EP0378236B1 - Silver halide color photographic light-sensitive material - Google Patents

Silver halide color photographic light-sensitive material Download PDF

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Publication number
EP0378236B1
EP0378236B1 EP90100640A EP90100640A EP0378236B1 EP 0378236 B1 EP0378236 B1 EP 0378236B1 EP 90100640 A EP90100640 A EP 90100640A EP 90100640 A EP90100640 A EP 90100640A EP 0378236 B1 EP0378236 B1 EP 0378236B1
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Prior art keywords
silver
silver halide
grains
grain
emulsion
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EP90100640A
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German (de)
English (en)
French (fr)
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EP0378236A1 (en
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Mikio Fuji Photo Film Co. Ltd. Ihama
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • 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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element

Definitions

  • the present invention relates to a silver halide color photographic light-sensitive material.
  • a compound which releases a development inhibitor in correspondence with an image density upon development is added to a photographic light-sensitive material.
  • This compound generally coupling-reacts with the oxidized form of a color developing agent and releases a development inhibitor.
  • Typical examples of a compound of this type are a compound which is coupled with the oxidized form of a color developing agent to form a dye and releases a development inhibitor as described in, e.g., U.S. Patents 3,148,062, 3,227,554, 3,701,783, and 3,733,201; and a compound which is coupled with the oxidized form of a color developing agent to release a development inhibitor without forming a dye as described in U.S.
  • Patents 3,632,345 and 3,928,041, and JP-A-49-77635, JP-A-49-104630, JP-A-50-36125, JP-A-50-15273, and JP-A-51-6724 ("JP-A" means unexamined published Japanese patent application). These compounds can effectively form a fine-grain image, improve the sharpness of an image by an edge effect, improve color reproduction by an interlayer effect, and enable to control the tone of an image.
  • EP-A-0326853 discloses silver halide photographic emulsions comprising a dispersion medium and silver halide grains, the silver halide grains of which include a silver halide localized region microscopically uniformly containing at least 3 mol% silver iodide.
  • This patent also relates to color photographic materials employing such emulsions. These materials may additionally comprise DIR compounds capable of releasing a development inhibitor along with coupling.
  • a silver halide color photographic light-sensitive material comprising at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive colloid layer on a support
  • said light-sensitive silver halide emulsion layer comprising silver halide grains containing a microscopically uniform silver halide localized region containing not less than 3 mol% of silver iodide, wherein said silver halide localized region has at most two lines indicating a microscopic silver iodide non-uniform distribution at an interval of 0.2 ⁇ m in a direction perpendicular to the lines in a transmission image of-the grains obtained by using a cryo-transmission electron microscope and the number of the silver halide grains having such a silver halide localized region account for at least 60% of the number of all the grains in the emulsion, said light-sensitive silver halide emulsion layer or said non-light-sensitive colloid layer containing at least one
  • the silver halide grains used in the silver halide color photographic light-sensitive material according to the present invention may be formed by supplying fine silver halide grains, formed beforehand by supplying and mixing an aqueous water-soluble silver salt solution and an aqueous halide solution into a mixer vessel provided outside a reactor vessel for causing nucleation and/or crystal growth, to the reactor vessel to cause nucleation and/or crystal growth of silver halide grains.
  • Silver halide grains used in the present invention will be described in detail below.
  • the crystal habit of the silver halide grains used in the present invention may or may not be a regular crystal, and may or may not have an internal structure.
  • the grain size distribution of the silver halide grains may be wide or narrow.
  • the total composition of the silver halide grains is silver iodobromide, silver iodochloride, or silver iodochlorobromide, and preferably silver iodobromide or silver iodochlorobromide.
  • the silver halide grains used in the present invention have a silver halide localized region microscopically uniformly containing silver iodide. In this case, 3 to 45 mol%, and preferably, 5 to 35 mol% of silver iodide are contained in the localized region.
  • the localized region can be present as a continuous or non-continuous phase inside a grain or on the surface of a grain. When the entire grain has only one phase without having an internal structure, this phase is considered as a localized region.
  • This localized region may be present at either a core or shell portion of a silver halide grain, may be non-continuously present at a corner of a cubic grain, and may be present at an edge or corner of a tabular grain.
  • the localized region need only be present at least at one position. A plurality of localized regions having different halogen compositions such as different silver iodide contents may be present.
  • 3 mol% or more of silver iodide are microscopically uniformly contained in the localized region of the silver halide grains.
  • This microscopic distribution of the silver iodide can be observed by a direct method at a low temperature using a transmission electron microscope as described in J.F. Hamilton, "Photographic Science and Engineering", Vol. 11, 1967, P. P57 or Takeaki Shiozawa, "Japan Photographic Society", Vol. 35, No. 4, 1972, P. P213. That is, silver halide grains, which have been extracted under safe light so that emulsion grains are not printed out, are placed on a mesh for electron microscopic observation, and this sample is observed by a transmission method while it is cooled by liquid nitrogen or liquid helium so as to prevent a damage (e.g., print out) caused by an electron beam.
  • a damage e.g., print out
  • the accelerated voltage is preferably 200 kV for a grain thickness of up to 0.25 ⁇ m, and is preferably 1,000 kV for a grain thickness exceeding this value. Since a damage to grains caused by an electron beam is increased as the accelerated voltage is increased, it is more preferable to cool the sample by liquid helium than by liquid nitrogen.
  • the photographing magnification can be arbitrarily changed in accordance with the grain size of a sample, it is 20,000 to 40,000 times.
  • Fig. 1 shows an example of this stripe pattern.
