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
  • G03C1/0051—Tabular grain emulsions

Definitions

• the present invention relates to a light-sensitive silver halide color photographic material, a silver halide emulsion and a process for preparing these. More particularly, it relates to a light-sensitive silver halide color photographic material, a silver halide emulsion and a process for preparing these, that can achieve a high sensitivity or speed, may cause less fog, and achieve a superior storage stability and processing stability.
• Light-sensitive silver halide photographic materials are required to have various performances such as speed, image quality and gradation. Fogging, storage stability, processing stability and so forth are also very important factors. Demands for improvement of these have become severer year by year.
• spectral sensitization that uses sensitizing dyes
• noble metal sensitization that uses salts of noble metals such as gold, platinum and iridium
• sulfur sensitization that uses active gelatin and besides sodium thiosulfate, thioacetamide, allylisothiourea, etc.
• selenium sensitization that uses colloidal selenium or selenourea
• reduction sensitization that uses monovalent tin salts, polyamines or hydrazine derivatives
• development acceleration that uses nitrogen, a polyonium salts of phosphorus or sulfur, or polyalkylene glycols.
• Grain techniques for increasing the speed of silver halide emulsions include those concerning core/shell grain emulsions of a monodisperse type or tabular type.
• the emulsions of this type have been improved so that the light absorbed in the inner part of a silver halide grain can be converted to a development center in a good efficiency.
• a further improvement, however, has been sought from the viewpoint of storage stability.
• Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 113934/1983, for example, discloses a method in which a silver halide emulsion comprising tabular grains having an average aspect ratio of 8 or more.
• the tabular grains having a high aspect ratio have an excessively high degree of development activity irrespective of their average silver iodide content, because of their configurational characteristics, and hence it is very difficult to obtain the desired gradation. In respect of processing stability also, it has not reached a well satisfactory level.
• the neutral method and the ammonia method are well known.
• a method in which no ammonia is used and an aqueous silver nitrate solution and an aqueous alkali halide solution are mixed in a substantially neutral solution is called the neutral method.
• a method in which an ammoniacal aqueous silver nitrate solution is used in place of the above aqueous silver nitrate solution is called the ammonia method. Since ammonia acts as a silver halide solvent, silver halides grow at a higher rate. Accordingly, the neutral method is too inefficient to obtain a large grain with a normal crystal of 1 ⁇ m or more, and hence the ammonia method has been preferred.
• Silver halide grains having a twin plane have a very higher growth rate than the normal crystal silver halide grains, so that the grains can grow to sufficiently large grains even when the neutral method is used.
• the silver halide grains grown by the neutral method have had no advantages of speed and fog restraint over those grown by the ammonia method.
• An object of the present invention is to provide a light-sensitive silver halide color photographic material, a silver halide emulsion and a process for preparing these, that can achieve a high speed and also a superior fog restraint, storage stability and processing stability.
• the light-sensitive silver halide photographic material of the present invention comprises a support and, provided thereon, at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer; wherein at least one of said layers comprises a silver halide emulsion mainly composed of twinned crystal grains and having a proportion of not more than 1/20 for the number of fogging grains to the number of total silver halide grains.
• the silver halide emulsion used in this light-­sensitive material is mainly composed of twinned crystal grains and having a proportion of not more than 1/200 for the number of fogging grains to the number of total silver halide grains when it is not subjected to chemical ripening.
• This emulsion is prepared under conditions of a pH value of from 1 to 5 in respect of not less than 50 mol % of the residual silver compound added in the course of the formation of silver halide grains, after at least 90 mol % of the silver compound has been added.
• the fogging grain herein referred to means a grain reduced to a silver atom by a silver halide present at an unexposed portion when color developing is carried out in order to form a dye image. It can be distinguished from a grain other than the fogging grain by counting the number of color points of dye-cloud or by directly observing developed silver itself with an electron-microscope.
• a color developing solution used in color photographic processing include the following: - Color developing solution 1 - Processing time: 3 minutes 15 seconds Processing temperature: 38°C 4-Amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine half-sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Trisodium nitrilotriacetate (monohydrate) 2.5 g Potassium hydroxide 1.0 g Made up to 1 liter by adding water and adjusted to pH 10.1.
• the rate of development of the fogging grains is so much higher than the rate of development of grains other than fogging grains that the fogging grains can be readily distinguished from other grains.
• the number of total silver halide grains and the number of fogging grains in a light-sensitive material can be confirmed, for example, by stopping the processing by the use of an aqueous 3 % acetic acid solution immediately after color development, followed by washing, and decomposition of gelatin with an aqueous actinase solution, and thereafter observing grains with a scanning type electron microscope.
