EP0591883A1 - Matériau photographique couleur à l'halogénure d'argent sensible à la lumière - Google Patents

Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0591883A1
EP0591883A1 EP93115962A EP93115962A EP0591883A1 EP 0591883 A1 EP0591883 A1 EP 0591883A1 EP 93115962 A EP93115962 A EP 93115962A EP 93115962 A EP93115962 A EP 93115962A EP 0591883 A1 EP0591883 A1 EP 0591883A1
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Prior art keywords
emulsion
silver halide
silver
grains
grain
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EP93115962A
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German (de)
English (en)
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Tadanobu c/o Konica Corporation Sekiya
Sadayasu C/O Konica Corporation Ishikawa
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Konica Minolta Inc
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Konica Minolta Inc
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    • 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
    • G03C1/0051—Tabular grain emulsions

Definitions

  • the present invention relates to a silver halide color photographic light-sensitive material having low processing variability and offering excellent color reproduction, particularly a high interimage effect (hereinafter referred to as IIE).
  • IIE interimage effect
  • the grain size of silver halide grains in the layer of higher sensitivity is decreased, or a layer of relatively low silver iodide content or a layer having an appropriate silver chloride content is formed on the surface of the grains.
  • grain size reduction or change in a halide content results in a loss of sensitivity and deterioration of granularity.
  • silver iodide content reduction generally results in deteriorated color reproduction because IIE decreases.
  • the present inventors first marked emulsions of tabular grains of high aspect ratio, which offer relatively high developing speed and are therefore advantageous form the viewpoint of sensitivity.
  • the inventors prepared emulsions comprising grains whose silver halide composition is varied therein to increase IIE, i.e., emulsions based on a combination of tabular twin crystal grain technology and core-shell grain technology as described in Japanese Patent Examined Publication No. 38692/1988 and Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 14636/1986, and tabular twin crystal emulsions wherein a layer of relatively high silver iodide content is formed on the grain surface as described in Japanese Patent O.P.I. Publication No. 284848/1989, and compared their photographic performances.
  • IIE improved, granularity deteriorated significantly probably because of the wider grain size distribution than in normal crystal emulsions, with almost no improvement in processing variability.
  • the inventors prepared a monodispersed emulsion of low aspect ratio having two mutually parallel twin crystal planes, as described in Japanese Patent O.P.I. Publication No. 163433/1991, and evaluated its photographic performance in each of the emulsion layers of the same spectral sensitivity. Although processing variability was successfully improved without deterioration of sensitivity or granularity, no sufficient IIE was obtained.
  • the present inventors then studied to improve IIE alone in such a monodispersed emulsion comprising grains of low aspect ratio having two mutually parallel twin crystal planes, and found that the essential object can be accomplished when each of the emulsion grains has a development starting point near the intersection of a line formed by a twin crystal plane exposed to the grain surface and a edge of the grain.
  • the object of the present invention to provide a silver halide color photographic light-sensitive material having suppressed processing variability and high IIE while maintaining a good balance between sensitivity and granularity.
  • a silver halide color photographic light-sensitive material having on its support a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer, at least one of which layers comprises two or more silver halide emulsion layers of different sensitivities, wherein at least one color-sensitive layer contains two or more emulsion layers each containing a silver halide emulsion meeting all the following requirements (i), (ii) and (iii):
  • Figure 1 is a graph for calculating IIE, wherein the numerical symbols have the following definitions: A1, B1: Cyan dye image density A2, B2: Magenta dye image density P: Exposure amount Q: Exposure amount corresponding to P + 1.5 D: Density logE: Logarithmic exposure amount
  • the term "monodispersed" used herein is defined to be not higher than 30%, preferably not higher than 20% in the coefficient of variation.
  • the coefficient of variation is obtained by dividing the dispersion (standard deviation) of grain diameter by average grain diameter.
  • Grain diameter is defined as the diameter of a circle having an area equal to the projected area of a silver halide grain under microscopic observation.