  • the tabular grain shown in the Fig. 1 is a tabular core/shell grains prepared by forming silver iodobromide shell containing 10 mol% of silver iodide as a shell around a tabular silver bromide grain core. This structure can be clearly observed by the transmission electron microscopic photograph. That is, since the core portion consists of silver bromide and therefore is naturally uniform, only a uniform flat image is obtained.
  • the annual ring-like stripe pattern indicating the non-uniformity of a silver iodide distribution of a tabular silver iodobromide emulsion grains described above is clearly observed also in a transmission electron microscopic photograph attached to JP-A-58-113927 obtained by measuring a silver iodide distribution by using a 0.2 ⁇ m electron beam spot.
  • This pattern is also clearly shown in a transmission electron microscopic photograph in topography studies of a silver iodide content in a silver iodobromide tabular grain described in M.A. King, M.H. Lorretto, T.J. Maternaghan, and F.J.
  • silver iodobromide grains prepared to have a determined silver iodide content in order to obtain a uniform silver iodide distribution have a very microscopically non-uniform distribution of silver iodide, contrary to its manufacture purpose.
  • an emulsion having a microscopically uniform silver iodide distribution is used.
  • a silver halide grain containing a silver halide localized region having a "microscopically uniform silver iodide distribution" used in the present invention can be clearly distinguished from a conventional silver halide grain by observing a transmission image of the grain by using a cooling type transmission electron microscope. That is, the silver halide localized region containing silver iodide of the grains used in the present invention has two or less, preferably one, and more preferably no microscopic line caused by the microscopic non-uniformity of silver iodide at an interval of 0.2 ⁇ m in the direction perpendicular to the line.
  • Lines constituting the annual ring-like stripe pattern indicating the microscopic non-uniformity of silver iodide are formed in a direction perpendicular to a grain growth direction and distributed concentrically from the center of a grain.
  • lines constituting the annual ring-like stripe pattern indicating the non-uniformity of silver iodide are perpendicular to a growth direction of the tabular grain, they are parallel to the edge of the grain.
  • a direction perpendicular to the lines is directed toward the center of the grain, the lines are distributed concentrically around the center.
  • the silver iodide content When the silver iodide content is substantially continuously changed during the growth of grains, the silver iodide content does not change abruptly. Therefore, no lines indicating the variation of the microscopic silver iodide content as described above are observed. Therefore, if at least three or more lines are present at an interval of 0.1 ⁇ m, the microscopic non-uniformity of a silver iodide content is present.
  • a silver halide localized region having a microscopically uniform silver iodide distribution is a grain having at most only two lines indicating a microscopic silver iodide distribution at an interval of 0.2 ⁇ m in a direction perpendicular to the lines in a transmission image of the grain obtained by using a cryo-transmission electron microscope.
  • the silver halide grain has preferably one, and more preferably, no such lines.
  • Such silver halide grains account for at least 60%, preferably, at least 80%, and more preferably, at least 90% of all the grains.
  • the microscopic uniformity of a halide distribution of a silver halide mixed crystal can be measured by utilizing X-ray diffraction.
  • a method of determining a halide composition by using an X-ray diffractometer is known to those skilled in the art.
  • the half-value width of a diffraction profile of a system in which no strain is caused by an external stress as in the form of a sample described in the present invention is determined not only by a halide distribution. That is, this half-value width includes, in addition to the above half-value width, the half-value width caused by an optical system of a diffractometer and the half-value width caused by the size of a crystallite of a sample. Therefore, in order to obtain the half-value width caused by a halide composition distribution, the contribution of the two half-value widths must be subtracted.
  • the half-value width by an optical system of a diffractometer can be obtained as the half-value width of a diffraction profile of a single crystal having no strain (not having a lattice constant variation) and having a grain size of 25 ⁇ m or more.
  • a material prepared by annealing ⁇ -quartz of 25 to 44 ⁇ m size (500 mesh on, 350 mesh under) at 800°C can be used. This is described in "X-ray Diffraction Handbook", revised, reprint, Chapter II, Paragraph 8, Rigaku Denki K.K. E.g., Si grains and a Si single-crystal wafer can also be used.
  • the half-value width by an optical system Since the half-value width by an optical system has a dependency on diffraction angle, it must be obtained at a plurality of points of diffraction profile. If necessary, extrapolation or interpolation is performed to obtain the half-value width by an optical system at a diffraction angle of a measuring system.
  • the half-value width by a halide composition distribution is obtained by subtracting the half-value widths by the optical system and the size of a crystallite, which are obtained by the above method, from the half-value width of the measured diffraction profile.
  • the half-value width by an optical system and the half-value width by the size of a crystallite for a mixed crystal grain to be measured are equal to the half-value width of a diffraction profile of a silver halide grain having the same crystallite size as the grain of interest and having a uniform halide composition distribution (that is, having constant lattice constant).
  • the size (e.g., an edge length and an equi-volume sphere-equivalent diameter) of a grain not having a lattice defect coincides with the size of a crystallite.
  • F.W. Willets reports that, although not in a diffractometer method but in a photographic method, the size of a crystallite of AgBr obtained by a diffraction ray width coincides with the size of the grain, in "British Journal of Applied Physics", 1965, Vol. 16, P. 323. In this report, not the half-value width but the standard deviation of a profile is used and 1.44 is selected as a sheller constant in the photographic method.
  • a diffractometer is used and it is found that the size of a crystallite obtained by the half-value width obtained by subtracting the half-value width by an optical system obtained by using a Si single crystal coincides well with the size of the grain in the case of AgBr grains prepared by a balanced double jet method.
  • the half-value width by an optical system and the half-value width by the size of a crystallite for a mixed crystal emulsion grain can be obtained as the half-value width of the diffraction profile of an AgBr grain, an AgCl grain, and an AgI grain having the same grain size as the mixed crystal emulsion grain.