• the silver halide grains used in the present invention are mainly composed of twinned crystals.
• What is herein meant by "mainly composed of twinned crystals” is that not less than 60 % of the total projected areas of silver halide grains are held by twinned crystals, and more preferably not less than 80 % thereof are held by twinned crystals. Particularly preferably not less than 90 % thereof are held by twinned crystals.
• twinned crystals herein referred to may be those in which a twin plane is included in a grain, irrespective of a tabular grain having an average aspect ratio of not less than 1.1 or a grain having an aspect ratio infinitely close to 1.
• the grains may preferably have an average aspect ratio of from 1.1 to 20, more preferably from 1.2 to 10, and particularly preferably from 1.5 to 8.
• the twinned crystal of the present invention may be a grain having uniform composition, or may be, e.g., a core-shell grain, having different composition between the inner part and the surface.
• the silver halide emulsion in the present invention its grain size distribution may be monodisperse or polydisperse.
• a monodisperse emulsion is preferred.
• the monodisperse emulsion has the properties that the fog is low and a higher speed can be obtained compared with a polydisperse emulsion.
• the emulsion of the present invention is monodisperse, the emulsion shows more preferable properties that it can obtain stable processing results even against variations of processing conditions.
• the grain size herein referred to is a diameter obtained by calculating a projected image of a grain into a circular image having the same area.
• the grain size can be determined, for example, by taking a photograph of the grains using an electron microscope with enlargement of from 10,000 magnifications to 50,000 magnifications, and actually measuring the diameters or the areas at the time of projection, of the grains taken on a print of the photograph.
• Statistical processing of the average or dispersity of the grain size is carried out by measuring 1,000 or more grains sampled at random.
• a highly monodisperse emulsion particularly preferred in the present invention is an emulsion having preferably not more than 20 %, and more preferably not more than 15 %, of the breadth of distribution which is calculated by the equation:
• the grain size is measured by the above measuring method, and the average grain size is expressed as a simple average.
• the silver halide emulsion of the present invention may preferably be mainly comprised of a twinned crystal having two or more parallel twin planes.
• the twinned crystal may preferably have an even-numbered twin planes, and particularly preferably two twin planes.
• mainly comprised of a twinned crystal having two or more parallel twin planes is that the number of a twinned crystal grain having two or more parallel twin planes is not less than 50 %, preferably not less than 60 %, and particularly preferably not less than 70 %, of the total number of grains.
• the proportion of the number of fogging grains to the number of the total silver halide grains contained in the light-sensitive material of the present invention is not more than 1/20, preferably not more than 1/30, and more preferably not more than 1/100.
• the following silver halide emulsion may preferably be used in view of the speed, fog restraint, storage stability and processing stability.
• This emulsion is mainly composed of the twinned crystals and has a proportion of 1/200 for the number of the fogging grains to the number of the total silver halide grains present when developing is carried out after the emulsion has been coated on a support without application of chemical ripening (hereinafter often called "the number of the fogging grains prior to chemical ripening").
• This silver halide emulsion is subjected to chemical ripening in an optimum, and then used in a light-sensitive material.
• the number of the fogging grains prior to chemical ripening can be readily calculated as the number of color points by carrying out, for example, the following photographic processing.
• An emulsion obtained by adding commonly available photographic additives such as a spreading agent, a thickening agent, a hardening agent and the following magenta coupler (M-1) is coated on a triacetyl cellulose film support so as to give a coating weight of silver of 7 mg/100 cm2, followed by drying.
• Sample A The resulting light-sensitive material is divided into two, which are designated as Sample A and Sample B.
• Sample A is then subjected to the following photographic processing. Processing steps (38°C): Color developing 5 min. 30 sec. Bleaching 4 min. 30 sec. Washing 3 min. Fixing 4 min. Washing 3 min. Stabilizing 2 min. Drying
• the processing solutions used in the respective processing steps each have the following composition.
• Color developing solution 4-Amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate 4.75 g
• Anhydrous sodium sulfite 4.25 g
• Hydroxylamine half-sulfate 2.0 g
• Anhydrous potassium carbonate 37.5 g
• Sodium bromide 1.3 g
• Trisodium nitrilotriacetate (monohydrate) 2.5 g Potassium hydroxide 1.0 g Made up to 1 liter by adding water and adjusted to pH 10.1.
