two kinds of silver halide emulsions, and the illuminance dependency of sensitivity of the samples in which one emulsion was used and that of the sample of the present invention were measured at the same time.
• Samples No. 301 to No. 311 were exposed and processed in the same manner as in Example 1, and evaluated.
• a method of making the illuminance dependency of sensitivity of the silver halide emulsion having lower sensitivity smaller than the illuminance dependency of sensitivity of the silver halide emulsion having higher sensitivity can be carried out not only by changing the amount of a water-soluble iridium compound to be added but also by changing the conditions of chemical sensitization, for example, extending the chemical ripening time or increasing the amount of sodium thiosulfate, but the method of changing the amount of a water-soluble iridium compound to be added is the most excellent.
• Example 3 The procedures were carried out in the same manner as in Example 3 except for changing the magenta coupler M-22 in Sample No. 311 to Exemplary compound 1, 4, 10, 20, 35, 59, 61 or 63, respectively, to prepare samples. When the samples were evaluated in the same manner, the effect of the present invention was obtained.
• the present invention can provide a novel technique for improving reciprocity law failure property of a light-sensitive material, whereby illuminance dependency of gradation can be improved without lowering sensitivity.
• a light-sensitive material having high sensitivity and excellent in gradation property and color reproducibility can be provided.

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• 1990
  • 1990-11-13 JP JP30641990A patent/JPH04177339A/ja active Pending
• 1991
  • 1991-11-07 EP EP91310310A patent/EP0487228A1/de not_active Withdrawn

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