  • the half-value width by only the halide composition distribution of the mixed crystal emulsion grain can be obtained by subtracting the half-value width of the diffraction profile of the AgBr grain, the AgCl grain, and the AgI grain having the same grain size as the interest grain from the half-value width of the measured diffraction profile.
  • the preferable half-value width of an X-ray diffraction profile of the silver iodobromide emulsion grain having the uniform microscopic halide composition used in the present invention obtained by the method described above is shown in Fig. 6.
  • the uniformity of a grain of the halide composition is represented by the value obtained by subtracting the half-value width of pure silver bromide having the same grain size from the half-value width of X-ray diffraction of the grain.
  • the grain used in the present invention has a half-value width indicated by the curve A or less, and preferably, a half-value width indicated by the curve B or less.
  • the silver halide grain conventionally called a silver halide grain uniformly containing silver iodide is simply prepared by adding silver nitrate and a mixture of halide salts having a determined composition (determined iodide content) to a reactor vessel upon growth of the grains in a double jet method.
  • a determined composition determined iodide content
  • the macroscopic silver iodide distribution is constant, the microscopic silver iodide distribution is not uniform.
  • such a grain is called a grain having a "determined halide composition" and is clearly distinguished from the "microscopically uniform" grain used in the present invention.
  • the silver iodide content in the localized region can be obtained by analysis using an electron microscope.
  • a very thin sample piece is cut from a portion to be measured as needed before measurement and measured by using a transmission electron microscope equipped with an energy dispersion type X-ray diffraction apparatus under cooling by liquid nitrogen at an acceleration voltage of 75 kV with a radiation current of 2.5 ⁇ A.
  • the silver iodide content of the localized region is 3 mol% or less, the influence of the microscopically non-uniform distribution is small.
  • an outermost layer of a silver halide grain is a localized region containing silver iodide.
  • the silver iodide content of the outermost layer is less than 3 mol%, the obtained sensitivity, fog, and rate of development are not much influenced regardless whether the silver iodide distribution of the silver halide phase is "microscopically uniform".
  • the silver iodide content of the silver halide phase of the outermost layer containing the silver iodide is 3 mol% or more, and particularly, 5 mol% or more, only a very low reached sensitive and a low rate of development can be obtained upon chemical sensitization by using conventional grains having a non-uniform silver iodide distribution. That is, the chemical sensitization of a grain having a silver halide phase of a conventional "determined halide composition of silver iodide" in its outermost layer is interfered.
  • the silver halide phase containing silver iodide is present inside the grain and the silver iodide content in the outermost layer is low or no silver iodide is present therein, it is assumed that a band structure is expected to be bent in the interface between the two phases, holes produced by light absorption caused by bending are directed toward the interior of the grain to accelerate the charge separation between electrons and holes, and silver iodide in the grain traps the holes to prevent recombination with the electrons, thereby increasing the sensitivity. It is found that the photographic sensitivity is high when the silver iodide distribution inside the grain is microscopically uniform and is low when the silver iodide distribution is non-uniform.
  • the obtained sensitivity is substantially not changed even if the uniformity of the silver iodide distribution is different.
  • the silver iodide content is 3 mol% or more, and particularly, 5 mol% or more, a grain having a microscopically uniform silver iodide distribution apparently has a higher sensitivity than that of a grain having a microscopically non-uniform silver iodide distribution.
  • the total silver iodide content of the emulsion grains used in the present invention is 2 mol% or more.
  • the total silver iodide content is preferably 4 mol% or more, and more preferably, 5 mol% or more.
  • the size of the silver halide emulsion grain containing a silver halide localized region having a microscopically uniform silver iodide distribution is not particularly limited, it is preferably 0.3 ⁇ m or more, more preferably, 0.8 ⁇ m or more, and most preferably, 1.4 ⁇ m or more.
  • the shape of the silver halide grain used in the present invention may be a regular crystal shape (regular crystal grain) such as a cube, an octahedron, a dodecahedron, a tetradecahedron, an icositetrahedron (a tri octa hedron, a tetra hexa hedron, and a rhombic icositetrahedron), and a tetrahexahedron, or an irregular crystal shape such as a sphere and a potato-like shape.
  • the silver halide grain may take various shapes having one or more twinned crystal faces, and more particularly, may be a hexagonal tabular grain or a triangular tabular grain having two or three parallel twinned crystal faces.
  • the method for preparing the grains is characterized in that except for adjustment of a pAg of an emulsion in the reactor vessel, no aqueous silver salt solution nor aqueous halide solution is added to a reactor vessel to perform nucleation and/or grain growth, and circulation of an aqueous protective colloid solution (containing silver halide grains) from the reactor vessel to a mixer vessel is not performed at all.
  • a system for grain formation as shown Fig. 2 can be preferably used in the present invention (a method of supplying fine silver halide grains immediately from a mixer vessel is called a "method A" hereinafter).
  • reference numeral 1 denotes a reactor vessel
  • 2 denotes an aqueous protective colloid solution
  • 3 denotes a propeller
  • 4 denotes an aqueous halide salt solution adding system
  • 5 denotes an aqueous silver salt solution adding system
  • 6 denotes a protective colloid adding system
  • 7 denotes a mixer vessel.
  • the reactor vessel 1 contains an aqueous protective colloid solution 2.
  • the aqueous protective colloid solution is stirred and mixed by a propeller 3 mounted on a rotating shaft.
  • a propeller 3 mounted on a rotating shaft.
  • an aqueous silver salt solution, an aqueous halide solution, and an aqueous protective colloid solution are introduced in the mixer vessel 7 located outside the reactor vessel by adding systems 4, 5, and 6, respectively (in this case, the aqueous protective colloid solution may be mixed in the aqueous halide solution and/or the aqueous silver salt solution and then added).
