JP2664278B2 - Silver halide photographic emulsions and photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic emulsion and a photographic light-sensitive material using the same, and more particularly, to a silver halide photographic emulsion having excellent photographic sensitivity and less occurrence of fog and using the same. It relates to a photographic material.

(Prior Art) In recent years, high sensitivity and small format of silver halide color light-sensitive materials have been advanced, and color photographic light-sensitive materials having higher sensitivity and excellent image quality have been strongly desired.

Therefore, silver halide emulsions having higher sensitivity and more excellent graininess are required, and conventional silver halide emulsions are insufficient to meet these requirements, and further improvement in performance is desired. .

The present invention relates to a technique for controlling and introducing dislocations near the vertices of silver halide grains. Dislocation refers to a misalignment of an atomic arrangement in a crystal lattice, and is a kind of lattice defect.

Regarding dislocations of silver halide crystals, see CRBerry, J. Appl. Phys., 27 , 636 (1956) CRBerry, DC Skilman, J. Appl. Phys., 35 , 2165 (19)
64) JFHamilton, Phot. Sci. Eng., 11 , 57 (1967) T. Shiozawa, J. Soc. Phot. Sci. Jap., 34 , 16 (1971) T. Shiozawa, J. Soc. Phot. Sci. Jap., 35 , 213 (1972), etc., that it is possible to observe dislocations in a crystal by X-ray diffraction or low-temperature transmission electron microscopy, and to intentionally strain the crystal. Describes that various dislocations occur in the crystal.

The silver halide grains in these documents are not those into which dislocations are intentionally introduced during the formation of a photographic emulsion, but the silver halide grains into which dislocations are positively introduced are described in JP-A-63-22023.
8, JP-A-1-201649. According to these patents, tabular grains into which dislocation lines have been introduced to a certain degree are superior to tabular grains without dislocation lines in photographic properties such as sensitivity and reciprocity, and when these are used as a sensitive material, sharpness and granularity are improved. Has been shown to be excellent.

Performing the chemical ripening of the particles in the presence of the dye enhances the adsorption of the dye and reduces the inherent desensitization due to the addition of the dye, thereby obtaining a color-sensitized emulsion having high sensitivity and good storability. For example, it is described in JP-A-55-26589, JP-A-61-103149 or JP-A-61-133941.

The dislocation introduction method according to the prior art is insufficient for recent demands for high-sensitivity and high-quality photographic light-sensitive materials, and the tendency is remarkable particularly when color sensitization is performed.

(Problems to be Solved by the Invention) An object of the present invention is to provide an emulsion comprising silver halide grains having high sensitivity and low fog generation.

The second object is to obtain an emulsion comprising silver halide grains having excellent reciprocity characteristics.

(Means for Solving the Problems) The above objects of the present invention are as follows: (1) A tabular silver halide grain having an aspect ratio of 2 or more, and dislocations being concentrated near the apex of the grain, and A silver halide photographic emulsion containing the silver halide grains chemically sensitized in the presence of a sensitizing dye.

(2) The particle thickness is less than 0.5 μm and the particle diameter is 0.3
The silver halide photographic emulsion according to the above (1), wherein tabular silver halide grains having an average aspect ratio of at least 2 and having a mean aspect ratio of at least 2 account for at least 50% of the projected area of all the silver halide grains.

(3) At least two light-sensitive silver halide emulsion layers having different color sensitivities are provided on a support, and at least one of these emulsion layers comprises the silver halide photographic emulsion described in (2) above and color development. A photographic light-sensitive material containing at least one kind of coupler that forms a color by coupling with an oxidized form of a base drug.

(4) A halogen containing normal silver halide grains in which dislocations are concentrated near the vertices of the grains, wherein the silver halide grains are chemically sensitized in the presence of a spectral sensitizing dye. Silver halide photographic emulsion.

(5) The silver halide photographic emulsion according to the above (4), which is a normal crystal grain in which at least 60% of the grain surface area is a (111) plane.

(6) The silver halide photographic emulsion according to the above (4), which is a normal crystal grain substantially consisting of silver iodide.

(7) At least two light-sensitive silver halide emulsion layers having different color sensitivity are provided on a support, and at least one of these emulsion layers is the silver halide photographic emulsion described in (4) above and a color developing agent. A photographic light-sensitive material containing at least one kind of coupler which forms a color by coupling with an oxidized product of the above.

 Achieved by

 Hereinafter, the present invention will be described in detail.