  • the average grain diameter is obtained by dividing the total value for the diameters of all grains in the emulsion by the total number of the grains.
  • An emulsion containing silver halide grains having two mutually parallel twin crystal planes and an aspect ratio of lower than 3.0 means that such grains account for not lower than 60%, preferably not lower than 70% by number of all grains.
  • development starting point it is necessary to determine the site at which development begin on the grain (hereinafter referred to as "development starting point”.
  • a development starting point is recognized as such by observation after developing and stopping thereof. Specifically, it can be determined as follows:
  • a light-sensitive material having on its support a photographic emulsion is processed as follows: The light-sensitive material is subjected to exposure through an optical wedge and then processed in a conventional manner to obtain its characteristic curve. The light-sensitive material is subjected in an amount of 10 times a minimal exposure amount required to obtain the maximum density. After this exposure, both light-sensitive material exposed are developed with a developer having substantially the same composition. After initiation of the development, the light-sensitive material is immersed in a 3% acetic acid solution to stop the development.
  • Developing conditions e.g., temperature, time, processing solution concentrations
  • Developing conditions e.g., temperature, time, processing solution concentrations
  • the present invention is characterized in that some or all of the above-described silver halide grains having two mutually parallel twin crystal planes and an aspect ratio of lower than 3.0 have a development starting point near the intersection of a line formed by a twin crystal plane exposed to the grain surface and a edge of the grain (this area is referred to as cross area).
  • “some or all” means that when twin crystal grain development starting points are observed by the above-described methods of exposure and development, at least 70% of the development starting points are present in the cross area. Preferably, not less than 80% of development starting points are present in the cross area.
  • a line formed by a twin crystal plane exposed to the grain surface is easily identifiable from the grain morphology when the twin crystal plane forms a clear edge on the grain surface, e.g., in the case of grains having only one twin crystal plane.
  • the line is easily identifiable by observing the grain by high-resolution scanning electron microscopy at low acceleration voltage. For this reason, "a line formed by a twin crystal plane exposed to the grain surface” include both of the above cases.
  • Near the intersection of a line formed by a twin crystal plane exposed to the grain surface and a edge of the grain mean the intersection of a line formed by a twin crystal plane exposed to the grain surface and a edge of the grain, and the vicinity thereof.
  • the vicinity is defined to be within the sphere whose radius is 1/3, preferably 1/4 of the grain thickness and whose center is the above-described intersection (hereinafter called as cross area center). More preferably, the radius is 1/5 of the grain thickness, whereby the desired effect is enhanced.
  • Japanese Patent O.P.I. Publication Nos. 305343/1988 and 77047/1989 disclose an art wherein the development starting point of a tabular grain is located on or near a edge or corner thereof, the information obtained thereby is substantially two-dimensional with respect to the development starting point of the tabular grain.
  • publication does not state whether the development starting point is present on or near a line formed by a twin crystal plane exposed to the grain surface.
  • the present invention is characterized by more precise determination of development starting points, offering improved IIE, as well as improved sensitizing effect and developing stability.
  • At least part of the process for silver halide grain formation should be carried out in the presence of an oxidant (or oxidizing agent), and/or an emulsion comprising fine silver halide grains should be added during formation of the outermost layer of the silver halide grains.
  • the oxidant relating to the present invention is a compound capable of converting metallic silver to silver ion.
  • Halogen elements are preferable oxidants for the present invention, with preference given to iodine.
  • the amount of oxidant added is preferably 10 ⁇ 7 to 10 ⁇ 1 mol, more preferably 10 ⁇ 6 to 10 ⁇ 2 mol, and still more preferably 10 ⁇ 5 to 10 ⁇ 3 mol per mol of silver.
  • the oxidant may be present in the reaction vessel before grain growth, or may be added at any time point from the start of grain growth to desalinization.
  • the oxidant for the present invention When the oxidant for the present invention is added during the emulsion production process, conventionally used methods for addition of additives to photographic emulsions can be used.