  • Fig. 3 shows the mixer vessel 7 in detail.
  • FIG. 3 reference numerals 4, 5, and 7 have the same meanings as in Fig. 1 and 8 denotes an introducing system for the reactor vessel, 9 denotes a stirring blade, 10 denotes a reactor chamber, and 11 denotes a rotating shaft.
  • the mixer vessel 7 has an internal reactor chamber 10. Stirring blades 9 mounted on a rotating shaft 11 are provided inside the reactor chamber 10.
  • the aqueous silver salt solution, aqueous halide salt solution, and aqueous protective colloid solution are added from three introducing ports (4 and 5, the remaining one is omitted from the drawing) to the reactor chamber 10.
  • the solution which is rapidly and strongly mixed and contains very fine grains by rotation of the rotating shaft at high speed (1,000 rpm or more, preferably, 2,000 rpm or more, and more preferably, 3,000 rpm or more), is exhausted from the external exhaust port 8.
  • a halide composition of the very fine grains is set to the same as that of an interest silver halide localized region in the silver halide grains.
  • the very fine grains introduced in the reactor vessel are scattered therein upon stirring, and halide ions and silver ions of the intented halide composition are released from each very fine grain.
  • the grains formed by the mixer vessel are very fine, and the number of the grains is very large.
  • silver and halide ions (having an intented halide ion composition in the case of growth of a mixed crystal) are released from each grain, and this reaction occurs throughout the protective colloid in the reactor vessel. Therefore, a microscopically uniform growth of grains can be achieved.
  • the fine grains formed as described above normally have substantially the same size as that of a so-called Lippmann emulsion.
  • the average grain size of the grains is 0.1 ⁇ m or less.
  • the fine grains formed in the mixer vessel have a high solubility since their grain size is very small. Therefore, when the grains are added to the reactor vessel, they are converted into silver and halide ions and precipitate on grains already existing in the reactor vessel to cause grain growth. During grain growth, the fine grains cause Ostwald ripening therebetween since they have a high solubility, thereby increasing the grain size. When the grain size of the fine grains is increased, the solubility is decreased to decelerate dissolution in the reactor vessel. When the speed of the grain growth is significantly low, the some grains are not dissolved but become a core to cause growth.
  • a low molecular weight gelatin is used as the protective colloid.
  • An average molecular weight of gelatin is preferably 30,000 or less, and more preferably, 10,000 or less.
  • the low molecular weight gelatin for use in the method used in the present invention can be normally prepared as follows. That is, gelatin which is normally used and has an average molecular weight of 100,000 is dissolved in water, and a gelatin-decomposing enzyme is added to the resultant aqueous gelatin solution, thereby decomposing gelatin molecules by the enzyme.
  • a gelatin-decomposing enzyme is added to the resultant aqueous gelatin solution, thereby decomposing gelatin molecules by the enzyme.
  • R.J. Cox. "Photographic Gelatin II", Academic Press, London, 1976, PP. 233 to 251 and PP. 335 to 346 is helpful. Since the bonding position to be decomposed by the enzyme is predetermined, low molecular weight gelatin having a comparatively narrow molecular weight distribution is preferably obtained. As the enzyme decomposition time is prolonged, the molecular weight is reduced.
  • the protective colloid when the protective colloid is to be added to the mixer vessel, its concentration is 0.2 wt% or more, preferably 1 wt% or more, and more preferably, 2 wt% or more.
  • the protective colloid when the protective colloid is to be added to the aqueous silver nitrate solution and/or aqueous halide solution, its concentration is 0.2 wt% or more, preferably, 1 wt% or more, and more preferably, 2 wt% or more.
  • the concentration of the aqueous protective colloid solution in the vessel (another reactor vessel or the mixer vessel of the present invention) upon preparation of the fine grain emulsion is 0.2 wt% or more, preferably, 1 wt% or more, and more preferably, 2 wt% or more.
  • the temperature of the mixer vessel is 40°C or less, and preferably, 35°C or less.
  • the temperature of the reactor vessel is 50°C or more, preferably, 60°C or more, and more preferably, 70°C or more.
  • the grain formation temperature of the fine grain emulsion prepared beforehand is 40°C or less, and preferably, 35°C or less.
  • the temperature of the reactor vessel to which the fine grain emulsion is added is 50°C or more, preferably 60°C or more, and more preferably, 70°C or more.
  • the grain size of the fine grain silver halide for use in the present invention can be confirmed by observing a grain placed on a mesh by a transmission electron microscope. In this case, a magnification is preferably 20,000 to 40,000 times.
  • the grain size of the fine grains used in the present invention is 0.06 ⁇ m or less, preferably, 0.03 ⁇ m or less, and more preferably, 0.01 ⁇ m or less.
  • a silver halide solvent is added to the reactor vessel, a higher fine grain dissolution speed and a higher growth speed of grains in the reactor vessel can be obtained.
  • silver halide solvent examples include a water-soluble bromide, a water-soluble chloride, a thiocyanate, ammonia, thioether, and thioureas.
  • examples of the silver halide solvent are thiocyanates (e.g., U.S. Patents 2,222,264, 2,448,534, and 3,320,069); ammonia; thioether compounds (e.g., U.S.
  • thion compounds e.g., JP-A-53-144319, JP-A-53-82408, and JP-A-55-77737
  • an amine compound e.g., JP-A-54-100717
  • a thiourea derivative e.g., JP-A-55-2982
  • the halide composition of the emulsion prepared by the method used in the present invention may be any of silver iodobromide, silver chlorobromide, silver chloroiodobromide, and silver chloroiodide.
  • Silver halide mixed crystal grains having a uniform microscopic distribution of a halide, i.e., "perfectly uniform" silver halide mixed crystal grains can be obtained as described in Japanese Patent Application Nos. 63-195778, 63-7851, 63-7852, 63-7853, 63-7451, and 63-7449.