The emulsion of the present invention has an aspect ratio of 2 or more, preferably 8 or more.
Contains one or more tabular silver halide grains of less than one. Here, the tabular silver halide grains are a general term for silver halide grains having one twin plane or two or more parallel twin planes. The twin plane refers to the (111) plane when ions at all lattice points on both sides of the (111) plane are in a mirror image relationship. These tabular grains have a triangular, hexagonal or rounded circular shape when the grains are viewed from above, and the triangular ones are triangular, the hexagonal ones are hexagonal, circular. Have circular outer surfaces parallel to each other.

In the present invention, the average aspect ratio of the tabular grains refers to a value (aspect ratio) obtained by dividing the grain diameter by the thickness of each tabular grain having a grain thickness of less than 0.5 μm and a grain diameter of 0.3 μm or more. It is an average value. The measurement of the particle thickness is performed by evaporating a metal from the diagonal direction of the particles together with the reference latex, measuring the shadow length on an electron micrograph, and calculating by referring to the shadow length of the latex. Easy.

The particle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle.

The projected area of the particle can be obtained by measuring the area on an electron micrograph and correcting the projection magnification.

The diameter of the tabular grains is preferably from 0.3 to 5.0 μm. The thickness of the tabular grains is preferably from 0.05 to 0.5 μm.

The proportion of the tabular grains of the present invention in the emulsion is preferably 50% of the projected area of all silver halide grains in the emulsion.
%, Particularly preferably 80% or more. Further, it is preferable that the average aspect ratio of the tabular grains occupying these fixed areas is 3 or more and less than 8. When monodisperse tabular grains are used, more preferable results may be obtained. The structure and production method of monodisperse tabular grains are described in, for example,
According to the description of -151618, etc., the shape is briefly described as follows. More than 70% of the total projected area of the silver halide grains is larger than the length of the side having the minimum length. Hexagons whose ratio is less than 2 and parallel 2
Coefficient of variation in the grain size distribution of the hexagonal tabular silver halide grains [variation in grain size represented by the circle-converted diameter of the projected area thereof]. (standard deviation)
Divided by the average particle size] is 20% or less.

One of the preferred particle shapes for the present invention is normal crystalline particles. Particles having a high (111) plane area ratio in the particle surface area have an octahedral shape. It is preferable that 60% or more of the particle area is the (111) plane. In other words, other planes may coexist with the (111) plane grains, but 40% or less, further 20%
The following is preferred.

The normal crystal silver halide grains of the present invention can be composed of silver chlorobromide, silver chloroiodobromide, and silver iodobromide. It preferably consists essentially of silver iodobromide. Here, “consisting substantially of silver iodobromide” means that a small amount of silver chloride may be contained, but the silver chloride content is preferably 2 mol% or less.

The present invention is applied to the case of particles whose shape is difficult to specify (111).
It is effective if the surface ratio is high and the vertex is clear.

Further, the tabular grains or normal crystal grains of the present invention have dislocations.

Dislocations of tabular grains are described, for example, in JF, Hamilton, Phot.
Sci.Eng., 11 , 57 (1967) and T.Shiozawa, J.Soc.Phot.Sc
It can be observed by a direct method using a transmission electron microscope at low temperature as described in i. Japan, 35 , 213, (1972). In other words, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for electron microscope observation, and the sample is placed in a manner to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a cooled state. In this case, the thicker the particle, the more difficult it is to transmit the electron beam.
The use of an electron microscope with a thickness of 200 kV or more for particles having a thickness of 3 mm enables more clear observation. From the photographs of the particles obtained by such a method, it is possible to determine the dislocation position of each particle as viewed from the method perpendicular to the main plane.

In the case of a normal crystal particle or a particle having an unspecified shape, the particle is often thick. Therefore, it is necessary to use a higher-pressure electron microscope or to devise a method such as partially etching the particle, but the observation is possible.

The dislocations of the silver halide grains of the present invention are substantially concentrated near the vertices of tabular grains or normal crystal grains. The vicinity of a vertex is defined as a point that is x% from the center of a straight line connecting the center of the particle and each vertex. In tabular grains, it refers to a three-dimensional region over the entire thickness of the grain. The value of x is preferably 50 or more and less than 100, and more preferably 75 or more and less than 100.

When the particle is rounded, each vertex is ambiguous, but in this case, a tangent to the outer periphery is obtained, and a straight line connecting the intersection of each tangent and the center of the particle is defined as the outer periphery of the particle. Intersection points can be determined as vertices.

