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
  • 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
• • 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain

Definitions

• This invention relates to a silver halide photographic light-sensitive material and, particularly, to a method for preparing a silver halide photographic emulsion which is improved upon illuminance intensity reciprocity law failure and is high in sensitivity.
• This invention relates to a method of preparing a silver halide photographic emulsion, which contains silver halide grains having different silver halide compositions mingled therein; wherein the grains are characterized in that the silver halide grains are grown in the presence of silver halide fine-grains having a solubility product smaller than that of the silver halide grains contained in the emulsion for at least one period in the course of growing the silver halide grains of the emulsion and iridium ions are made present at the time when or after starting the growth of the silver halide grains.
• uch emulsion grains as described above is hereinafter sometimes referred to as 'the emulsion of the invention'.
• the above described object of the invention can be achieved in the above-described constitution.
• a light-sensitive material having low fog level can be obtained and any desensitization produced by a dye adsorption can be prevented.
• the emulsion of the invention contains silver halide grains each having different compositions mingled together therein.
• the expression, the cases, where silver halide grains each having different compositions are mingled together include a case where silver halide grains each having different compositions are mingled together, for example, where those grains each have one silver halide composition in the inner portion thereof and another different silver halide composition in the outer portion thereof. In the invention, it is permitted to mingle the silver halide compositions together in any embodiments.
• the silver halide grains thereof are grown up in at least one period in the course of growing the silver halide grains contained in the emulsion in the presence of the silver halide fine grains ⁇ hereinafter referred to as AgX grains (2), for convenience' sake> having a solubility product equivalent to or less than that of the silver halide grains contained in the emulsion ⁇ hereinafter referred to as AgX grains (1), for convenience' sake>.
• AgX grains (1) are allowed to have themselves two or more silver halide compositions in the grains.
• the two or more kinds of silver halides mingled therein are allowed to be distributed in the grains either uniformly or ununiformly.
• the ununiform distributions such as those of the core/shell and epitaxial types are preferable and, among the types, the core/shell type is particularly preferable.
• silver halide compositions of AgX grains (1) there is no special limitation to the silver halide compositions of AgX grains (1), and any AgX grains (1) may be used, provided the grains have phases different in silver halide compositions.
• silver iodobromide, silver chlorobromide and silver chloroiodobromide are preferable and, inter alia, silver iodobromide is particularly preferable.
• any ones such as mixedly crystallized silver iodobromide or silver chlorobromde can be used. It is, however, preferable to use silver iodobromide having a core/shell structure in which the cores each have a silver iodide content within the range of not less than 15 mol% to not more than 40 mol%.
• the grain-sizes of AgX grains (1) are preferable to be not more than 3.0 ⁇ m in terms of a sphere-equivalent diameter.
• AgX grains (1) may be either of the poly- and mono-­disperse type and the mono-disperse type is more preferable.
• 'mono-disperse' expressed herein means that not less than 95% of all the grains have the grain-sizes within the range of ⁇ 40% of an average grain-size.
• grain configura there is no special limitation to the grain configura strictlytions.
• they may be in any configurations such as a cube, an octahedron, a tetradecahedron, a tabular-shape, a potato-shape, and so forth.
• Emulsion of the invention containing the above-described AgX grains (1) can be used in at least one of the silver halide emulsion layers of a light-sensitive material and, in the case of two or more emulsion layers, it is preferable to use the emulsion of the invention in every emulsion layer.
• AgX grains (1) amount to at least not less than 30 mol% of all the grains and, particularly, to not less than 60 mol% thereof.
• AgX grains (1) are grown up under the presence of AgX grains (2), provided that AgX grains (2) having a solubility product smaller than those of AgX grains (1) are made present at least for a period in the course of growing AgX grains (1).
• AgX grains (2) may be so used as to grow up AgX grains (1), upon making AgX grains (2) present until a water-soluble halide solution and a water-soluble silver salt solution (hereinafter refered to as grain-growing elements) are completely supplied.
• the average grain-sizes of AgX grains (2) are smaller than those of AgX grains (1). However, there may also be some instances where the average grain-sizes of AgX grains (2) are larger than those of AgX grains (1).