  • the grains can be obtained for any halide composition.
  • the method used in the present invention is very effective in the manufacture of pure silver bromide or pure silver chloride.
  • the conventional manufacturing method local distributions of silver ions and halide ions are inevitable in a reactor vessel. Therefore, the silver halide grains in the reactor vessel are placed in an environment different from another uniform portion through such a local non-uniform portion. As a result, not only the non-uniformity of growth is caused, but also reduced silver or fogged silver is produced at the portion having a high silver ion concentration. Therefore, in silver bromide and silver chloride, although the non-uniform distribution of the halide is not caused, non-uniformity of another sense as described above is caused. This problem, however, can be perfectly solved by the method used in the present invention.
  • the grain growth is performed in accordance with the following arrangement.
  • silver chloride need only be added to the above arrangement.
  • the silver chloride containing layer may be any of the 1st, 2nd, and 3rd coating layers.
  • the ratio of the microscopically uniform AgBrI phase in the grains is preferably 5 to 95 mol%.
  • development inhibitor releasing compound e.g. represented by the following formula:
  • a (or B)-P-Z wherein A represents a coupling component which reacts with the oxidized form of a color developing agent to release -P-Z, B represents a redox component which undergoes oxidation-reduction reaction with the oxidized form of a color developing agent and alkali hydrolysis to release -P-Z, Z represents a development inhibitor or a precursor of a development inhibitor, -P-Z represents a group which is cleaved from A or B and reacts with the oxidized form of a colour developing agent to release Z, and P represents a moiety which undergoes a bimolecular reaction with the oxidized form of a colour developing agent to release Z.
  • Z may be a diffusible development inhibitor or a development inhibitor having a slightly diffusible property.
  • the diffusible property of -P-Z the distance which diffusion-resistant compound A (or B)-P-Z can exert its inter-layer effect can be changed.
  • the development inhibitor represented by Z includes a development inhibitor as described in Research Disclosure, Vol. 176, No. 17643, (December, 1978).
  • the development inhibitor are mercaptotetrazole, selenotetrazole, mercaptobenzothiazole, selenobenzothiazole, mercaptobenzooxazole, selenobenzooxazole, mercaptobenzimidazole, selenobenzimidazole, benzotrrazole, mercaptotriazole, mercaptooxadiazole, mercaptothiadiazole, and their derivatives.
  • Preferable development inhibitors are represented by the following formulas:
  • R11 and R12 each represent alkyl, alkoxy, acylamino, a halogen atom, alkoxycarbonyl, thiazolilideneamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, sulfonamido, N-alkylcarbamoyloxy, ureido, hydroxy, alkoxycarbonylamino, aryloxy, alkylthio, arylthio, anilino, aryl, imido, a heterocyclic ring, cyano, alkylsulfonyl, or aryloxycarbonylamino.
  • n 1 or 2.
  • R11 and R12 may be the same or different.
  • the total number of the carbon atoms contained in n R11 and R12 is 0 to 20.
  • R13, R14, R15, R16, and R17 each represent alkyl, aryl, or a heterocyclic group.
  • each of R11 to R17 represents an alkyl group
  • the alkyl may be substituted or nonsubstituted, or chained or cyclic.
  • substituting group are a halogen atom, nitro, cyano, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, sulfamoyl, carbamoyl, hydroxy, alkanesulfonyl, arylsulfonyl, alkylthio, and arylthio.
  • R11 to R17 each represent an aryl group
  • the aryl may be substituted.
  • substituting group are alkyl, alkenyl, alkoxy, alkoxycarbonyl, a halogen atom, nitro, amino, sulfamoyl, hydroxy, carbamoyl, aryloxycarbonylamino, alkoxycarbonylamino, acylamino, cyano, and ureido.
  • R11 to R17 each represent a heterocyclic group, it represents a 5- or 6-membered single- or condensed-ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom.
  • the heterocyclic group are pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imido, and oxadine. These compounds may be substituted by the substituting groups enumerated above for the aryl group.
  • the number of carbon atoms contained in R11 and R12 is 1 to 20, and more preferably, 7 to 20.
  • the total number of carbon atoms contained in R13 to R17 is 1 to 20, and more preferably, 4 to 20.
  • a preferable development inhibitor is a compound which is released upon reaction with the oxidized form of a color developing agent and diffuses from a layer in which it is contained upon development to another layer, thereby exhibiting a development inhibiting effect.
  • a compound having a small diffusing property is also used.
  • coupler component represented by A examples include dye forming couplers such as acylacetoanilides, malondiesters, malondiamides, benzoylmethanes, pyrazolones, pyrazolotriazoles, pyrazolobenzimidazoles, indazolones, phenols, and naphthols; and coupler components essentially not forming a dye such as acetophenones, indanones, and oxazolones.
  • couplers such as acylacetoanilides, malondiesters, malondiamides, benzoylmethanes, pyrazolones, pyrazolotriazoles, pyrazolobenzimidazoles, indazolones, phenols, and naphthols
  • coupler components essentially not forming a dye such as acetophenones, indanones, and oxazolones.
  • Examples of the preferable coupler components are formulas (V) to (IX).
  • R30 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and each of R31 and R32 independently represents an aromatic group or a heterocyclic group.
  • the aliphatic group represented by R30 preferably has 1 to 20 carbon atoms, and is substituted or nonsubstituted and chained or cyclic.
  • Examples of the preferable substituting groups on the alkyl group are groups of alkoxy, aryloxy, and acylamino.
  • R30, R31, or R32 is an aromatic group, it represents, e.g., phenyl or naphthyl.
  • phenyl is effective.