"Dislocations are substantially concentrated near the apex" means that the dislocation density near the apex is higher than the portion other than the vicinity of the apex of the particle. The dislocation density is defined by the number of dislocation lines included in a certain projected area. The dislocation density near the apex is preferably at least twice, more preferably at least 10 times, the dislocation density of the portion other than the vicinity of the apex.

In the case where the tabular silver halide grain has an n-sided outer surface, it is sufficient that n vertexes exist and dislocations are concentrated near each vertex. Of the n vertices, it is not necessary for dislocations to be concentrated at all vertices, and the effect of the present invention can be obtained even when dislocations are concentrated near at least one vertex.

 The method for producing the tabular grains of the present invention will be described.

The tabular grains of the present invention are described in Cleeve, "Theory and Practice of Photography".
(Cleve, Photography Theory and Practice (1930)),
P. 131; Gatoff, Photographic Scienc
s and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,048
No. 4,439,520 and British Patent No. 2,112,157.

The tabular silver halide emulsion used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide. Preferred silver halides are
Silver iodobromide containing 30 mol% or less of silver iodide or silver iodochlorobromide.

The silver halide emulsion of the present invention may have a structure with respect to the halogen composition in the grains.

In order to introduce dislocations near the apex, silver iodide or silver halide having a high silver iodide content is once bonded to the apex of the grain, and the grain is grown again.

In order to join silver iodide or silver iodobromide or silver iodochlorobromide or silver iodochloride having a silver iodide content higher than the silver iodide content of the host grain at the top of the grains, Either indirectly or via an indirect method via halogen transformation.

A method of bonding a guest, which is silver iodide, to a host grain having a face-centered cubic rock salt crystal structure by epitaxial growth,
This is disclosed in a broad sense in JP-A-59-162540 (US Pat. No. 4,463,087). According to this method, it is described that deposition by epitaxial growth can be performed by selecting a silver salt that is not isomorphous to the host particle crystal structure. However, in the examples, only edge selective growth such as local selective epitaxial growth of silver thiocyanate on octahedral silver bromide grains is disclosed. Only an example in which silver thiocyanate is selectively epitaxially grown on the edge of a tabular grain of silver iodobromide (AgI 6 mol%) is disclosed. A specific example of growing silver iodobromide at the top of the grain is as follows. No specific disclosure is made.

The inventors of the present invention have conducted intensive studies and have found that a tabular grain of silver iodobromide is used as a host, and 0.5 to 10 mol%, preferably 1 to 6 mol%, of both aqueous solutions of potassium iodide and silver nitrate are rapidly double-coated. By jet addition, direct bonding can be achieved by epitaxially generating silver iodide or silver halide having a high silver iodide content at the top of the grains without using any orientation director (site director). I found The preferred addition time is 0.2 to
It is 5 minutes, more preferably 0.5 to 2 minutes.

The following method may be used to grow silver iodide or silver halide having a high silver iodide content at the top of the grains.
That is, after adding a silver halide solvent to a solution containing host grains, both aqueous solutions of potassium iodide and silver nitrate are added. After the addition of the silver halide solvent, the vertices of the grains dissolve. In this case, it is not necessary to add both aqueous solutions rapidly. Both aqueous solutions are added at 0.5 to 10 mol%, preferably 2 to 6 mol% of the host.

Examples of the silver halide solvent include water-soluble iodides, thiocyanates, ammonia, thioethers and thioureas.

For example, thiocyanates (U.S. Pat. Nos. 2,222,264, 2,448,534, and 3,320,069), ammonia,
Thioether compounds (for example, US Pat. No. 3,271,157,
No. 3,574,628, No. 3,704, No. 130, No. 4,297,439
No. 4,276,347, etc.), thione compounds (for example, JP-A-53-144319, JP-A-53-82408, JP-A-55-77737, etc.), and amine compounds (for example, JP-A-54-100717, etc.)
Examples thereof include thiourea derivatives (for example, JP-A-55-2982), imidazoles (for example, JP-A-54-100717), and substituted mercaptotetrazole (for example, JP-A-57-202531).

Next, an indirect method will be described in which silver iodide or a silver halide portion having a high silver iodide content is epitaxially bonded to the apex of a grain via halogen conversion.