• the average grain-sizes of AgX grains (2) are within the range of, preferably, 0.001 to 0.7 ⁇ m, more preferably, 0.01 to 0.3 ⁇ m and, further preferably, 00.1 to 0.1 ⁇ m.
• the first method of growing AgX grains (1) seed silver halide grains are grown up by making use of both of a solution of water-soluble silver salts and a water-soluble halide solution which are the grain growing elements so that AgX grains (1) can be prepared.
• silver halide nuclei are produced without making use of any seed grains but by making use of the above-described two the grain growing elements and the grains are then grown up so that AgX grains (1) can be prepared. From the viewpoint of the reproducibility of the grain-sizes of AgX grains (1), the first method may advantageously be used.
• AgX grains (2) are required to make them present in a suspension system (hereinafter referred to as a mother liquor) in which AgX grains (1) are prepared, for at least one period of time in the course of growing AgX grains (1), or until the time at latest when AgX grains (1) are grown up completely.
• a mother liquor a suspension system in which AgX grains (1) are prepared
• AgX grains (2) may be made present in a mother liquor before making the seed grains present therein; and, AgX grains (2) may also be added into a mother liquor containing seed grains, prior to the addition of a grain growing element also, AgX grains (2) may be added into a mother liquor in the course of adding the grain growing elements; further, AgX grains (2) may be added separately two or more times selected from the above-described points of time of addition.
• AgX grains (2) may be added before adding the grain growing elements or in the course of adding the elements, and further they may be added separately two or more times.
• AgX grains (2) and the grain growing elements may be added collectively, continuously or intermittently.
• AgX grains (2) and seed silver halide grains into a mother liquor with a multi-jet precipita­tion method such as a double-jet precipitation method, at an adding rate suitable for growing grains under the conditions where pH, pAg, temperatures and so forth are controlled.
• AgX grains (2) and seed silver halide grains may be prepared in a mother liquor or may be added into the mother liquor after they are prepared outside the mother liquor.
• an ammoniacal silver salt solution may preferably be used.
• silver halide compositions of AgX grains (2) it is preferable to use silver iodide or silver iodobromide having a iodide content higher than that of silver iodobromide being grown, in the case, for example, that AgX grains (1) is silver iodobromide; and it is preferable to use silver bromide or silver chlorobromide having a bromide content higher than that of silver chlorobromide grains being grown, in the case, for example, that AgX grains (1) is silver chlorobromide.
• AgX grains (1) is silver iodobromide
• AgX grains (1) is silver iodobromide or silver chloroiodobromide
• AgX grains (2) are preferable to be excellent in mono-­dispersibility.
• compositions of seed silver halide grains a variety of silver halides such as silver chloride, silver bromide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide may freely be used as desired.
• the temperatures of the mother liquor are within the range of, preferably, 10 to 70°C and, more preferably, 20 to 60°C; and the pAg values thereof are within the range of, preferably, 6 to 11 and, more preferably, 7.5 to 10.5; and the pH values thereof are within the range of, preferably, 5 to 11 and, more preferably, 7 to 10.
• the emulsions of the invention are those in which iridium ions are made present therein at least at the time when or after starting the growth of AgX grains (1).
• the iridium ions may be made present by adding a water-­soluble iridium salt.
• water-soluble iridium salts include, for example, Na3IrCl6, K3IrCl6, K2IrCl6, (NH4)2IrCl6 and Na2IrCl6.
• iridium compounds may be used upon dissolving them in water or in a suitable solvent.
• aqueous hydrogen halide solution such as that of HCl, HBr or HF, or an alkali halide solution such as that of KCl, NaCl, KBr or NaBr is added into the iridium compound solution.
• the iridium ions applicable to the invention may be added in an amount of, preferably, not more than 1x10 ⁇ 4 mols per mol of the whole silver halide ultimately produced, more preferably, not more than 1x10 ⁇ 5 mols and, further preferably, not more than 1x10 ⁇ 7 mols.