  • a phenyl group may have a substituting group. Examples of the substituting groups are alkyl, alkenyl, alkoxy, alkoxycarbonyl, and alkylamido having 30 or less carbon atoms.
  • Phenyl represented by R30, R31, and R32 may be substituted by alkyl, alkoxy, cyano, or a halogen atom.
  • R33 represents, e.g., a hydrogen atom, alkyl, a halogen atom, carbonamido, or a sulfonamido, and l represents an integer of 1 to 5.
  • Each of R34 and R35 independently represents hydrogen, alkyl or aryl. Phenyl is preferred as aryl.
  • Alkyl and aryl may have substituting groups. Examples of the substituting groups are a halogen atom, alkoxy, aryloxy, and carboxyl.
  • R34 and R35 may be the same or different.
  • P is preferably a group serving as a redox group or coupler after itM s cleaved from A or B.
  • Patent 4,248,962 JP-A-56-114946, JP-A-57-154234, JP-A-58-98728, JP-A-58-209736, JP-A-58-209737, JP-A-58-209738, JP-A-58-209740, Japanese Patent Application No. 59-278,853, JP-A-61-255342, and JP-A-62-24252.
  • development inhibitor releasing compounds are added in amounts of 0.0001 to 0.5 mol, and preferably, 0.01 to 0.3 mol per mol of silver in the light-sensitive silver halide emulsion layer, or if the compounds are to be added to a non-light-sensitive colloid layer, per mol of silver in adjacent light-sensitive silver halide emulsion layers.
  • the development inhibitor releasing compounds of the present invention may be used in combination of two or more thereof.
  • the most significant effect can be obtained when the development inhibitor releasing compounds are added to a layer using emulsion grains containing microscopically uniform silver iodide.
  • a compound which releases a development inhibitor as a split-off group having a large diffusion property is preferable. More specifically, the diffusion property of a development inhibitor, described in JP-A-59-129849, is preferably 0.4 to 0.95. If the layers of the multilayered light-sensitive material contain the emulsion used in the invention, it suffices to use the development inhibitor releasing compound in at least one of the layers, thereby to attain the object of the invention.
  • the above development inhibitor releasing compounds can be introduced to a light-sensitive silver halide emulsion layer and/or a non-light-sensitive colloid layer by known methods to be described in detail later, e.g., a method described in U.S Patent 2,322,027.
  • the silver halide multilayered color photographic light-sensitive material of the present invention preferably has a multilayered structure in which the emulsion layers containing binders and silver halide grains for independently recording blue light, green light, and red light are stacked.
  • Each emulsion layer preferably consists of at least two layers, i.e., high- and low-sensitivity layers. Examples of a most practical layer arrangement are:
  • B represents a blue-sensitive layer
  • G a green-sensitive layer
  • R a red-sensitive layer
  • H a high-sensitivity layer
  • M a medium-sensitivity layer
  • L a low-sensitivity layer
  • S a support.
  • Non-light-sensitive layers such as a protective layer, a filter layer, an interlayer, an antihalation layer, and a subbing layer are omitted from the above layer arrangements.
  • a preferable layer arrangement is (1), (2), or (4).
  • CL represents an interlayer effect imparting layer
  • the other reference symbols are as described above.
  • an emulsion used in the present invention is used in at least one layer of BH, BL, GH, GL, RH, and RL.
  • an emulsion used in the present invention having an aspect ratio of 5 to 8 is used in BH and BL, and an emulsion used in the present invention having an aspect ratio of 5 or less is used in GH, GL, RH, and RL.
  • An emulsion used in the present invention having an aspect ratio of 5 or less is preferably used in all of GH, GL, RH, and RL.
  • Monodisperse silver halide grains may be used in BH as disclosed in Japanese Patent Application No. 61-157656.
  • a monodisperse emulsion may be used in a low-sensitivity layer.
  • the monodisperse emulsion may contain twinned or regular crystals, and preferably, regular crystals.
  • Two or more different types of emulsions may be mixed in a single layer. For example, any mixing such as mixing of monodisperse emulsions or tabular emulsions having different grain sizes can be performed.
  • the layer arrangement is (5), an emulsion used in the present invention is preferable used in also CL.
  • an emulsion used in the present invention especially, an emulsion having an aspect ratio of 5 or less is preferably used in CL.
  • emulsions for use in layers except for CL are similar to those used in (1).
  • high- and low-sensitivity layers having the same color sensitivity may be arranged in a reverse order. If high-, medium-, and low-sensitivity layers are present, all possible arrangements may be allowed.
  • Additives RD No.17643 RD No.18716 1. Chemical sensitizers page 23 page 648, right column 2. Sensitivity increasing agents do 3. Spectral sensitizers, super sensitizers pages 23-24 page 648, right column to page 649, right column 4. Brighteners page 24 5. Antifoggants and stabilizers pages 24-25 page 649, right column pages 24-25 6. Light absorbent, filter dye, ultraviolet absorbents pages 25-26 page 649, right column to page 650, left column 7. Stain preventing agents page 25, right column page 650, left to right columns 8. Dye image stabilizer page 25 9. Hardening agents column page 26 page 651, left 10. Binder page 26 do 11. Plasticizers, lubricants page 27 page 650, right column 12. Coating aids, surface active agents pages 26-27 do 13. Antistatic agents page 27 do
  • a compound which can react with and fix formaldehyde as described in U.S. Patent 4,411,987 or 4,435,503 is preferably added to the light-sensitive material.
  • various color couplers can be used in the light-sensitive material. Specific examples of these couplers are described in the above-described Research Disclosure, No. 17643, VII-C to VII-G as patent references.
  • yellow couplers are described in, e.g., U.S. Patents 3,933,501, 4,022,620, 4,326,024, and 4,401,752, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968, 4,314,023, and 4,511,649, and EP 249,473A.
