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
  • G03C1/035—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 high in photosensitive speed and excellent in latent-image preservability.
• the photosensitivity of tetradecahedral silver halide grains has been improved by making use of a compound (for example, a dye) having a characteristic of selectively working on a specific crystal face (the characteristic is hereinafter referred to as a face-selectivity) or by controlling a chemical sensitization to be caused on a specific face by making use of a sulfur sensitizer having a face-selectivity.
• a compound for example, a dye having a characteristic of selectively working on a specific crystal face (the characteristic is hereinafter referred to as a face-selectivity) or by controlling a chemical sensitization to be caused on a specific face by making use of a sulfur sensitizer having a face-selectivity.
• JP OPI Publication Japanese Patent Publication Open to Public Inspection Nos. 64-62631/1989, 64-62632/1989, 64-40938/1989, 64-74540/1989, 63-305343/1988, 64-77047/1989, 3-204633/1991 and so forth.
• a silver halide photographic light sensitive material comprising a silver halide emulsion, wherein the silver halide emulsion contains silver halide grains having one or two development initiating points in each of the grains, accounting for at least 75% of the whole silver halide grain, based on number of grains.
• the silver halide emulsions relating to the invention may be those either having or not having a twin plane and the emulsions may also contain both of them.
• the emulsions may have any shapes including, for example, the so-called tabular, octahedral and tetradecahedral shapes.
• the above-mentioned twin plane may be (111) twin plane, (100) twin plane or both of the above-mentioned two twin plane. Among them, the (111) twin plane is preferred. When each grain has not less than two twin planes, it is preferable that the twin planes are in parallel to each other. It is particularly preferable to be twinned crystal grains having each two parallel (111) twin planes (hereinafter abbreviated to 'parallel two-plane twinned crystal grains') are preferred.
• the grains each having a twin plane may take any one of various shapes.
• the grains are tabular-shaped grains having each an aspect ratio of less than 3.0.
• the aspect ratios mentioned herein can be expressed as a ratio of the diameter of a circle correspondingly converted from a projected area (circular-equivalent diameter) to thickness of a tabular-shaped grain.
• the particularly preferable grains are twinned crystal grains having an aspect ratio within the range of 1.0 to 2.5.
• the apparent shapes thereof are observed as the octahedron or one having the apices so scraped off as to be slightly distorted.
• the diameter thereof can be expressed by the diameter of a circle having the same projected area as that of the tabular-shaped silver halide grain when the same tabular-shaped silver halide grain is so oriented as to set horizontally the two principal planes facing each other to the plane.
• a diameter as mentioned above is to be within the range of, preferably 0.1 to 5.0 ⁇ m, more preferably 0.2 to 4.0 ⁇ m and particularly preferably 0.3 to 3.0 ⁇ m.
• the grain size distribution is preferable to be monodispersive.
• the variation coefficient (v) thus defined is preferably less than 20%, more preferably less than 18% and most preferably less than 15%.
• the above-mentioned diameter can be obtained in the following manner that a silver halide emulsion containing the tabular-shaped silver halide grains of the invention is projected by magnifying 10,000 to 50,000 times through an electron microscope and the area of the grains projected on a print is practically measured, (provided that the numbers of the measured grains are to be not less than 1000 grains at random).
• the silver halide emulsions relating to the invention may have any one of halogen compositions.
• the halogen compositions thereof are to be composed of silver iodobromide having an average silver iodide content within the range of, preferably 4 to 20 mol% and more preferably in particular 5 to 15 mol%.
• the silver halide emulsion grains are to have a high silver iodide containing phase inside the grains thereof.
• the silver iodide content of the high silver iodide containing phase is to be within the range of, preferably 15 to 45 mol%, more preferably 20 to 42 mol% and particularly preferably 25 to 40 mol%.
• the silver halide grains relating to the invention and having a high silver iodide containing phase inside the grains are those comprising a high silver iodide containing phase covered by the other lower silver iodide containing phase having a silver iodide content lower than that of the former high silver iodide containing phase.
• the average silver iodide content of the outer phase is preferably not higher than 6 mol% and preferably in particular within the range of 0 to 4 mol%. It is also allowed to interpose a further silver iodide containing phase (that is called an intermediate phase) between the outer phase and the high silver iodide containing phase.
• the silver iodide content of the intermediate phase is to be within the range of, preferably, 10 to 22 mol% and, more preferably in particular, 12 to 20 mol%.
• the silver iodide contents are preferable to have a difference of not less than 6 mol% and preferable in particular to have a difference of not less than 10 mol%, respectively.
• a further separate silver halide phase may be made present in the central portion of the internal high silver iodide containing phase, between the internal high silver iodide containing phase and the intermediate phase and between the intermediate phase and the outermost phase.