• Bleaching solution Ferric ammonium ethylenediaminetetraacetic acid 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Made up to 1 liter by adding water, and adjusted to pH 6.0 using ammonia water.
• Sample B is fogged with light, and thereafter processed using the same color developing solution as in the above, followed by stopping using an aqueous 3 % acetic acid, and then washing.
• the resulting sample is photographed using an optical microscope in the same manner as Sample A, and the number of color points similarly counted is regarded as the number of the total silver halide grains.
• used is an emulsion in which the proportion of the number of the fogging grains prior to chemical ripening is not more than 1/200, preferably not more than 1/500, and more preferably not more than 1/1,000.
• At least 50 mol % of silver compound among the residual silver compound to be added for the formation of silver halide grains is added at a pH value of from 1 to 5 of an aqueous solution in a mixing vessel, after at least 90 mol % of silver compound to be initially used has been added.
• the amount of the silver compound added at this relatively low pH value is preferably 50 mol % of the compound, which is added in the latter stage, among the silver compound. More preferably, the whole silver compound to be added after the initial 10 mol % of silver compound has been added is added in this solution of a low pH value.
• the pH value may more preferably be 1.5 to 4.0.
• the silver halide emulsion is often prepared by first forming fine grains called nuclei and then making them to grow. It is also carried out to make nuclei to grow to a certain extend to form grains called seeds, and then make the seeds to grow to grains having the desired size.
• the preparation process of the present invention includes a process in which, for example, the nuclei and the seeds are formed using a halide and a silver compound in small amounts and thereafter a silver compound and a halide are added at such a low pH value to make grains to grow. In this instance, among the silver compound used in the growth of grains, not less than 50 mol % of the residual silver compound is added at a pH value of from 1 to 5. The whole silver compound used for growing seeds may preferably be added at a pH value of from 1 to 5.
• seed grains When such seed grains are formed, it is preferred to first wash with water an emulsion containing the seed grains formed (i.e., a seed emulsion) and thereafter carry out the growth.
• a seed emulsion containing the seed grains formed
• a twinned crystal seed emulsion formed by the ammonia method is washed with water and thereafter a silver compound and a halide are added at the low pH value to make grains to grow so that grains with the desired grain size can be obtained.
• an inorganic acid such as nitric acid, sulfuric acid and hydrochloric acid can be used to lower the pH. It is particularly preferred to use nitric acid.
• the twinned crystals according to the present invention may be any of those comprised of a ⁇ 111 ⁇ plane, those comprised of a ⁇ 100 ⁇ plane, or those comprised of the both.
• Iodine may be fed to the system in the form of silver iodide. They should be added at the rate that may not cause generation of new nuclei and at the rate that may give no breadth of grain size distribution as a result of Ostwald ripening, in other words, may preferably be added at a rate within the range of from 30 to 100 % of the rate that causes generation of new nuclei.
• Research Disclosure RD-29945 discloses a technique by which a silver halide emulsion comprising grains with a high aspect ratio is prepared at a low pBr value.
• nuclei are generated at a low pH value of from 1.6 to 3, and an example is described in which the growth process is carried out at a pH value of from 5.9 to 6 depending on the properties of gelatins used.
• stirring conditions at the time of preparation are very important.
• the apparatus as disclosed in Japanese Patent O.P.I. Publication No. 160128/1987 can be preferably used, which is an apparatus in which a nozzle from which solutions are added is disposed in the liquid, in the vicinity of a mother liquor inlet of a stirrer.
• the stirring may preferably be carried out at a revolution number of from 400 to 1,200 rpm.
• silver halide photographic emulsion of the present invention known photographic additives can be used.
• the proportion of the number of fogging grains it is also possible to decrease the proportion by using fog restrainers such as 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene or DIR compounds or by making silver halide grains to have a smaller grain size.
• fog restrainers such as 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene or DIR compounds
• dye forming couplers are used, that form a dye upon coupling reaction with an oxidized product of an aromatic primary amine developing agent (as exemplified by a p-phenylenediamine derivative or an aminophenol derivative) in the course of color photographic processing.
• These dye forming couplers should preferably have in the molecule a group having 8 or more carbon atoms, capable of making a coupler non-diffusible, which is called a ballast group.
• These dye forming couplers may be either four-equivalent couplers in which silver ions of four molecules must be reduced in order for a dye of one molecule to be formed, or two-equivalent couplers in which silver ions of two molecules may only be reduced.