  • magenta couplers are preferably 5-pyrazolone and pyrazoloazole compounds, and more preferably, compounds described in, e.g., U.S. Patents 4,310,619 and 4,351,897, EP 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 2422 (June 1984), JP-A-60-33552, RD No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, and U.S. Patents 4,500,630, 4,540,654, and 4,556,630.
  • cyan couplers are phenol and naphthol couplers, and preferably, those described in, e.g., U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, EP 121,365A and 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199, and JP-A-61-42658.
  • OLS West German Patent Application
  • the colored couplers for correcting additional, undesirable absorption of a colored dye are those described in Research Disclosure No. 17643, VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258, and British Patent 1,146,368.
  • couplers capable of forming colored dyes having proper diffusibility are those described in U.S. Patent 4,366,237, British Patent 2,125,570, EP 96,570, and West German Patent Application (OLS) No. 3,234,533.
  • Couplers releasing a photographically useful moiety upon coupling are preferably used in the present invention.
  • couplers imagewise releasing a nucleating agent or a development accelerator upon development are those described in British Patent 2,097,140, 2,131,188, and JP-A-59-157638 and JP-A-59-170840.
  • the couplers for use in this invention can be introduced in the light-sensitive materials by various known dispersion methods.
  • phthalic esters e.g., dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, bis(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthalate, and bis(1,1-diethylpropyl)phthalate
  • phosphates or phosphonates e.g., triphelphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridodecylphosphate, tributoxyethylphosphate, trichloropropylphosphate, and di-2
  • An organic solvent having a boiling point of about 30°C or more, and preferably, 50°C to about 160°C can be used as a co-solvent.
  • Typical examples of the co-solvent are ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexanone, 2-ethoxyethylacetate, and dimethylformamide.
  • the present invention can be applied to various color light-sensitive materials.
  • the material are a color negative film for a general purpose or a movie, a color reversal film for a slide or a television, color paper, a color positive film, and color reversal paper.
  • the color photographic light-sensitive materials of this invention can be processed by the ordinary processes as described, for example, in the above-described Research Disclosure, No. 17643, pages 28 to 29 and ibid., No. 18716, page 651, left to right columns.
  • a conventional color negative light-sensitive material processing method can be adopted (e.g., CN-16 and CN-16Q available from Fuji Photo Film Co., Ltd.; C-41 and C-41RA available from Eastman Kodak Co.; and CNK-4 available from KONICA CORP.)
  • the developing agent As the developing agent, the developing solution additive, the bleaching agent, the bleach accelerator, the fixing agent, and the washing/stabilizing step, materials and the step described in JP-A-63-298344 (Japanese Patent Application No. 62-134402) page 14, lower left column to page 18, upper right column can be used.
  • Layers having the following compositions were formed on an undercoated cellulose triacetate film support to form a multilayered color photographic light-sensitive material.
  • the composition of the layer 11 was changed to form various types of samples.
  • the coating amounts of the silver halide and colloid silver are represented in units of g/m of silver, those of the coupler, the additive, and gelatin are represented in units of g/m and that of the sensitizing dye is represented by the number of mols per mol of silver halide in the same layer.
  • the stabilizing agent Cpd-3 (0.04 g/m) for the emulsion and the surface active agent Cpd-4 (0.02 g/m) were added to the layers as coating aids.
  • a 1.0 M silver nitrate solution was added to adjust the pBr to be 2.55, and 150 g of silver nitrate were added at an accelerated flow rate (the final flow rate was ten times an initial flow rate) over 60 minutes, and potassium bromide was simultaneously added by a double jet method so that the pBr was adjusted to be 2.55.
  • the emulsion was cooled to 35°C and washed by a conventional flocculation method, and 60 g of gelatin were added and dissolved at 40°C.
  • the pH and the pAg were adjusted to be 6.5 and 8.6, respectively.
  • the obtained tabular silver bromide grains were monodisperse tabular grains having an average circle-equivalent diameter of 1.4 ⁇ m, a grain thickness of 0.2 ⁇ m, and a variation coefficient of the circle-equivalent diameter of 15%.
  • the emulsion I-B containing silver bromide corresponding to 50g of silver nitrate was added and dissolved in 1.1 l of water, and the temperature and the pBr were kept at 75°C and 1.4, respectively.
  • 1 g of 3.6-dithioctane-1,8-diol was added, and immediately an aqueous silver nitrate solution containing 100 g of silver nitrate and a potassium bromide solution containing 10 M% of potassium iodide were added in an equimolar amount with respect to silver nitrate at constant flow rates over 50 minutes.
  • the emulsion was washed by a conventional flocculation method, and the pH and the pAg were adjusted to be 6.5 and 8.6, respectively.
  • the obtained silver bromide tabular grains were silver iodobromide in which its central portion comprises silver bromide and its outer annular portion comprises silver iodobromide containing 10 M% of silver iodide.
  • the average circle-equivalent grain size of the grains was 2.3 ⁇ m, and-their grain thickness was 0.26 ⁇ m.
  • An emulsion I-D was prepared following the same procedures as for the emulsion I-C except for the following process. Instead of adding an aqueous silver nitrate solution and an aqueous halide solution to a reactor vessel, the fine grain emulsion I-A was added in an amount corresponding to 100 g of silver nitrate to the reactor vessel at a constant flow rate over 50 minutes.
  • the obtained tabular grains had an average circle-equivalent diameter of 2.5 ⁇ m and a grain thickness of 0.23 ⁇ m.