• the volume of the outermost phase may be within the range of, preferably 4 to 70 mol% of the whole volume of the grain and, more preferably 10 to 50 mol% thereof.
• the volume of the high silver iodide containing phase is to be within the range of, preferably 10 to 80% of the whole volume of the grain, more preferably 20 to 50% thereof and, further preferably 20 to 45% thereof.
• the volume of the intermediate phase is to be within the range of, preferably 5 to 60% of the volume of the whole grain and, more preferably 20 to 55% thereof.
• the above-mentioned phases may also be any one of a single phase having a uniform composition, the group consisting of the plural phases each having a uniform and stepwise varying composition, a continuous phase having a continuously varying composition in any desired phase and the combinations thereof.
• the other embodiments of the silver halide emulsions of the invention include an embodiment in which silver iodide localized inside the grain does not form any substantially uniform phase, but the silver iodide content changes continuously from the center of each grain toward the outside. In this case, it is preferable that the silver iodide content is reduced monotonously from the point having a maximum silver iodide content inside the grain toward the outside of the grains.
• the silver iodide content is to be within the range of, preferably 15 to 45 mol% and, more preferably 25 to 40 mol%.
• the silver iodide content in the grain surface phase is to be, preferably not more than 6 mol% and, more preferably within the range of 0 to 4 mol%.
• the silver halide emulsions of the invention are preferable to satisfy at least one of the following requirements (1) through (4).
• an emulsion is pretreated as follows. First, a pronase solution is added to the emulsion and the resulting mixture is stirred at 40°C for one hour to hydrolyze gelatin. Next, the emulsion grains are so centrifuged as to be precipitated. After the resulting supernatant liquid is removed, an aqueous pronase solution is added thereto and another gelatin hydrolysis is then carried out again under the above-mentioned conditions. The resulting sample is centrifuged again and, after the supernatant liquid is removed, distilled water is added to disperse the emulsion grains again in distilled water. The resulting dispersion is centrifuged and the supernatant liquid is removed.
• the emulsion grains are redispersed in ethanol.
• the resulting dispersion is thinly coated over a specularly-polished silicon wafer, so that a sample subject to measurement can be prepared.
• the above-mentioned XPS measurements are carried out, for example, by making use of Model ESCA/SAM 560 manufactured by PHI Co. and under the conditions of Mg-K ⁇ rays as the excitation X-rays, 15Kv of the X-ray source voltage, 40mA of the X-ray source current and 50eV of the pass energy.
• composition ratios are calculated from the integrated intensities of each peak and by making use of a relative photosensitive speed coefficient method.
• a relative photosensitive speed coefficient method As the relative photosensitive speed coefficients of Ag3d, Br3d and I3d3/2, 5.10, 0.81 and 4,592 are used, thereby the composition ratios can be given by an atomic percentage as the unit, respectively.
• An average silver iodide content (J 1 ) is obtained in the aforementioned X-ray fluorescence analysis and an average silver iodide content (J 3 ) is measured, in an X-ray microanalysis, on a silver halide crystal 80% or more apart from the center in the grain diameter direction of a silver halide grain.
• the term, 'diameter', stated herein means the diameter of a circle circumscribed with a grain where the projected area of the grain can be maximized.
• Silver halide grains are dispersed to a grid for electron-microscopic observation use equipped with an electron microscope to which an energy-dispersion type X-ray analyzer was attached.
• the magnification is set so that one grain can be made to come within the range of the electron microscope by a liquid nitrogen cooling treatment.
• the intensities of AgL ⁇ and IL ⁇ rays are integrated for a certain time.
• a subject silver iodide content can then be calculated out by making use of the intensity ratio of the AgL ⁇ rays/the IL ⁇ rays and a calibration curve made out in advance.
• Another preferable embodiment of the silver halide emulsions of the invention is that the above-mentioned (420) X-ray diffraction signal, in which CuK ⁇ rays are used as the radiation source, have two or three peaks and, more preferably in particular, three peaks.
• any X-rays having a variety of characteristics can be used.
• CuK ⁇ rays targeting for Cu have been used most popularly.
• Silver iodobromide has a rock-salt structure and the (420) diffraction signal made out by CuK ⁇ rays is observed at an angle within the range of 71 to 74 degrees (2 ⁇ ). As the signal intensity thereof is relatively strong and at a high angle, the resolving power is also excellent and it is optimum for investigating crystal structures.
• the relative standard deviations of the measured values are each not more than 20%, preferably not more than 15% and, particularly not more than 12%.
• the term, 'a relative standard deviation', stated herein shall be defined as a value (obtained as follows) x 100.
• the above-mentioned value can be obtained by dividing the standard deviation of the subject silver iodide contents by the average silver iodide content.