• Iridium ions may be made present at the time when or after starting the growth of grains. In other words, they are also allowed to be made present at the point of time when starting the growth of grains, in the course of growing them, or after grains are grown up. Iridium ions may be added in such a manner that the whole amount of the ions are added at any points of time when forming AgX grains (1), they are added separately several times, or they are added successively.
• Iridium ions are also allowed to add in the mixture with an aqueous halide solution that is a silver halide grain growing element.
• iridium ions it is preferable to add the iridium ions either at the time when or after 70% of the ultimate grain-size thereof are formed or prior to a chemical ripening treatment.
• the positions in AgX grains (1) where iridium is contained may depend upon the various points of time when adding iridium ions in the course of growing grains. It is allowed that iridium may be contained in any positions of grains, namely, in the center thereof concentrically, on the surfaces thereof, or in all the portions thereof. It is particularly preferable that an iridium-containing layer is made present in about several hundreds ⁇ from each of the grain surfaces. To be more concrete, it is most preferable to make iridium present in a layer about several hundreds ⁇ apart from the surface of each grain. To make them present in this way, it will do that iridium is added immediately before completing the crystal grain growth and the grains are then grown for about several hundreds ⁇ .
• the adsorptive substances include, for example, a sensitizing dye, an antifoggant and a stabilizer which are commonly used in the art, or heavy metal ions may advantageously be used.
• the typical examples of these adsorptive substances are given in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 62-7040/1987.
• each of the antifoggants and stabilizers selected from among the adsorptive substances when preparing a seed emulsion.
• heterocyclic mercapto compounds and/or azaindene compounds are particularly preferable to be used. More preferable examples of the heterocyclic mercapto compounds and azaindene compounds are detailed in, for example, Japanese Patent O.P.I. Publication No. 63-41848/1988 and they may be used in the invention.
• the amounts of the above-described heterocyclic mercapto compounds and azaindene compounds to be added shall not be limitative. However, they may be added in an amount within the range of, preferably, 1x10 ⁇ 5 to 3x10 ⁇ 2 mols per mol of silver halides used and, more preferably, 5x10 ⁇ 5 to 3x10 ⁇ 3 mols.
• the above given amounts may suitably be selected according to the variations of the preparation conditions of silver halide grains, an average grain-sizes of silver halide grains and the kinds of the above-described compounds.
• an emulsion When an emulsion is completed to form silver halide grains, it is then desalted in a well-known method.
• desalting methods applicable thereto a method described in Japanese Patent Application Nos. 62-81373/1987 and 63-­9047/1988 may be used, in which a gelatin coagulant for desalting the grains serving as seed grains may be used; a noodle-washing method may also be used, in which gelatin is gelated to desalt an emulsion; and a coagulation methos may further be used, in which inorganic salts comprising a polyvalent anion, including, for example, sodium sulfate, an anionic surfactant and anionic polymers (such as polystyrenesulfonic acid) are utilized.
• a polyvalent anion including, for example, sodium sulfate, an anionic surfactant and anionic polymers (such as polystyrenesulfonic acid) are utilized.
• the emulsions applicable to the invention may be chemically sensitized in any ordinary methods including, namely, a sulfur sensitizing method in which a sulfur-­containing compound capable of reacting with silver ions or active gelatin is used; a selenium sensitizing method in which a selenium compound is used; and a noble-metal sensitizing method in which a gold or other noble metal compound is used; independently or in combination.
• chalcogens sensitizers for example, may be used.
• a sulfur sensitizer and a selenium sensitizer are preferably used.
• the sulfur sensitizers include, for example, a thio­sulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate and rhodanine.
• a sulfur sensitizer described in U.S. Patent Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313 and 3,656,955, West German (OLS) Patent No. 1,422,869, and Japanese Patent O.P.I. Publication Nos. 56-24937/1981 and 55-­45016/1980 each may be used.
• the amounts of the sulfur sensitizer to be added are varied to a considerable extent according to the various conditions such as pH values, temperatures and the sizes of silver halide grains. As a rough standard, an amount thereof to be added is preferably within the extent of the order of 10 ⁇ 7 to 10 ⁇ 1 mols per mol of silver halides used.