  • An emulsion I-E was prepared following the same procedures as for the emulsions I-C and I-D except for the following process. Equimolar amounts of a solution containing 100 g of silver nitrate and a potassium bromide solution containing 10 M% of potassium iodide were added at constant flow rates to a powerful mixer vessel provided near the reactor vessel and having a high stirring efficiency, thereby forming silver iodobromide fine grains. At this time, 300 ml of a 2 wt% gelatin solution were mixed in the aqueous halide solution prior to the above addition. Very fine grains formed by the mixer vessel were immediately, continuously introduced from the mixer to the reactor vessel containing the core emulsion I-B. During this process, the mixer vessel was kept at 40°C. The obtained tabular grains had an average circle-equivalent diameter of 2.6 ⁇ m and a grain thickness of 0.21 ⁇ m.
  • An emulsion I-F was prepared following the same procedures as for the emulsion I-E except that the pBr was adjusted to be 2.6 during grain growth and no 3,6-dithioctane-1,8-diol was added. 86% of the obtained tabular grains were occupied by hexagonal tabular grains.
  • the obtained tabular grains were a monodisperse tabular silver iodobromide emulsion having an average circle-equivalent diameter of 2.1 ⁇ m, a variation coefficient of the circle-equivalent diameter of 17%, and an average grain thickness of 0.23 ⁇ m.
  • the grains of the emulsions I-C, I-D, I-E, and I-F were sampled and their transmission images were observed by a 200 kvolt transmission electron microscope while they were cooled by liquid nitrogen. A clear annular ring-like stripe pattern was observed in the emulsion I-C, while no such pattern was observed in the emulsions I-D, I-E, and I-F used in the present invention. That is, it was confirmed that a tabular silver iodobromide emulsion containing a silver halide localized region having a microscopically uniform silver iodide distribution was obtained by the method used in the present invention.
  • Fig. 4 The transmission electron microscopic photographs of the emulsions I-C, I-D, and I-E are shown in Fig. 4.
  • the core is a pure silver bromide not containing silver iodide, therefore, no stripe pattern indicating non-uniformity was found, and an outer annular portion (shell) was a silver iodobromide phase containing 10% of silver iodide.
  • the core/shell ratio was 1 : 2.
  • Vu-D, Vu-E, and Vu-F are summarized in Table 2 below.
  • Table 2 Emulsified Dispersion No. Yellow Coupler Development Inhibitor Releasing Compound Vu-D ExY-15 T-144 Vu-E ExY-15 T-104 Vu-F ExY-15 T-158
  • the sample Nos. 101 to 112 prepared as described above were imagewise-exposed by using white light and developed as described below, thereby obtaining cyan, magenta, and yellow image characteristic curves.
  • the color development processing was performed in accordance with the following processing steps at 38°C. Color Development 3 min. 15 s Bleaching 6 min. 30 s Washing 2 min. 10 s Fixing 4 min. 20 s Washing 3 min. 15 s Stabilizing 1 min. 05 s
  • the processing solution compositions used in the respective steps are as follows.
  • each sample of the present invention had a small inhibiting effect of the blue-sensitive layer and a large inhibiting effect of the green-sensitive layer.
  • the inhibiting effect was increased.
  • the coating silver amounts of the emulsions Em-C to Em-F of the layer 11 were increased so that the ⁇ values of the yellow images of the sample Nos. 101 to 104 are adjusted to be substantially 0.70.
  • gray gradation of the blue-, green-, and red-sensitive layers were adjusted to be substantially the same.
  • ⁇ x represents the degree of the interlayer effect for inhibiting a uniformly fogged magenta emulsion layer when the blue-sensitive layer, from the non-exposed portion (point A) to the exposed portion (point B), is exposed. That is, in Fig.5, the curve A-B is the characteristic curve concerning the yellow image of the blue-sensitive layer, and the curve a-b represents the magenta image density of the green-sensitive layer obtained by uniform green exposure.
  • the point A represents the fogged portion of the yellow image
  • the point B represents the portion of the exposure amount for providing a yellow image density of 2.5.
  • the difference (a - b) between the magenta density (a) at the exposure portion A and the magenta density (b) at the portion B was used as a scale representing the degree of the interlayer effect from the blue-sensitive layer to the green-sensitive layer.
  • the samples 102, 103 and 104 had a larger interlayer effect and higher sharpness represented by MTF values than those of the comparative sample 101.
  • a silver halide color photographic light-sensitive material having an improved interlayer effect can be obtained.

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DE69131785T2 (de) * 1990-08-20 2000-05-11 Fuji Photo Film Co Ltd Datenbehaltendes photographisches Filmerzeugnis und Verfahren zur Herstellung eines Farbbildes
JPH0519428A (ja) * 1991-07-16 1993-01-29 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JP2675941B2 (ja) * 1991-08-29 1997-11-12 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
JP2675933B2 (ja) * 1991-09-05 1997-11-12 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
US5275929A (en) * 1992-04-16 1994-01-04 Eastman Kodak Company Photographic silver halide material comprising tabular grains of specified dimensions
US5302499A (en) * 1992-04-16 1994-04-12 Eastman Kodak Company Photographic silver halide material comprising tabular grains of specified dimensions in several color records
JPH063782A (ja) * 1992-06-16 1994-01-14 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
US5385815A (en) 1992-07-01 1995-01-31 Eastman Kodak Company Photographic elements containing loaded ultraviolet absorbing polymer latex
EP0695968A3 (en) 1994-08-01 1996-07-10 Eastman Kodak Co Viscosity reduction in a photographic melt
JPH08202001A (ja) 1995-01-30 1996-08-09 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料

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DE1472745B2 (de) * 1965-03-09 1973-03-15 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur herstellung von dispersionen lichtempfindlicher silbersalze
US4433048A (en) * 1981-11-12 1984-02-21 Eastman Kodak Company Radiation-sensitive silver bromoiodide emulsions, photographic elements, and processes for their use

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