  • the oxidant may be added in an appropriate concentration of aqueous solution, or in a solution in an appropriate water-miscible organic solvent which does not adversely affect photographic performance, such as an alcohol, a glycol, a ketone, an ester or an amide.
  • the oxidant may also be added in a solid form directly to the emulsion.
  • the oxidant may be added by rush addition, constant rate addition or functional addition.
  • the emulsion relating to the present invention which comprises fine silver halide micrograins, is an emulsion wherein the average diameter of the micrograins, taken as true spheres, is not greater than 0.1 ⁇ m, preferably not greater than 0.07 ⁇ , and still more preferably not greater than 0.05 ⁇ .
  • Its halogen composition may be any one of silver iodochloride, silver iodobromide, silver bromide and silver chloroiodobromide.
  • emulsion layer containing a silver halide emulsion meeting all the following requirements (i), (ii) and (iii) as described in the scope of claims of the present invention need not always be composed solely of a silver halide emulsion meeting all requirements (i), (ii) and (iii), implying that said emulsion may be used in combination with other emulsions which fail to meet one or more or all of requirements (i), (ii) and (iii).
  • the ratio of the emulsion relating to the present invention to non-inventive emulsions in the emulsion layer relating to the invention is preferably not lower than 3/7, more preferably not lower than 1/1, and most preferably not lower than 3/2, as of silver weight.
  • the silver halide grains relating to the present invention preferably comprise a silver iodobromide having an average silver iodide content of 1 to 20 mol%, particularly 3 to 15 mol%. Also, silver chloride may be contained, as long as the desired effect of the present invention is not interfered with. Also, the silver halide grains used for the present invention preferably consist of at least two layers of different silver iodide contents, since this is favorable from the viewpoint of sensitivity and granularity. In this case, the maximum silver iodide content layer of the two or more layers is preferably a layer other than the grain surface layer.
  • the silver iodide content gradient from layers of higher silver iodide contents to those of lower silver iodide contents may be in steps separated by sharp borders, or may be continuous without clear borders.
  • the silver iodide content of the outermost layer of the silver halide grains relating to the present invention is preferably not higher than 6 mol%, more preferably not higher than 4 mol%, and still more preferably not higher than 2 mol%.
  • the silver iodide content of each silver halide grain and the average silver iodide content of silver halide grains can be obtained by the EPMA (electron probe microanalyzer) method.
  • EPMA electron probe microanalyzer
  • a sample is prepared by thoroughly dispersing emulsion grains to avoid mutual contact, and this method allows elemental analysis for smaller portions than in X-ray analysis based on electron beam excitation.
  • This method makes it possible to determine the halogen composition of each grain by determining the intensities of silver- and iodine-characteristic X-rays radiated from each grain. If the silver iodide contents of at least 50 grains are determined by the EPMA method, the average silver iodide content can be obtained from the mean thereof.
  • the emulsion of the present invention is preferably uniform as to grain-to-grain iodine content distribution.
  • relative standard deviation is preferably not higher than 35%, more preferably not higher than 20%.
  • the emulsion relating to the present invention is prepared in the presence of a dispersant, or in a solution containing a dispersant.
  • An aqueous solution containing a dispersant is an aqueous solution in which a protective colloid of gelatin or another substance capable of forming a hydrophilic colloid (e.g., binder substance) has been formed, and it is preferably an aqueous solution containing a protective gelatin in a colloid form.
  • gelatin When gelatin is used as such a colloid in carrying out the present invention, the gelatin may have been treated with lime or acid. Preparation of gelatin is described in detail by Arthur Veis in "The Macromolecular Chemistry of Gelatin", Academic Press, 1964.
  • Non-gelatin hydrophilic colloidal substances which can be used as protective colloids include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, and various synthetic hydrophilic homopolymers or copolymers such as polyvinyl alcohol, partially acetalized polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole.
  • gelatin derivatives graft polymers of gelatin and other polymers
  • proteins such as albumin and casein
  • cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates
  • sugar derivatives such as sodium alginate and starch derivatives
  • gelatins it is preferable to use a gelatin having a jelly strength, as determined by the PAGI method, of not lower than 200.