• the requirement for growing the grains may be any one of acidic method, neutral method and ammoniacal method. It is allowed to use the known methods including, for example, those described in JP OPI Publication Nos. 61-6643/1986, 61-14630/1986, 61-112142/1986, 62-157024/1987, 62-18556/1987, 63-92942/1988, 63-151618/1988, 63-1613451/1988, 63-220238/1988 and 63-311244/1988.
• a method of adding an aqueous solution of the water-soluble iodide may be used as one of the iodide supply methods.
• the grains can also be grown up in an Ostwald ripening treatment after adding it in the forms of fine silver halide grains (such as silver iodide or silver iodobromide). It is further preferable to use a method of supplying it in the form of fine silver halide grains.
• any known silver halide solvents such as ammonia, thioether and thiourea can be made present. It is further allowed to use a crystal-form controller.
• a metal ion may be added to the above-mentioned silver halide grains in the courses of forming and/or growing the grains by making use of at least one selected from the group consisting of cadmium salts, zinc salts, the complex salts thereof, thallium salts including the complex salts thereof, iridium salts, rhodium salts and iron salts, so that the above-mentioned metal element can be contained in the inside of the grains and/or on the surfaces of the grains.
• reduction-sensitization nuclei can be provided to the inside of the grains and/or the surfaces of the grains.
• 'a development initiating point' is recognized as a point at which a development is initiated by developing silver halide grains, development-stopping and thereafter observing them. To be more concrete, it can be specified as follows.
• a light sensitive material comprising a support coated thereon with an photographic emulsion is treated as follows.
• the light sensitive material is exposed to light and then developed with Kodak MAA-1 developer as below.
• the characteristic curve is made out of the resulting developed light sensitive material.
• Metol-ascorbic acid developer MAA-1
• Methyl N-methyl para-aminophenol sulphate
• Ascorbic acid 2.5 g Ascorbic acid
• 10.0 g Potassium bromide 2.5 g
• Potassium bromide 2.5 g
• Kodalk Sodium metaborate
• Distilled water 35.0 g Distilled water to make 1 liter
• the development processing requirements for specifying the development initiating point can suitably be so selected as to make the initiation point observation easier.
• the developing conditions are to be set so that developed silver may be grown up with developer (A) to have some extent of the length, so that the developed silver can be discriminated from a little bit of print-out silver produced in the course of an electron microscopic observation.
• each point there is no limitation to the location of the development initiating point on a grain. When there are two development-initiating points on a single grain, it is preferable to locate each point as farther as possible.
• the development initiating point(s) is preferable to be located at the corner or edge of grains, or in the neighborhood thereof.
• the development initiating point(s) is preferable to be located on a line formed by exposure of the twin plane in the surface of the grain, or in the neighborhood thereof.
• the ratio of the grains having each one or two development-initiating points to the whole grains is preferably not less than 75% and, more preferably, not less than 85%.
• the pAg during the ripening treatment is within the range of, preferably not less than 8 and not more than 12, more preferably not less than 9 and not more than 11 and, particularly not less than 9.5 and not more than 10.5.
• the temperature during the ripening treatment is within the range of, preferably not lower than 50°C and not higher than 75°C and, more preferably not lower than 60°C and not higher than 70°C.
• the silver halide emulsions of the invention can be spectrally sensitized by making use of a sensitizing dye, and the emulsions can also be chemically sensitized.
• the silver halide emulsions of the invention are preferable to be chemically sensitized in the presence of a sensitizing dye and, more preferably in the presence of not less than two kinds of sensitizing dyes.
• a silver halide solvent is made present at the initial point of time for the chemical sensitizing treatment.
• any known treatment methods such as a sulfur sensitizing method, a selenium sensitizing method, a reduction-sensitization method and a gold sensitizing method can be used, and these sensitizing methods may be used independently or in combination.
• the above-mentioned gold sensitizing method is one of the typical noble-metal sensitizing methods.
• gold compounds including typically a gold complex salt are used.
• the preferable gold sensitizers include typically chloroauric acid and the salts thereof. It is also useful that a gold sensitization is enhanced by making combination use of thiocyanate. It is also allowed that the complex salts of other noble metals than gold, such as platinum, palladium and iridium, are used independently or in combination as a gold sensitizer.
• the concrete examples thereof are given in U.S. Patent No. 2,448,060, British Patent No. 618,061 and so forth.
• the chalcogenite sensitizers applicable thereto include, for example, sulfur compounds contained in gelatin and, besides, various sulfur compounds such as inorganic sulfur compounds, e.g., thiosulfates, thioureas, thiazoles and rhodanines, a dithiacarbamic acid derivative, selenourea and tellurourea.