• the dye forming couplers include colored couplers having the effect of color correction, and compounds capable of releasing photographically useful fragments such as a development restrainer, a development accelerator, a bleach accelerator, a developing agent, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifogant, a chemical sensitizer, a spectral sensitizer and a desensitizing agent, upon coupling reaction with an oxidized product of a developing agent.
• a development restrainer a development accelerator, a bleach accelerator, a developing agent, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifogant, a chemical sensitizer, a spectral sensitizer and a desensitizing agent, upon coupling reaction with an oxidized product of a developing agent.
• a coupler capable of releasing a development restrainer with progress of development to improve the sharpness of an image or the grainines of an image is called a DIR coupler.
• a DIR compound capable of releasing a development restrainer at the same time with the formation of a colorless compound upon coupling reaction with an oxidized product of a developing agent may also be used in place of the DIR coupler.
• the DIR coupler and DIR compound that can be used include those in which a restrainer has been directly attached to the coupling position, and those in which a restrainer is attached to the coupling position through a divalent group so that the restrainer is released upon intramolecular nucleophilic reaction, intramolecular electron transfer reaction or the like that takes place in the group having been split off upon the coupling reaction (i.e, those called a timing DIR coupler and a timing DIR compound).
• a timing DIR coupler and a timing DIR compound those which are diffusible after being split off and those which are not so diffusible may be used alone or in combination.
• a colorless coupler also called a competing coupler
• a colorless coupler that undergoes coupling reaction with an oxidized product of an aromatic primary amine developing agent but does not form a dye may also be used in combination with the dye forming coupler.
• acylacetanilide couplers can be preferably used. Of these, it is advantageous to use benzoylacetanilide compounds and pivaroylacetailide compounds.
• magenta dye forming coupler As a magenta dye forming coupler, it is possible to use known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrozolotriazole couplers, ring-opening acylacetonitrile couplers, and indazolone couplers.
• cyan dye forming coupler known phenyl or naphthol couplers can be used.
• phenol couplers substituted with an alkyl group, an acylamino group or a ureido group naphthol couplers formed of a 5-­aminonaphthol skeleton, and two-equivalent type naphthol couplers in which an oxygen atom has been introduced as a split-off group.
• Suitable supports that can be used in the light-­sensitive material of the present invention include polymer films and paper. These may have been subjected to treatment for improving adhesion properties, antistatic properties and so forth.
• a monodisperse spherical twinned crystal seed emulsion was prepared by the method as described below.
• Solution A Ossein gelatin 150 g Potassium bromide 53.1 g Potassium iodide 24 g Using water, made up to 7.2 lit.
• Solution B Silver nitrate 1.8 g Using water, made up to 6 lit
• Solution C Potassium bromide 1,327 g 1-Phenyl-5-mercaptotetrazole (dissolved with methanol) 0.3 g Using water, made up to 3 lit.
• Solution D Ammonia water (28 %) 705 ml
• Solution B To Solution A vigorously stirred at 40°C, Solution B and Solution C were added in 30 seconds by double-jet precipitation to effect formation of nuclei.
• the pBr at this time was 1.09 to 1.15.
• Solution D was added in 20 seconds followed by ripening for 5 minutes.
• concentration of KBr at the time of ripening was 0.071 mol/lit.
• concentration of ammonia was 0.63 mol/lit.
• the pH was adjusted to 6.0, and immediately desalting and washing with water were carried out.
• the grains of the resulting seed emulsion were observed with an electron microscope to reveal that the emulsion was a monodisperse spherical twinned crystal emulsion having an average grain size of 0.36 ⁇ m and a breadth of grain size distribution (standard deviation of grain size/average grain size x 100) of 18 %.
• Solution E1 Gelatin 35 g Disodium propyleneoxy-polyethyleneoxydisuccinate (an aqueous 10 % methanol solution) 10 ml Potassium bromide 85 g Aqueous 56 % acetic acid solution 62 ml Aqueous 28 % ammonia solution 103 ml Seed emulsion A (corr.
• Solution F1 and Solution G1 were added in 60 minutes by double jet precipitation. During the addition, the solution temperature was maintained at 49°C with vigorous stirring. The pAg was kept at 10.5, and the pH which was 9.0 when the addition was started was continuously changed to 8.0 at the time the addition was completed. The rate of addition of Solution F1 and Solution G1 was linearly increased so that the rate at the final stage was 17 times that of the initial stage.
• the resulting emulsion was observed with an electron microscope to reveal that the emulsion had an average grain size of 1.3 um, a breadth of grain size distribution of 15 %, a proportion of 85 % for the tabular grains having an aspect ratio of not less than 2, and an average aspect ratio of 3.5 for the grains having an aspect ratio of not less than 2.