  • the silver halide emulsion of the present invention may be grown from a seed crystal, or may be grown via nucleation. Also, the silver halide emulsion may comprise grains of any form, whether cubic, octahedral, tetradecahedral, tabular or the like.
  • the silver halide emulsion prepared in the present invention may be of any one of silver iodochloride, silver iodobromide, silver chlorobromide and silver chloroiodobromide, with preference given to silver iodobromide because of high sensitivity.
  • a monodispersed emulsion can be prepared by adding a solution of a water-soluble silver salt and a solution of a water-soluble halide to a gelatin solution containing seed grains by the double jet method while controlling the pAg and pH.
  • the addition rate can be determined with reference to Japanese Patent O.P.I. Publication Nos. 48521/1979 and 49938/1983.
  • pAg control during crystal growth is critical.
  • the pAg during crystal growth is preferably 6 to 12.
  • the pAg during silver halide formation may be constant, or may be changed in steps or continuously. When the pAg is changed, it is preferable to raise it as silver halide grains are formed.
  • stirring conditions are also critical. It is preferable to use the mechanical stirrer described in Japanese Patent O.P.I. Publication No. 160128/1987, which feeds an aqueous silver salt solution and an aqueous halide solution by the double jet method. at a rotation rate of 200 to 1000 rpm.
  • a known silver halide solvent such as ammonia, thioether or thiourea may be present or not.
  • the silver halide grains may be supplemented with metal ions using a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof to contain such metal elements in and/or on the grains during formation and/or growth thereof.
  • reduction sensitization specks can be provided in and/or on the grains by bringing the grains into an appropriate reducing atmosphere.
  • the silver halide grains may be grains wherein latent images are formed mainly on the surface thereof or grains wherein latent images are formed mainly therein, with preference given to silver halide grains having a size of 0.05 to 5.0 ⁇ m, preferably 0.1 to 3.0 ⁇ m.
  • the silver halide emulsion relating to the present invention may be treated to remove unwanted soluble salts after completion of silver halide grain growth, or may retain them. Removal of such salts can be achieved in accordance with the method described in term II, Research Disclosure (hereinafter abbreviated RD) No. 17643. More specifically, soluble salt removal from the emulsion after precipitation or physical ripening may be achieved by the noodle washing method, in which gelatin is used in a gel form, or by the flocculation method utilizing an inorganic salt, an anionic surfactant, an anionic polymer such as polystyrenesulfonic acid, or a gelatin derivative such as acylated gelatin or carbamoylated gelatin.
  • RD Research Disclosure
  • the silver halide emulsion relating to the present invention may be chemically sensitized by a conventional method. Specifically, sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, which uses gold or another noble metal, and other sensitizing methods can be used singly or in combination.
  • the silver halide emulsion relating to the present invention may also be optically sensitized in the desired wavelength band using a sensitizing dye.
  • Sensitizing dyes may be used singly or in combination.
  • non-spectral sensitizing dyes, and/or supersensitizers which are compounds having substantially no absorption of visible light and enhancing the sensitizing action of sensitizers may be incorporated in the emulsion.
  • the silver halide emulsion relating to the present invention may be supplemented with an antifogging agent, a stabilizer and other additives. It is advantageous to use gelatin as a binder for the emulsion.
  • Emulsion layers and other hydrophilic colloidal layers may be hardened, and may contain a plasticizer and a dispersion (latex) of a water-insoluble or soluble synthetic polymer.
  • At least one of color-sensitive layers comprises two or more silver halide emulsion layers different in sensitivity from each other.
  • the silver halide emulsion of the present invention is applicable to at least two of these layers.
  • the silver halide emulsion of the invention is applicable to any of color-sensitive layers, including blue-sensitive, green-sensitive and red-sensitive layers, or others such as a layer having negative spectral sensitivity.
  • the inventive silver halide emulsion is employed in a green-sensitive or red-sensitive layer.