• sulfur compounds contained in gelatin e.g., sulfur compounds contained in gelatin and, besides, various sulfur compounds such as inorganic sulfur compounds, e.g., thiosulfates, thioureas, thiazoles and rhodanines, a dithiacarbamic acid derivative, selenourea and tellurourea.
• inorganic sulfur compounds e.g., thiosulfates, thioureas, thiazoles and rhodanines, a dithiacarbamic acid derivative, selenourea and tellurourea.
• Organic sulfur sensitizers including particularly thiourea type sulfur sensitizers are preferable for chemically sensitizing the silver halide emulsions of the invention.
• the compounds preferable for the thiourea sensitizers include, for example, the exemplified compounds given in JP OPI Publication Nos. 55-45016/1980, 58-80634/1983, 62-196645/1987 and 1-114839/1989.
• the reduction sensitizers applicable thereto include, for example, stannous salts, amines, formamidine sulfinic acid and silane compounds.
• the sulfur sensitizers are used in an amount, that is converted into the active sulfur content, within the range of, preferably 1x10 -7 mols to 1x10 -4 mols and, further preferably, 1x10 -6 mols to 5x10 -5 mols, each per mol of silver halide used.
• the gold sensitizers are used in an amount within the range of, preferably 1x10 -7 mols to 1x10 -4 mols and, further preferably 5x10 -7 to 5x10 -5 mols, each per mol of silver halide used.
• the ratio of the former to the latter is preferably within the range of 3:1 to 1:1.
• a sulfur sensitizer and a gold sensitizer When making combination use of a sulfur sensitizer and a gold sensitizer, they may be mixed up together and then added or they may be added separately. It is preferable to add them separately. When adding them separately, they may be added at the same time or may also be added one first and then the other next. The effects of the invention can more advantageously be displayed when a sulfur sensitizer is added first.
• silver halide solvent such as a thiocyanate, a thioether compound, thiazolidinethione and quadrisubstituted thiourea
• thiocyanates, tetra-substituted thiourea and thioether are preferable solvents.
• These silver halide solvents may be made present when carrying out a chemical sensitization or any points of time. However, it is particularly effective to make them present before the chemical sensitization.
• a spectrally sensitizing dye is preferable to be added thereto, for the purpose of providing a spectral sensitivity to a desired light wavelength region.
• the spectrally sensitizing dyes applicable thereto include, for example, a variety of dyes such as cyanine, merocyanine, holopolar cyanine, compounded cyanine, compounded merocyanine, oxonol, hemioxonol, styryl, merostyrol, streptocyanine and the group consisting of polymethine dyes containing pyrylium.
• cyanine dyes are particularly preferable.
• the cyanine dyes preferably applicable thereto are represented by the following Formula [I].
• Z 1 and Z 2 represent each the group consisting of the atoms necessary to form a heterocyclic nucleus.
• the cyanine dyes represented by Formula [I] include S-1 through S-71 given in JP Application No. 3-231739/1991, in the upper right column of p.313 through the left lower column of p.318.
• any commonly known methods may be used. To be more concrete, the following method may be used.
• a sensitizing dye is dissolved in a suitable solvent (that is methanol, ethanol, propanol, alcohol fluoride, 1-methoxyethanol, ethyl acetate, water or an aqueous acid or alkali solution having a suitable pH value) and, the resulting solution is adjusted to have a suitable concentration.
• the solution is then added into a silver halide emulsion or an aqueous hydrophilic colloid solution.
• the above-mentioned solution is added in any desired step among the steps of preparing a silver halide emulsion.
• the preferred steps include, for example, a step before, during or after the silver halide grains are formed, a step during a physical ripening treatment, a step before, during or after a chemical ripening treatment and before or when a coating solution is prepared.
• a stabilizer and an antifoggant are preferable to be added when forming the grains or before a chemical sensitizing reaction is started in a chemical ripening treatment, thereby the chemical sensitization can be performed in the presence of a sensitizing dye (more preferably in the presence of two or more kinds of sensitizing dyes), so that the advantages of the invention can more effectively be displayed.
• sensitizing dyes may be used independently. It is, however, particularly effective when two or more kinds of sensitizing dyes are used in combination.
• the amounts of the sensitizing dyes may be widely changed as the case may be. However, they are usually used in an amount within the range of, preferably 1x10 -5 mols to 1x10 -2 mols and, more preferably 1x10 -4 mols to 1x10 -3 mols, each per mol of silver halide used.
• the spectrally sensitizing dyes in the combination capable of showing a supersensitization.
• the combination thereof capable of showing a supersensitization two or more kinds of them are selected from the above-mentioned dyes so that they may be used in combination. Any compounds other than the above-mentioned compounds may be used as supersensitizers.