• the selenium sensitizers applicable thereto include, for example, aliphatic isoselenocyanates such as allylisoseleno­cyanate, selenoureas, selenoketones, selenoamides, seleno­carboxylates and the esters thereof, selenophosphates, and selenides such as diethylselenide and diethyldiselenide.
• aliphatic isoselenocyanates such as allylisoseleno­cyanate, selenoureas, selenoketones, selenoamides, seleno­carboxylates and the esters thereof, selenophosphates, and selenides such as diethylselenide and diethyldiselenide.
• aliphatic isoselenocyanates such as allylisoseleno­cyanate, selenoureas, selenoketones
• a reduction sensitizer may be used in combination.
• the reduction sensitizers include, for example, stannous chloride, thiourea dioxide, hydrazine and polyazine.
• noble-metal compounds other than those of gold such as a palladium compound, may be used in combina­tion.
• AgX grains (1) contain a gold compound.
• the gold compounds preferably applicable to the invention include, for example, various kinds of gold compounds which may have the oxidation number of either +1 or +3 valency.
• the typical examples thereof include a chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric azide, ammonium aurothiocyanate, pyridyl tri­chlorogold, gold sulfide and gold selenide.
• the gold compounds may be so used as not only to sensi­tize grains, but not to substantially contribute to any sensitization.
• the amounts of the gold compounds to be added are varied according to the various requirements. As a rough standard, they are added in an amount within the range of 10 ⁇ 8 to 10 ⁇ 1 mols per mol of silver halides used and, preferably, 10-7 to 10 ⁇ 2 mols. These compounds may be added at any points of time when forming AgX grains, when physically or chemically ripening, and when completing the chemical ripening treatment.
• the emulsions may be spectrally sensitized to any desired wavelength regions by making use of sensitizing dyes.
• the sensitizing dyes are allowed to use either independently or in combination.
• a supersensitizer for enhancing the sensitizing functions of the sensitizer that is, a dye having no spectrally sensitizing function in itself or a compound incapable of substantially absorbing any visible rays of light.
• the silver halide photographic light-sensitive materials relating to the invention can be used for any light-sensitive materials including, for example, black-and-white silver halide photographic light-sensitive materials (such as an X-­ray or lithographic light-sensitive materials and black-and-­white photographing negative films), and color photographic light-sensitive materials (such as color negative films, color reversal films and color print papers).
• black-and-white silver halide photographic light-sensitive materials such as an X-­ray or lithographic light-sensitive materials and black-and-­white photographing negative films
• color photographic light-sensitive materials such as color negative films, color reversal films and color print papers.
• diffusion-transfer type light-sensitive materials such as color diffusion-transfer elements and silver salt diffusion-transfer elements
• thermal-development type light-sensitive materials such as those for black-and-white or color use.
• multicolor photographic light-sensitive materials they are each comprised of a support multilayered thereonto with the suitable numbers of blue-, green- and red-­sensitive AgX emulsion layers in suitable order which contain usually yellow, magenta and cyan couplers, respetively, as the photographic couplers and, if required, with the suitable numbers of non-light-sensitive layers so that a color repro­duction may be performed in a substractive color process.
• the numbers of the layers and the multilaying order thereof may suitably be changed to meet the priority characteristics and the purpose of application.
• the photographic light-sensitive materials of the inven­tion are permitted to use therein any desirable additives including, for example, an antifoggant, a hardener, a plasticizer, a latex, a surfactant, an antistain agent, a matting agent, a lubricant and an antistatic agent.
• the photographic light-sensitive materials of the invention may be subjected to a variety of black-and-white or color developing treatments so that images may be formed.
• the color developing agents applicable to the color developing treatmented are allowed to use the derivatives of the aminophenol and p-phenylenediamine types, which are widely used in a variety of color photographic processes.
• the color developers applicable to treat the photographic light-sensitive materials are allowed to contain the known compounds for the components of the developers, as well as an aromatic primary amine type color developing agent. Such treatments may also be performed in a system in which any benzyl alcohol having the problem of pollution load is not contained.
• pH values of such a developer as mentioned above are usually not less than 7 and, most generally, within the range of about 10 to 13.