  • the emulsion layer of a color light-sensitive material incorporates a coupler. Also incorporatable are a competitive coupler having a color correcting effect, and a compound which releases a photographically useful fragment such as a developing accelerator, a developing agent, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifogging agent, a chemical sensitizer, a spectral sensitizer or a desensitizer, upon coupling with the oxidation product of a developing agent.
  • the light-sensitive material of the present invention may be provided with auxiliary layers such as a filter layer, an anti-halation layer and an anti-irradiation layer. These layers and/or emulsion layers may contain a dye which oozes out or becomes bleached from the light-sensitive material during processing.
  • the light-sensitive material of the present invention may incorporate a matting agent, a lubricant, an image stabilizer, a formalin scavenger, an UV absorbent, a brightening agent, a surfactant, a developing accelerator and a developing inhibitor.
  • the light-sensitive material of the present invention can be color-developed by a common color developing process after exposure.
  • the light-sensitive material is first developed with a black-and-white negative developer, followed by white light exposure or immersion in a bath containing a fogging agent, after which it is color-developed with an alkaline developer containing a color developing agent.
  • Any processing method can be used without limitation. Typically, color development is followed by bleach-fixation and, where necessary, washing and stabilization, or color development is followed by bleaching and fixation and, where necessary, washing and stabilization.
  • Seed emulsion T-1 comprising grains having two mutually parallel twin crystal planes was prepared as follows:
  • Silver nitrate 1200.0 g Water was added to make a total quantity of 1600.0 ml.
  • the mixture was adjusted to pH 6.0 and then desalinized by a conventional method. Electron microscopy of these seed emulsion grains identified them as hexahedral tabular grains having two mutually parallel twin crystal planes.
  • These seed emulsion grains had an average grain size of 0.236 ⁇ m and a twin crystal plane ratio of 75% by number relative to the total number of grains.
  • Twin crystal seed emulsion T-2 was prepared in the same manner as for twin crystal emulsion T-1 except that the pBr was 1.80. These seed emulsion grains had an average grain size of 0.232 ⁇ m and a twin crystal ratio of 62% by number relative to the total number of grains.
  • monodispersed emulsion EM-1 relating to the present invention which comprised octahedral twin crystal grains having two mutually parallel twin crystal planes, was prepared.
  • Fine grain emulsion comprising 3% by weight gelatin and grains of silver iodide (average grain size 0.05 ⁇ m) 1.40 mol
  • This fine grain emulsion was prepared as follows: To 5000 ml of a 6.0% by weight gelatin solution containing 0.06 mol of potassium iodide, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of potassium iodide were added over a period of 10 minutes. During fine grain formation, a pH of 2.0 was maintained with nitric acid, and temperature maintained at 40°C. After grain formation, an aqueous solution of sodium carbonate was added to obtain a pH of 6.0.
  • Fine grain emulsion comprising silver iodobromide grains having a silver iodide content of 2 mol% and an average grain size of 0.04 ⁇ m, prepared in the same manner as for the fine grain silver iodide emulsion prepared with solution D 3.68 mol
  • solutions B, C and D were added by the triple jet precipitation method over a period of 128 minutes, followed by addition of solution E at constant rate over a period of 7 minutes, to grow the seed crystal until its size became 0.878 ⁇ m.
  • Solutions B and C were added at an appropriate rate changed as a function of time according to the critical rate of grain growth to prevent both the occurrence of small grains other than growing seed crystals and polydispersion due to Ostwald ripening.
  • Supply of solution D i.e., the silver iodide fine-grain emulsion
  • Monodispersed emulsion EM-2 relating to the present invention which comprised octahedral twin crystal grains having two mutually parallel twin crystal planes, was prepared in the same manner as for emulsion EM-1.
  • solutions B, C and D were added by the triple jet precipitation method at an appropriate rate changed as a function of time in the same manner as for emulsion EM-1 over a period of 70 minutes, to grow the seed crystal to 0.513 ⁇ m.