• a substance such as a dye that can be used together with sensitizing dyes, but does not have any spectrally sensitizing function in itself, or another substance incapable of substantially absorbing any visible rays of light, but capable of displaying a supersensitization.
• the above-mentioned substances include, for example, aromatic organic acid formaldehyde condensates (such as those given in U.S. Patent No. 3,437,510), cadmium salts, azaindene compounds, and aminostilbene compounds each substituted with a nitrogen-containing heterocyclic group (such as those given in U.S. Patent Nos. 2,933,390 and 3,635,721).
• aromatic organic acid formaldehyde condensates such as those given in U.S. Patent No. 3,437,510
• cadmium salts such as those given in U.S. Patent Nos. 2,933,390 and 3,635,721
• azaindene compounds such as those given in U.S. Patent Nos. 2,933,390 and 3,635,721
• the combinations thereof given in U.S. Patent Nos. 3,615,613, 3,615,641, 3,617,295 and 3,635,721 are particularly useful.
• the silver halide emulsions of the invention are chemically sensitized in the presence of the nitrogen-containing heterocyclic compounds described in JP OPI Publication No. 58-126526/1983.
• the advantages of the invention can more effectively be displayed.
• the above-mentioned nitrogen-containing heterocyclic compound, that is to be applied thereto in the presence of two or more kinds of sensitizing dyes, is used in various amounts as the case may be.
• the silver halide fine grains as described in JP Application No. 3-238444/1991, are added to the silver halide emulsion of the invention, in the course between a chemical ripening step and a coating step. It is particularly effective to use silver iodide grains.
• finely grained silver halide grains may be added in an amount of, preferably not more than 1/100d mols, more preferably within the range of 1/20000d to 1/300d mols and, most preferably 1/5000d to 1/500d mols, each per mol of the twinned crystal grains.
• a silver halide may be added at any point of time from a chemical ripening step to the point of time immediate before starting a coating step and, preferably during the chemical ripening step. It is particularly preferable to add finely grained silver halide before adding a sulfur sensitizer or within 30 minutes after adding the sulfur sensitizer.
• a stabilizer may be added to the silver halide emulsions of the invention.
• couplers When the silver halide emulsions of the invention are used in color photographic light sensitive materials, a variety of couplers may be used therein.
• the concrete examples of the couplers are detailed in the above-given Research Disclosures.
• the additives applicable to the invention can be added in such a method as detailed in RD 308119, XIV.
• auxiliary layers such as a filter layer and an intermediate layer, as described in RD 308119, VII-K.
• the light sensitive materials of the invention can have various layer-arrangements such as the regular, inverted and unit layer arrangements, as described in RD 308119, VII-K.
• This invention can be applied to a variety of color light sensitive materials typified by color negative film for general or cinematographic use, color reversal film for slide or TV use, color paper, color positive film and color reversal paper.
• the light sensitive materials of the invention can be developed in the ordinary processes described in RD 17643, pp.28 to 29, RD 18716, p.615 and RD 308119, XIX.
• silver halide emulsion Em-1 was prepared by making use of three kinds of aqueous solutions, an emulsion solution containing fine silver iodide grains, and seed grain emulsion (B), each detailed as follows.
• seed emulsion (B) in an amount equivalent to 0.407 mols was added to violently stirred aqueous solution (b-1) having the above-mentioned composition.
• the pH and pAg of the resulting solution were adjusted by making use of acetic acid and an aqueous KBr solution.
• aqueous solutions (b-2) and (b-3) and emulsion solution (b-4) containing fine grains of silver iodide were each added thereto in a triple-jet method at the flow rates shown in Tables 2, 3 and 4, respectively.
• an aqueous solution of phenyl carbamyl gelatin was added.
• the grains were precipitated and coagulated by controlling the pH of the resulting mixed solution and the desalting and washing treatments were then carried out. After that, the pH was adjusted to be 5.80 at 40°C.
• Em-1 a monodispersed silver iodobromide emulsion having an average grain size of 0.99 ⁇ m, an average silver iodide content of 8.0 mol% and a grain size distribution of 11.2% was prepared.
• the resulting emulsion is herein named Em-1.
• Table 1 Grain-growth conditions of Em-1 Ag (%) 0 29 29 56 100 pH 7.0 ⁇ 7.0 ⁇ 6.0 ⁇ 6.0 ⁇ 6.0 pAg 7.8 ⁇ 7.8 ⁇ 9.7 ⁇ 10.1 ⁇ 10.1
• a silver iodobromide emulsion containing silver iodide in a proportion of 2.0 mol% was prepared in a controlled ⁇ double-jet method under the conditions of 40°C, pH8.0 and pAg 9.0. The resulting emulsion was then so washed as to remove the excessive salts therefrom.