• the proportion of the number of the grains having two parallel twin planes was 75 %.
• Solution E2 Ossein gelatin 37 g Disodium propyleneoxy-polyethyleneoxydisuccinate (an aqueous 10 % methanol solution) 10 ml Seed emulsion A 81 ml Using water, made up to 4,000 ml
• Solution F2 Ossein gelatin 109 g Potassium bromide 804 g Potassium iodide 23.1 g Using water, made up to 4,628 ml
• Solution G2 Silver nitrate 1,168 g Using water, made up to 4,000 ml
• Solution F2 and Solution G2 were added in 112 minutes by double jet precipitation. During the addition, the pH was adjusted to 5.8 until 9/10 of Solution G2 had been added, and to 2.0 until more than 9/10 of the solution had been completely added. The pAg was kept at 9.0 from beginning to end. The rate of addition of Solution F2 and Solution G2 was linearly increased so that the rate at the final stage was 6.4 times that of the initial stage.
• the pH was adjusted to 6.0.
• Desalting was carried out in the same manner as in the twinned crystal emulsion 1.
• the resulting emulsion was observed with an electron microscope to reveal that the emulsion had an average grain size of 1.3 ⁇ m, a breadth of grain size distribution of 17 %, a proportion of 85 for the tabular grains having an aspect ratio of not less than 2, and an average aspect ratio of 3.5 for the grains having an aspect ratio of not less than 2.
• the proportion of the number of the grains having two parallel twin planes was 75 %.
• twinned crystal emulsion 3 When 1/2 of the total weight of silver nitrate had been added in the same manner as the twinned crystal emulsion 2, the pH was adjusted to 2.0 with nitric acid, and then the silver nitrate was continued to be fed while the pH was maintained at 2.0. An emulsion thus obtained is designated as a twinned crystal emulsion 3. The resulting emulsion was observed with an electron microscope to reveal that the emulsion had an average grain size of 1.3 ⁇ m, a breadth of grain size distribution of 15 %, a proportion of 87 % for the tabular grains having an aspect ratio of not less than 2, and an average aspect ratio of 4.0 for the grains having an aspect ratio of not less than 2. The proportion of the number of the grains having two parallel twin planes was 75 %.
• a twinned crystal emulsion 4 This emulsion was observed with an electron microscope to reveal that the emulsion had an average grain size of 1.3 ⁇ m, a breadth of grain size distribution of 15 %, a proportion of 91 % for the tabular grains having an aspect ratio of not less than 2, and an average aspect ratio of 4.3 for the grains having an aspect ratio of not less than 2.
• the proportion of the number of the grains having two parallel twin planes was 75 %.
• Photographic processing A Processing steps (38°C): Color developing 5 min. 30 sec. Bleaching 4 min. 30 sec. Washing 3 min. Fixing 4 min. Washing 3 min. Stabilizing 2 min. Drying
• the processing solutions used in the respective processing steps each have the following composition.
• Color developing solution 4-Amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate 4.75 g
• Anhydrous sodium sulfite 4.25 g
• Hydroxylamine half-sulfate 2.0 g
• Anhydrous potassium carbonate 37.5 g
• Sodium bromide 1.3 g
• Trisodium nitrilotriacetate (monohydrate) 2.5 g Potassium hydroxide 1.0 g Made up to 1 liter by adding water and adjusted to pH 10.1.
• - Bleaching solution Ferric ammonium ethylenediaminetetraacetic acid 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Made up to 1 liter by adding water, and adjusted to pH 6.0 using ammonia water.
• Fixing solution Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.5 g Sodium metasulfite 2.3 g Made up to 1 liter by adding water, and adjusted to pH 6.0 using acetic acid.
• Stabilizing solution - Formalin (an aqueous 37 % solution) 1.5 ml Konidax (produced by Konica Corporation) 7.5 ml Made up to 1 liter by adding water.
• Sample B was fogged with light, and thereafter processed using the same color developing solution as in the above, followed by stopping using an aqueous 3 % acetic acid, and then washing.
• the resulting sample was photographed using an optical microscope in the same manner as Sample A, and the number of silver halide grains was counted.
• Table 2 Sample No. Twinned crystal emulsion No. Number of Color points of Sample A Number of silver halide grains of Sample B Proportion of fogging grains 101 1 48 7,200 1/150 102 2 30 7,400 1/250 103 3 14 7,200 1/530 104 4 7 7,400 1/1060
• Table 2 shows that the emulsions, Samples 102 to 104, prepared according to the present invention have a smaller proportion of the number of the fogging grains prior to chemical ripening, than Sample 101.