  • Emulsion EM-3 having an average grain size of 0.88 ⁇ m, a distribution width of 13% and an average aspect ratio of 1.7 was prepared in the same manner as for emulsion EM-1 except that the 33.7 ml methanol solution containing 0.001 mol of iodine was removed from solution A, and that grains were grown by simultaneously adding solutions B and C by the double jet method rather than by addition of solution E alone.
  • Emulsion EM-4 having an average grain size of 0.515 ⁇ m, a distribution width of 29% and an average aspect ratio of 1.8 was prepared in the same manner as for emulsion EM-2 except that the 33.7 ml methanol solution containing 0.001 mol of iodine was removed from solution H.
  • Emulsion EM-5 having an average grain size of 0.873 ⁇ m, a distribution width of 10% and an average aspect ratio of 1.5 was prepared in the same manner as for emulsion EM-1 except that seed emulsion T-1 for solution A was replaced with seed emulsion T-2.
  • Emulsion EM-6 having an average grain size of 1.11 ⁇ m, a distribution width of 24% and an average aspect ratio of 3.2 (grains exceeding 3.0 in aspect ratio accounted for 95% of the total number of grains) was prepared in the same manner as for emulsion EM-1 except that pAg was changed as a function of time from 9.0 to 9.7 during crystal growth, and that the rates of additions of solutions B, C and D were changed according to the critical growth speeds at respective time points.
  • Emulsion EM-7 having an average grain size of 0.875 ⁇ m, a distribution width of 8% and an average aspect ratio of 1.1 was prepared in the same manner as for emulsion EM-1 except that seed emulsion T-1 for solution A was replaced with a monodispersed emulsion comprising tetradecahedral normal crystal grains having an average grain size of 0.230 ⁇ m and containing 6 mol% silver iodide.
  • the thus-obtained emulsions EM-1 through EM-7 were each chemically ripened as described below to yield emulsions EM-A through EM-G.
  • emulsion EM-1 A portion of emulsion EM-1 was dissolved at 50°C. After adsorption of the below-described sensitizing dyes S-6, S-7 and S-8, each in an amount of 50 mg, for 15 minutes, the solution was ripened with 1.0 ⁇ 10 ⁇ 5 mol sodium thiosulfate pentahydrate, 3.6 ⁇ 10 ⁇ 6 chloroauric acid and 5.0 ⁇ 10 ⁇ 4 mol ammonium thiocyanate. The chloroauric acid and ammonium thiocyanate, together in a mixed solution, were added simultaneously with addition of the sodium thiosulfate pentahydrate.
  • Emulsions EM-2 through EM-7 were chemically ripened in the same manner as for emulsion EM-1 to yield emulsions EM-B through EM-G.
  • each of the thus-obtained emulsions EM-A through EM-G was coated and dried on a triacetyl cellulose film support, subbed with the following coating solution composition, to yield sample Nos. 101 through 107.
  • the amount of addition in silver halide photographic light-sensitive material is expressed in gram per m2, unless otherwise stated.
  • the figures for silver halide have been converted to the amounts of silver.
  • a coating aid Su-1 a dispersing agent Su-2 and a hardener H-1 were added to appropriate layers.
  • each of the thus-obtained coated sample Nos. 101 through 107 was subjected to green light exposure through an optical wedge, after which it was processed as described below. From the characteristic curve, determinations were made of the relative sensitivity (expressed as the reciprocal of the exposure amount yielding a density equivalent to fogging + 0.1), and the minimum exposure amount required to obtain the maximum density.
  • compositions of the processing solutions used in the respective processes are as follows:
  • each of coated sample Nos. 101 through 107 was subjected to exposure in an exposure amount 10 times the previously determined minimum exposure amount required to obtain the maximum density, after which it was processed as follows:
  • the color developer had the same composition as of the processing solution used to draw the characteristic curve, but it was used after 10-fold dilution with water.
  • a 3% aqueous acetic acid solution was used as a stopping bath.