• the resulting grains were proved to have an average grain size of 0.335 ⁇ m and a grain size distribution of 12.5%.
• the resulting emulsion is herein named Seed Emulsion (B).
• aqueous solution containing gelatin of 5 wt% was added into a reaction chamber, and 1 mol each of both aqueous 3.5N solutions of silver nitrate solution and potassium iodide solution were then added thereto at a fixed rate by taking a time for 30 minutes, with stirring at 40°C.
• the pAg of the mixed solution was kept to be 13.5 during the addition of the solutions, by making use of an ordinary pAg controlling means.
• the resulting fine grains of silver iodide were proved to be a mixture of ⁇ -AgI and ⁇ -AgI having an average grain size of 0.06 ⁇ m.
• the resulting emulsion was made to contain silver in the amount equivalent to 400g of silver nitrate, and the emulsion was then prepared to be a finely grained silver iodide. The completed amount thereof was 4178 g.
• Emulsion Em-2 having an average silver iodide content of 8.0% was prepared by making use of each of the following solutions.
• solutions B 2-1 and C 2-1 were each added in a double-jet method so that the addition rate thereof could be 11.62 ml/min at the beginning of the addition and 22.9 ml/min at the completion of the addition.
• the addition rate thereof during the addition was linearly increased to the adding time and the pAg thereof was kept at 8.3.
• the stirring speed was increased to 500 rpm.
• solutions B 2-2 and C 2-2 were added to the above-mentioned stirred solution in a double-jet method so that the addition rate could be 22.91 ml/min at the beginning of the addition and 30.27 ml/min at the completion of the addition.
• the rate during the addition was increased linearly to the adding time and the pAg was kept at 8.3.
• the pAg was adjusted to be 8.6 with an aqueous 3.5N potassium bromide solution.
• solutions B 2-3 and C 2-3 were added to the above-mentioned stirred solution in a double-jet method so that the addition rate could be 16.71 ml/min at the beginning of the addition and 18.63 ml/min at the completion of the addition.
• the rate during the addition was increased linearly to the adding time and the pAg was kept at 8.6.
• the stirring speed was increased to be 550 rpm.
• solutions B 2-4 and C 2-4 were added to the above-mentioned stirred solution in a double-jet method so that the addition rate could be 41.19 ml/min at the beginning of the addition and 68.14 ml/min at the completion of the addition.
• the rate during the addition was increased linearly to the adding time and the pAg was kept at 8.6.
• the pH was adjusted to be 6.0 by making use of an aqueous (1.78N) potassium hydroxide solution and a desalting treatment was carried out in an ordinary method.
• Monodisperse type globular-shaped seed emulsion [A] was prepared in the following procedures.
• Solutions B and C were added to solution A vigorously stirred at 40°C in a double-jet method by taking 11 minutes, so that the nuclei could be produced. In the courses thereof, the pBr was kept at 1.60.
• the pH was adjusted to be 6.0 and a desalting treatment was then carried out in an ordinary method.
• the resulting seed emulsion was observed through an electron microscope, it was proved to be a globular-shaped emulsion having a couple of twin plane parallel to each other and an average grain size of 0.318 ⁇ m.
• the objective globular-shaped emulsion (A) could be prepared.
• Octahedral, twinned crystal and monodisperse type emulsion Em-3 was prepared by making use of the following 7 kinds of solutions.
• Fine grain emulsion comprising gelatin in a proportion of 3 wt% and silver iodide grains (having an average grain size of 0.05 ⁇ m) 0.844 mols
• Fine grain emulsion comprising (an average grain size of 0.04 ⁇ m) silver iodobromide grains each containing silver iodide content 1 mol%, that was prepared in the same manner as in the fine grains silver iodide emulsion of Solution D as described above, 2.20 mols, provided therein the temperature was controlled to be 3.0°C in the course of producing the fine grains.
• Solutions B, C and D were added by a double-jet method over a period of 163 minutes.
• Solution E was independently added at a constant rate over a period of 12 minutes, so that the seed crystals were grown up to be 1.0 ⁇ m in an average size.
• Solutions B and C were each added at an accelerated adding-rate to meet the critical growth rate and neither to produce any other smaller grains than the growing seed crystals nor to polydisperse the resulting emulsion in an Ostward ripening treatment.
• Solution D a fine silver iodide grain emulsion
• the addition rate ratio (mol ratio) thereof to the aqueous ammoniacal silver nitrate solution (Solution D) were changed in proportion to the grain sizes (or the adding time) as shown in the following Table 5. Thereby, a core/shell type silver halide emulsion having a multilayered structure was prepared.