• the color developing temperatures are usually not lower than 15°C and, more usually, within the range of 20 to 50°C. It is preferable to develop at a temperature of not lower than 30°C in a rapid developing treatment. Meanwhile, it takes 3 to 4 minutes to perform a conventional treatment. However, when using an emulsion prepared for a rapid treatment, the color developing time may be generally saved to be 20 to 60 seconds and, further, within 30 to 50 seconds.
• a bleaching treatment and a fixing treatments are carried out, generally, after they are color developed.
• the bleaching and fixing treatments are also allowed to perform at the same time.
• a washing treatment follows after the fixing treatment.
• a stabilizing treatment may be made in place of the washing treatment, or the both treatments may be made together.
• N-1 The resulting emulsion was named N-1.
• N-1 was proved to be a monodisperse type emulsion having an average grain-size of 0.093 ⁇ m.
• AgBrI seed emulsion N-1 having an average grain-size of 0.27 ⁇ m and a silver iodide content of 2 mol% was prepared.
• Emulsion EM-1 the grains thereof were of the core/shell type silver iodobromide having an average grain-size of 0.38 ⁇ m and an average AgI content of 8.46 mol%.
• Solutions C-1 and D-1 were added with a double jet precipitation method while controlling the pAg, pH of the mixture and the flow rates of Solutions C-1 and D-1, as shown in Table-1.
• silver bromide was produced.
• silver iodobromide was grown up, because AgI grains had already been made present at this stage.
• AgI grains were consumed by keeping the additions of the both solutions on, silver bromide was produced successively. Therefore, the resulting grains each had the silver halide compositions different from each other, that is, they were comprised of silver iodobromide to serve as the cores thereof and silver bromide as the shells.
• the pAg and pH were adjusted by the flow rates of Solutions E-1 and F-­1 by means of a variable flow-rate roller tube pump. Two minutes after completing the addition of Solution C-1, the pAg was adjusted to be 10.4 with Solution E-1 and then two minutes after, the pH was adjusted to be 6.0 with Solution F-1.
• Emulsions EM-2 through EM-4 were prepared in the proce­dures described below.
• EM-2 was prepared in the procedures that the grains were grown up in quite the same manner as in EM-1 and silver was added in an amount of 98.5% of the whole amount of silver to be added until the crystal growth is to be completed and, at the point where the silver was so added, K2IrCl6 was added in an amount of 6.5x10 ⁇ 6 mols per mol of AgX.
• EM-3 was prepared in the procedures that the grains were grown up in quite the same manner as in EM-2 and silver was added in an amount of 98.5% of the whole amount of silver to be added until the crystal growth is to be completed and, at the point where the silver was so added, K2IrCl6 was added in an amount of 6.5x10 ⁇ 8 mols per mol of AgX.
• EM-4 was prepared in the procedures that the grains were grown up in quite the same manner as in EM-3 and silver was added in an amount of 90.0% of the whole amount of silver to be added until the crystal growth is to be completed and, at the point where the silver was so added, K2IrCl6 was added in an amount of 6.5x10 ⁇ 8 mols per mol of AgX.
• a core/shell type silver iodobromide emulsion was so prepared as to have the AgI contents of 15 mol%, 5 mol% and 3 mol% in order from the inside of the grains, an average grain-­size of 0.38 ⁇ m and an average AgI content of 8.46 mol%, by making use of the 7 kinds of solutions given below.
• Each part inside the grain had a different silver iodide content and aqueous gelatin solutions were used in every part of the grains. The emulsion could therefore be used for the purpose of the comparison.
• the pAg and pH values were controlled by changing the flow-rates of Solutions F-5 and G-5 by means of a variable flow-rate roller tube pump.
• EM-5 The resulting emulsion is called EM-5.
• Emulsion EM-6 was prepared in the following procedures. EM-6 was prepared in the manner that grains were grown up under quite the same conditions as in EM-5 and then by adding K2IrCl6 in an amount of 6.5x10 ⁇ 8 mols per mol of AgX when an amount of 98.5 % of the whole silver was added.