  • sample Nos. 101, 102, 105 and 106 are light-sensitive materials wherein the development starting point is present near the intersection of a line formed by a twin crystal plane exposed to the grain surface and a edge of the grain.
  • the amount of addition in silver halide photographic light-sensitive material is expressed in gram per m2, unless otherwise stated.
  • the figures for silver halide and colloidal silver have been converted to the amounts of silver.
  • the figures for sensitising dyes are expresses as molar number per mol of silver halide.
  • composition of multiple-layered color photographic light-sensitive material sample No. 201 (incorporating inventive emulsions EM-1 and EM-2) is as follows:
  • Sample Nos. 202 through 206 were prepared in the same manner as for sample No. 201 except that emulsion EM-2 in layer 7 and emulsion EM-1 in layer 8 were replaced with respective emulsions listed in Table 3. Table 3 Sample No. Emulsion in layer 7 Emulsion in layer 8 201 EM-2 EM-1 202 EM-2 EM-5 203 EM-4 EM-3 204 EM-2 EM-3 205 EM-2 EM-6 206 EM-2 EM-7
  • Layer 1 Anti-halation layer HC Black colloidal silver 0.16 g UV absorbent UV-1 0.30 g Gelatin 1.70 g
  • Layer 2 First interlayer IL-1 Gelatin 0.80 g
  • Layer 3 Low speed red-sensitive emulsion layer R-L Silver iodobromide emulsion (average grain size 0.36 ⁇ m) 0.40 g Sensitizing dye S-1 1.2 ⁇ 10 ⁇ 4 (mol/mol silver) Sensitizing dye S-2 0.2 ⁇ 10 ⁇ 4 (mol/mol silver) Sensitizing dye S-3 2.0 ⁇ 10 ⁇ 4 (mol/mol silver) Sensitizing dye S-4 1.2 ⁇ 10 ⁇ 4 (mol/mol silver) Cyan coupler C-1 0.33 g Colored cyan coupler CC-1 0.05 g High boiling solvent Oil-1 0.30 g Gelatin 0.55 g
  • Layer 4 Moderate speed red-sensitive emulsion layer
  • R-M Silver iodobromide emulsion average grain size 0.51 ⁇ m) 0.48
  • compositions In addition to these compositions, a coating aid Su-1, a dispersing agent Su-2, hardeners H-1 and H-2 and dyes AI-1 and AI-2 were added to appropriate layers.
  • Each of the thus-prepared samples was evaluated as to relative sensitivity, granularity, processing variability and IIE.
  • each sample was processed as shown in Table 4 below.
  • the developer had a pH value of 10.1 (processing 1).
  • Relative sensitivity or the reciprocal of the exposure amount yielding a density equivalent to D min + 0.15, is expressed in percent ratio relative to the green light sensitivity of sample No. 206. The results are given in Table 5.
  • each of silver halide color photographic light-sensitive material sample Nos. 201 through 206 was processed as directed in Table 4 below. Also, to assess stability to pH fluctuation in the developer, color developers of different pH values were used. Table 4 Procedure Processing time Processing temperature (°C) Amount of replenisher (ml) Color development 3 minutes 15 seconds 38 ⁇ 0.3 780 Bleaching 6 minutes 30 seconds 38 ⁇ 2.0 150 Washing 3 minutes 15 seconds 20 ⁇ 10 200 Fixation 6 minutes 30 seconds 38 ⁇ 2.0 830 Washing 3 minutes 15 seconds 20 ⁇ 10 200 Stabilization 1 minute 30 seconds 38 ⁇ 5.0 830 Drying 2 minutes 55 ⁇ 5.0 -
  • the color developer, bleacher, fixer, stabilizer and replenishers therefor were prepared as follows:
  • Magenta color stability to pH change was determined from the sensitometric curve variation width and the width of difference ⁇ of ⁇ B in processing 1 (pH 10.1) from ⁇ A in processing 2 (pH 9.9) (see the following equation).