• Solutions F and G By making use of Solutions F and G, the pAg and pH in the course of growing the crystals were controlled as shown in Table 5.
• the pAg and pH were measured in an ordinary method by making use of a silver sulfide electrode and a glass electrode.
• Emulsion Em-3 was prepared as described above.
• Emulsions Em-1 through Em-3 prepared in Example 1 were each subjected to the following chemical sensitization [A] through [D], so that Emulsions [1-A] through [3-D] could be prepared.
• Emulsion Em-1 was heated up to 65°C to be dissolved. Thereto added with sensitizing dyes (SD-1) in an amount of 1.2x10 -4 mols, (SD-3) in an amount of 1.5x10 -5 mols and (SD-2) in an amount of 1.4x10 -4 mols, each per mol of silver halide used. Thirty (30) minutes thereafter, sodium thiosulfate pentahydrate in an amount of 3.4x10 -6 mols was added and, further 10 minutes after, chloroauric acid in an amount of 3.6x10 -6 mols and ammonium thiocyanate in an amount of 5.0x10 -4 mols were mixedly added. A ripening treatment was then carried out for a suitable time.
• Emulsions Em-2 and Em-3 By making use of Emulsions Em-2 and Em-3, Emulsions [2-A] and [3-A] were each obtained in the same manner as in the case of the above-described Emulsion [1-A].
• Emulsion Em-1 was heated up to 65°C to be dissolved and a KBr solution was added to the resulting solution to adjust the pAg to be 10. Thereto added with sensitizing dyes (SD-1) in an amount of 1.2x10 -4 mols, (SD-3) in an amount of 1.5x10 -5 mols and (SD-2) in an amount of 1.4xI0 -4 mols, each per mol of silver halide used.
• SD-1 sensitizing dyes
• sodium thiosulfate pentahydrate was added in an amount of 2.0x10 -5 mols and, further 10 minutes after, chloroauric acid in an amount of 3.6x10 -6 mols and ammonium thiocyanate in an amount of 5.0x10 -4 mols were mixedly added thereto.
• a ripening treatment was then carried out for a suitable time.
• Emulsions Em-2 and Em-3 By making use of Emulsions Em-2 and Em-3, Emulsions [2-B] and [3-B] were each obtained in the same manner as in the case of the above-described Emulsion [1-B].
• Emulsion Em-1 was heated up to 65°C to be dissolved. Thereto added with sensitizing dyes (SD-1) in an amount of 1.2x10 -4 mols, (SD-3) in an amount of 1.5x10 -5 mols and (SD-2) in an amount of 1.4x10 -4 mols, each per mol of silver halide used. Thirty (30) minutes thereafter, 1-ethyl-3-thiazolylthiourea was added in an amount of 3.7x10 -6 mols and, further 10 minutes after, chloroauric acid in an amount of 3.6x10 -6 mols and ammonium thiocyanate in an amount of 5.0x10 -4 mols were mixedly added thereto. A ripening treatment was then carried out for a suitable time.
• SD-1 sensitizing dyes
• SD-3-thiazolylthiourea was added in an amount of 3.7x10 -6 mols and, further 10 minutes after, chloroauric acid in an amount of 3.6x
• Emulsions Em-2 and Em-3 By making use of Emulsions Em-2 and Em-3, Emulsions [2-C] and [3-C] were each obtained in the same manner as in the case of the above-described Emulsion [1-C].
• Emulsion Em-1 was heated up to 65°C to be dissolved and a KBr solution was added thereto to adjust the pAg to be 10. Thereto added with sensitizing dyes (SD-1) in an amount of 1.2x10 -4 mols, (SD-3) in an amount of 1.5x10 -5 mols and (SD-2) in an amount of 1.4x10 -4 mols, each per mol of silver halide used.
• SD-1 sensitizing dyes
• 1-ethyl-3-thiazolylthiourea was added in an amount of 3.7x10 -6 mols and, further 10 minutes after, chloroauric acid in an amount of 3.6x10 -6 mols and ammonium thiocyanate in an amount of 5.0x10 -4 mols were mixedly added thereto.
• a ripening treatment was then carried out for a suitable time.
• Emulsions Em-2 and Em-3 By making use of Emulsions Em-2 and Em-3, Emulsions [2-D] and [3-D] were each obtained in the same manner as in the case of the above-described Emulsion [1-D].
• Samples 101 through 112 were each prepared in the manner that Emulsions [1-A] through [3-D] prepared in the aforementioned procedures were coated and then dried on subbed triacetyl cellulose film supports in the following coating formula, respectively.
• the amounts of the materials thereof will be indicated in terms of grams per sq.meter, unless otherwise expressly stated.
• the silver halides used therein will be indicated in terms of the silver contents thereof.