• AgX grains (those of the core/shell type AgBrI) were so prepared as to have an average grain-size of 0.65 ⁇ m and an average AgI content of 7.16 mol%.
• the preparation was carried out in the same procedures as in Manufacturing Example 1, except that 201 ml of Solution C-3 was added into Solution A-3 by taking one minute at a temperature of 40°C.
• the pAg, pH and flow-rate thereof are shown in Table-3.
• the resulting emulsion is called EM-7.
• the grains contained in this emulsion were mixedly comprised of silver iodobromide in the cores thereof and silver bromide in the shells thereof.
• the resulting grains were grown up under quite the same conditions as in EM-7 and then by adding K2IrCl6 in an amount of 6.5x10 ⁇ 8 mols per mol of AgX when an amount of 98.5 % of the whole silver was added.
• the resulting emulsion is called EM-8.
• a silver iodobromide emulsion (for comparative use) was so prepared as to have the AgI contents of 15 mol%, 5 mol% and 3 mol% in order from the inside of the grains thereof, an average grain-­size of 0.65 ⁇ m and an average AgI content of 7.16 mol%.
• the resulting emulsion is hereinafter called EM-9.
• EM-10 Another emulsion was prepared by growing the grains thereof in quite the same manner as in EM-9 and by adding K2IrCl6 in an amount of 6.5x10 ⁇ 8 mols per mol of AgX at which 98.5% of the whole silver to be added.
• the resulting emulsion is hereinafter called EM-10.
• an octahedral monodisperse type emulsion, EM-11, for comparative use was so prepared as to have a silver iodide content of 2 mol% and an average grain-size of 0.65 ⁇ m.
• EM-12 Another emulsion was prepared by growing the grains thereof in quite the same manner as in EM-11 and by adding K2IrCl6 in an amount of 6.5x10 ⁇ 8 mols per mol of AgX at which 98.5% of the whole silver to be added.
• the resulting emulsion is hereinafter called EM-12.
• Each of EM-1 through EM-6 described in Manufacturing Examples 1 and 2 was subjected to an optimum gold-sulfur sensitization, so that six kinds of chemically sensitized emulsions were obtained.
• EM-1 and -5 separate from the above emulsions, two kinds of emulsion were obtained of EM-1 by adding K2IrCl6 in an amount of 6.5x10 ⁇ 6 mols per mol of AgX and K2IrCl6 in an amount of 6.5x10 ⁇ 8 mols per mol of AgX, respectively, and the other two kinds of emulsion were obtained of EM-5 in the same manner.
• the resulting emulsions were ripened for 30 minutes and then subjected to gold-sulfur sensitizations, respectively, so that four kinds in total of sensitized emulsions were obtained.
• Each of these emulsions was spectrally sensitized to blue rays of light by adding the following Sensitizing Dyes (I) and (II) in an amount of 350 mg per mol of AgI, respectively.
• the emulsions were each stabilized by adding TAI and 1-phenyl-5-mercaptotetrazole.
• the photographic additives such as a spreading agent and a layer hardener so as to prepare the coating solutions.
• the coating solutions were coated over to the sublayered film bases and were then dried up in an ordinary method, respectively, so that Samples No. 1 through No. 10 were prepared.
• the yellow coupler (Y-1) was dissolved in ethyl acetate and dioctyl phthalate in an amount by weight equi­valent to that of the coupler.
• the resulting solution was emulsified by dispersing it and, after adding it into each of the emulsions, the resulting coating solutions were coated and dried in the same manner as in Sample No. 1 through No. 10, so that Sample No. 11 through No. 20, respectively.
• Sample No. 1 through No. 20 was exposed to light through an wedge by using a blue filter under the 3 kinds of exposure conditions of 8 seconds, 1/12.5 seconds and 1x10 ⁇ 4 seconds.