  • ⁇ [( ⁇ B - ⁇ A )/ ⁇ A ] ⁇ 100 (%)
  • the results are given in Table 5. Stability increases as the value for ⁇ decreases.
  • the curve A1-B1 is a characteristic curve for red-sensitive layer cyan dye images, the curve A2-B2 representing the magenta dye image density of the green-sensitive layer after uniform exposure to green light.
  • P indicates a cyan dye image fog density (or minimum density) portion;
  • Q represents an exposure amount (P + 1.5) for a cyan dye density equivalent to fog density + ⁇ b.
  • magenta dye image density A2 at exposure amount P and magenta dye image density B2 at exposure amount Q is expressed in the notation of ⁇ a.
  • the IIE of the red-sensitive layer on the green-sensitive layer was determined in percent ratio relative to the IIE value of sample No. 206. The results are given in Table 5. IIE improves as this value increases.
  • Photographic material samples 301 through 308 were prepared in the same manner as in sample 203 of Example 2, except that emulsions of layers 3 to 5 were replaced with respective silver halide emulsions listed in Table 6. Thus prepared samples were subjected to exposure and processing, and evaluated in the same manner as in Example 2. Results thereof are given in Table 7. Table 6 Sample No.
  • inventive samples 301 through 305 achived improvements in processing stability and IIE without deteriorating sensitivity and granularity.
  • Photographic material sample 401 was prepared in the same manner as in sample 201 of Example 2, except that the emulsions in layer 3 and 4 were replaces with emulsion EM-2, and the emulsion in layer 5 was replaced with emulsion EM-1.
  • prepared sample was subjected to exposure and processing, and evaluated in the same manner as in Example 2. Similarly as shown in sample 201 and 301, improved results were achieved.

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  • Engineering & Computer Science (AREA)
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  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP93115962A 1992-10-06 1993-10-02 Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Withdrawn EP0591883A1 (fr)

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JP290886/92 1992-10-06
JP4290886A JPH06118584A (ja) 1992-10-06 1992-10-06 ハロゲン化銀カラー写真感光材料

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JP3359464B2 (ja) * 1995-02-07 2002-12-24 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料及び画像形成方法
WO2020142110A1 (fr) * 2018-12-31 2020-07-09 Intel Corporation Systèmes de sécurisation utilisant une intelligence artificielle

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2206974A (en) * 1987-06-05 1989-01-18 Fuji Photo Film Co Ltd Silver halide photographic emulsions
JPS6477047A (en) * 1987-06-18 1989-03-23 Fuji Photo Film Co Ltd Silver halide photographic emulsion
EP0421740A1 (fr) * 1989-10-03 1991-04-10 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière à haute sensibilité et voile et granularité améliorés, et méthode pour sa fabrication
EP0480294A1 (fr) * 1990-10-03 1992-04-15 Konica Corporation Emulsion photographique à l'halogénure d'argent et matériau photographique couleur à l'halogénure d'argent sensible à la lumière incorporant celle-ci

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3787088T2 (de) * 1986-12-26 1993-12-09 Fuji Photo Film Co Ltd Photographische Emulsionen mit Silberhalogenid vom Eckenentwicklungstyp.
JPH0652397B2 (ja) * 1987-09-11 1994-07-06 富士写真フイルム株式会社 感光材料包装ユニット

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2206974A (en) * 1987-06-05 1989-01-18 Fuji Photo Film Co Ltd Silver halide photographic emulsions
JPS6477047A (en) * 1987-06-18 1989-03-23 Fuji Photo Film Co Ltd Silver halide photographic emulsion
EP0421740A1 (fr) * 1989-10-03 1991-04-10 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière à haute sensibilité et voile et granularité améliorés, et méthode pour sa fabrication
EP0480294A1 (fr) * 1990-10-03 1992-04-15 Konica Corporation Emulsion photographique à l'halogénure d'argent et matériau photographique couleur à l'halogénure d'argent sensible à la lumière incorporant celle-ci

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JPH06118584A (ja) 1994-04-28

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