• the resulting coated samples 101 through 112 were each exposed wegdewise to red light and were then developed at 20°C for 10 minutes with Kodak Formula MAA-1 developer. From the characteristic curves made out of the resulting developed samples, the minimum exposure amounts necessary to obtain the maximum densities were obtained, respectively.
• coated samples 101 through 112 were each exposed to light respectively having the light quantities each 50 times as much as the minimum light quantities necessary to obtain the maximum densities each already obtained as mentioned above.
• the exposed samples were developed and stopped in the following processing steps. Processing steps (at 20°C) Developing (with developer [A]) 15min.00sec. Stopping (in an aqueous 3% acetic acid solution) 2min.00sec. Washing 5min. Drying
• the resulting samples were each gelatin-decomposed by making use of enzyme.
• the development initiating points were observed by observing the silver halide grains of each sample through a high-resolution scanning type electron microscope (Model S-900 manufactured by Hitachi, Ltd.).
• Multilayered color photographic light sensitive material samples 201 through 212 were each prepared by coating each of the layers having the following compositions in the order from the side of a triacetyl cellulose film-made support, wherein Emulsions [1-A] through [3-D] prepared in Example 2 were used as the high speed red-sensitive emulsions for Layer 5, respectively.
• the amounts of each of the compositions added thereto will be indicated by grams per sq.meter.
• the colloidal silver amounts added thereto will be each indicated by the silver contents thereof.
• the sensitizing dye amounts added thereto will be indicated by mols per mol of the silver halides used therein.
• Layer 1 An antihalation layer (HC-1) Black colloidal silver 0.16 UV absorbent (UV-1) 0.20 High-boiling solvent (Oil-1) 0.16 Gelatin 1.23
• Layer 2 An intermediate layer Compound (SC-1) 0.15 High-boiling solvent (Oil-2) 0.17 Gelatin 1.27
• Layer 3 A low-speed red-sensitive layer Silver iodobromide emulsion (having an average grain size of 0.38 ⁇ m and a silver iodide content of 8.0 mol%) 0.50 Silver iodobromide emulsion (having an average grain size of 0.27 ⁇ m and a silver iodide content of 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8x10 -4 Sensitizing dye (SD-2) 1.9x10 -4 Sensitizing dye (SD-3) 1.9x10 -5 Sensitizing dye (SD-4) 1.0x10 -4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14
• compositions of the processing solutions each used in the above-mentioned processing steps were as follows.
• the resulting latent image preservabilities thereof were expressed by the relative values of their photosensitive speeds so that the control photosensitive speeds of these samples were each regarded as a value of 100.
• Table 7 shows the relative red sensitivities and those obtained after the latent images were each preserved.
• Table 7 Sample No. Relative speed* Latent image preservability** Remarks For 30 days at 23°C/55%RH For 3 days at 55°C/55%RH 201 100 77 70
• Invention * A relative speed when regarding the speed of sample 201 as a value of 100.
• ** A relative speed when regarding the control speed of each sample as a value of 100.
• the samples of the invention each can be higher in photosensitive speed and superior in latent image preservability, as compared to the comparative samples, when the samples of the invention contain such an emulsion containing the silver halide grains having one or two development initiating points, in each of the grains, in an amount of not less than 75% of the whole grain of the emulsion.
• samples 301 through 312 each provided with a single-coated layer were prepared by making use of the emulsions prepared in the same manners as in Samples 101 through 112, except that the sensitizing dyes were replaced by the sensitizing dyes used in Layer 9 of Example 3, respectively.
• samples 401 through 412 each provided with a single-coated layer were prepared by making use of the emulsions prepared in the same manners as in Samples 101 through 112, except that the sensitizing dyes were replaced by the sensitizing dyes used in Layer 14 of Example 3, respectively.
• Multilayered sample 501 was prepared by making use of the emulsion used in Layer 5 of Sample 209, the emulsion used in Layer 9 of Sample 309 and the emulsion used in Layer 14 of Sample 409, each prepared in Example 3.
• multilayered samples 502, 503 and 504 were each prepared by making use of the emulsion used in Samples 210, 310 and 410, the emulsion used in Samples 211, 311 and 411, and the emulsion used in Samples 212, 312 and 412, respectively.
• the silver halide photographic emulsions of the invention can display a high photosensitive speed and an excellent latent image preservability.
• the light sensitive material applied therewith can also similarly display the excellent advantages.

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• 1992
  • 1992-06-01 JP JP4163392A patent/JPH05333464A/ja active Pending
• 1993
  • 1993-05-26 DE DE1993609539 patent/DE69309539T2/de not_active Expired - Fee Related
  • 1993-05-26 EP EP19930108510 patent/EP0572912B1/en not_active Expired - Lifetime

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