• the layers each composed as follows were formed from the support side to prepare a multi-layer color light-sensitive photographic material 201.
• Second layer Intermediate layer Gelatin 1.0
• Third layer First red-sensitive emulsion layer AgBrI (AgI: 7 mol %; octahedron; grain size calculated as a cube: 0.3 ⁇ m) 0.6 Gelatin 1.2 Sensitizing dye (S-1) 8 x 10 ⁇ 4 Sensitizing dye (S-2) 5 x 10 ⁇ 4 Sensitizing dye (S-3) 3 x 10 ⁇ 4 Coupler (C-1) 0.10 Coupler (C-3) 0.25 Colored coupler (CC-1) 0.04 DIR coupler (D-2) 0.05
• a coating aid Su-2 dispersing agents Su-2 and Su-3, hardening agent H-1 and H-2, a stabilizer Stab-1, antifoggants AF-1 and AF-2 and an anticeptic agent DI-1 were added to each layer.
• the sensitizing dyes S-1, S-2 and S-3 were each used in an amount 1.4 times the amount in Sample 201.
• Samples 202 to 205 The samples thus obtained are designated as Samples 202 to 205.
• Samples 201 to 205 were subjected to developing for 3 minutes and 15 seconds using the color developing solution used in the photographic processing A in Example 1, immediately followed by stopping with an aqueous 3 acetic acid solution, and then washing. The resulting samples were put in an aqueous 0.1 % actinase solution, and only fifth layers were separated. Silver halides from which a gelatin was decomposed were photographed using an electron microscope, and the number of fogging grains and the total number of silver halide grains were counted.
• Table 3 shows that the emulsions, Samples 203 to 205, prepared according to the present invention have a smaller proportion of the number of the fogging grains, than Samples 201 and 202.
• Samples similar to those in Example 2 were prepared, and were designated as Samples 301 to 305, respectively. Each sample was divided into two groups, which were designated as Sample A and Sample B. Sample A was left to stand in a thermostatic chamber kept at a temperature of 55°C, and Sample B at room temperature, for 7 days. Thereafter, each sample was subjected to white-light sensitometry exposure for 1/100 seconds, followed by photographic processing under the following conditions. Processing conditions (38°C): Color developing 3 min. 15 sec. Bleaching 6 min. 30 sec. Washing 3 min. 15 sec. Fixing 6 min. 30 sec. Stabilizing 1 min. 30 sec. Drying
• Each processing solution had the same composition as in the photographic processing A in Example 1.
• Density of red color was measured on each sample to obtain the results as shown in Table 4.
• the fog is indicated as a value obtained by subtracting a measured value of transmission density of a sample on which processing was started from the bleaching step without the color developing, from a measured value according to the transmission density.
• the sensitivity or speed is expressed as a reciprocal of the amount of exposure necessary to give a fog density of +0.1, and indicated as a relative value of the speed of Sample 301, which was regarded as 100.
• Table 4 Sample No. Fog Fog increase due to high temperature Speed of Sample A Sample B Sample C 301 0.14 0.24 0.10 100 302 0.14 0.23 0.09 110 303 0.09 0.16 0.07 108 304 0.06 0.10 0.04 105 305 0.06 0.10 0.04 105
• Table 3 shows that Samples 303 to 305 bring about less increase in fog and no lowering of speed, compared with Comparative Samples 310 and 302.
• Samples similar to those in Example 2 were prepared, and were designated as Samples 401 to 405, respectively. Each sample was divided into three groups, which were designated as Sample A, Sample B and Sample C. These were subjected to the same exposure as in Example 3, and then processed in the same manner as in Example 3 except that the color developing times were respectively changed as shown below.
• Table 5 shows that Samples 403 to 405 according to the present invention have superior processing stability compared with Comparative Samples 401 and 402.
• the twinned crystal emulsions 1 to 4 as shown in Example 1 was optimally chemically sensitized, which were then added to the ninth layer of Sample 201 in Example 1. Evaluation was made in the same manner as in Examples 2 to 4 to confirm that the effect of the present invention was similarly obtained.
• the twinned crystal emulsions 1 to 4 as shown in Example 1 was optimally chemically sensitized, which were then added to the thirteenth layer of Sample 201 in Example 1. Evaluation was made in the same manner as in Examples 2 to 4 to confirm that the effect of the present invention was similarly obtained.

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