• Sample No. 1 through No. 10 were treated in a 90-second process with the following processing solutions in the processing steps (I) given below by making use of a KX-500 automatic processor manufactured by Konica Corp, thereby determining the photographic sensitivities of the processed samples. Processing steps (I) (35°C) Developing 25 seconds Fixing 25 seconds Washing 25 seconds Drying 15 seconds
• Processing steps (II) 38°C) Color developing 3min.15sec. Bleaching 6min.30sec. Washing 3min.15sec. Fixing 6min.30sec. Washing 3min.15sec. Stabilizing 1min.30sec. Drying
• Table-4 shows the results of fog (Dmin) and the sensitivities obtained by exposing each sample to light.
• Table-4 No. Emulsion Ir content of surface (mol/molAgX) Dmin Sensitivity Distinction between Invention and Out of Invention 8-sec. exposure 1/12.5-sec. exposure 1x10 ⁇ 4-sec.
• the sensitivities are shown in such a manner that, taking the reciprocal number of the exposure required to give a density of fog +0.1 in each of the cases where the couplers were added and not added, the sensitivies of Samples No. 1 through No. 10 are each indicated by a value relative to the sensitivity of Sample No. 1, which is set at a value of 100, obtained by exposing it to light for 1/12.5 seconds and the sensitivies of Samples No. 11 through No. 20 are each indicated by a value relative to the sensitivity of Sample No. 11, which is set at a value of 100, obtained by exposing it to light for 1/12.5 seconds.
• the samples using the emulsions of the invention are higher in sensitivity than any Comparative Sample. It can be understood that the invention can be effectual in improving an illuminance reciprocity law failure.
• Samples No. 11 through No. 20 to each of which couplers were added can display the same effects as in the case where no coupler was added. It was proved that the samples of the invention are low in fogginess and high in sensitivity.
• Samples No. 21 through No. 26 were prepared in the manner that the emulsions EM-7 through EM-12 each described in Manufacturing Examples 3 and 4 were each subjected to the chemical and spectral sensitization in the same way as in Example 1 and magenta couplers were then added thereto as shown in Table-5, provided, as for the spectral sensitization, the following sensitizing dyes (III) and (IV) were used in the amounts of 300 mg and 30 mg per mol of AgI, respectively.
• each resulting sensitivity is represented by the reciprocal number of an exposure required to give a density of fog +0.1
• the resulting blue sensitivity is represented by a value relative to the blue sensitivity value set at a value of 100 of Sample No. 21 not yet added thereto any spectral sensitizing dye
• the resulting minus-blue sensitivity is represented by a value relative to the minus-blue sensitivity set at a value of 100 of Sample No. 21.
• Sample No. 22 of the invention which used the emulsion grain doped therein with iridium inside the crystals thereof is characterized in that a decrease in the intrinsic sensitivity by dyes is less extent than that in Comparative Samples and that not only the sensitivity is higher in the spectrally sensitized regions but the fog is lower.
• a multilayered color light-sensitive material No. 27 was so prepared as to be coated over a subbed cellulose acetate support and to comprise the layers having the following corresponding compositions.
• the amounts of silver halide and colloidal silver each coated are expressed in terms of the g/m2 unit of silver contained therein; the amounts of additives and gelatin each used are expressed in terms of the g/m2 unit thereof; and the amounts of sensitizing dyes and couplers each used are expressed in terms of the mol numbers thereof in one and the same layer per mol of silver halides used.
• Samples No. 28 through No. 30 were prepared in the following procedures:
• Sample No. 28 was a sample prepared in quite the same manner as in Sample No. 27, except that EM-1 and EM-7 of Sample No. 27 were replaced by EM-3 and EM-8, respectively.
• Sample No. 29 was a sample prepared in quite the same manner as in Sample No. 27, except that EM-1 and EM-7 of Sample No. 27 were replaced by EM-5 and EM-9, respectively.
• Sample No. 30 was a sample prepared in quite the same manner as in Sample No. 27, except that EM-1 and EM-7 of Sample No. 27 were replaced by EM-6 and EM-10, respectively.
• the sensitivities of B, G and R are indicated each by a value relative to the sensitivity value set at a value of 100 of Sample No. 27.

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• 1989
  • 1989-06-27 JP JP1165080A patent/JP2719540B2/ja not_active Expired - Fee Related
• 1990
  • 1990-06-27 EP EP19900307019 patent/EP0405938A3/en not_active Withdrawn

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