JP-A-58-108526 (US Pat. No. 4,435,501) describes a method of epitaxially growing silver chloride at the top of tabular grains. If the tabular grains of the host consist essentially of at least 8 mol% iodide on the surface, the silver chloride will be epitaxially grown adjacent to the corner (apex) without the presence of an orientation controlling substance, the corner or The use of an aqueous iodide or an adsorptive orientation controlling substance is also described to restrict the epitaxial growth more narrowly at the edge.

The present inventors adsorbed a cyanine dye to tabular grains as described in Example 4 of JP-A-58-108526,
It has been found that the method of epitaxially growing silver chloride at a corner is not preferable for achieving the object of the present invention. That is, even if a tabular grain is grown after halogen conversion of the thus obtained epitaxial grains with iodide, dislocations are introduced not only near the apex but also on the sides and the main surface. This is presumed to be because the sensitizing dye itself has a function of introducing dislocation.

The present inventors have found that it is preferable to use a water-soluble iodide as an alignment controlling substance in order to epitaxially grow silver chloride. That is, potassium iodide is typically used. It is preferable to use 0.03 to 3 mol%, preferably 0.5 to 1.5 mol% of potassium iodide based on the host particles. This amount preferably corresponds to about 50-200% of the surface monoatomic coverage of the particles. Thereafter, when silver nitrate and potassium chloride are added by a double jet method, silver chloride for the purpose of the present invention can be grown at the top of the grains. The amount of silver nitrate added here is preferably 0.1 to 10 mol% based on the host (tabular) grains.

The halogen conversion of silver chloride by potassium iodide will be described. Highly soluble silver halide is converted to less soluble silver halide by adding halide ions that can form less soluble silver halide. This process is called halogen conversion and is described, for example, in US Pat. No. 4,142,900. In the present invention, a β-AgI phase is formed at the apex of a grain by selectively halogen-converting silver chloride epitaxially grown with potassium iodide. If the amount of potassium iodide for the halogen conversion is too large, dislocations will be dispersed, and if it is too small, the desired dislocations will disappear due to recrystallization occurring in the subsequent grain growth stage. If an appropriate amount of the silver chloride phase does not exist in this process, potassium iodide causes halogen conversion with silver bromide, so that dislocations do not concentrate in the subsequent grain growth. The amount of potassium iodide for halogen conversion is preferably from 0.1 to 10 mol% based on the host tabular grains.

 Next, dislocation growth will be described.

Directly bonding silver iodide by the direct method,
And at the stage of halogen conversion, a β-AgI phase having a crystal form different from that of silver bromide or silver iodobromide or silver chlorobromide or silver chloroiodobromide of the base (host grain) or a high silver iodide content A silver halide phase forms at the top of the grains. Subsequently, when silver nitrate and potassium bromide or silver nitrate and a mixture of potassium bromide and potassium iodide are simultaneously added, the grains further grow, but at this time, a β-AgI phase or a silver halide phase having a high silver iodide content is obtained. Dislocations are introduced starting from. β-
Since the AgI phase is localized near the apex, dislocations are concentrated near the apex. The amount of silver nitrate added at this time is arbitrary as long as it is 5 mol% or more based on the substrate. When a mixture of potassium bromide and potassium iodide is added, the mixing ratio of potassium bromide to potassium bromide is preferably 0 to 0.4.

It is essential that the step of chemical sensitization (chemical ripening) in the method for producing an emulsion of the present invention includes a step performed in the presence of a spectral sensitizing dye until the end of post-ripening. However, the case where the step of chemical sensitization is terminated by adding a spectral sensitizing dye is also included in the above-mentioned step.

Chemical sensitization was written by James (THJames), The Photographic Process, 4th Edition, published by Macmillan,
1977, (THJames, The Theory of the Photographic
Process, 4th ed, Macmillan. 1977), using active gelatin as described on pages 67-76, and also in Research Disclosure, Volume 120, April 1974, 1974.
2008; Research Disclosure, Volume 34, June 1975
Moon, 13452, U.S. Pat.Nos. 2,642,361, 3,297,446,
3,772,031, 3,857,711, 3,901,714, 4,2
Nos. 66,018 and 3,904,415, and British Patent 1,31
At pAg 5-10, pH 5-8 and temperature 30-80 ° C. as described in 5,755, sulfur, selenium, tellurium, gold, platinum,
It can be carried out using palladium, iridium or a combination of these sensitizers.

As the gold sensitizer used in the present invention, a gold complex salt (for example, see US Pat. No. 2,399,083) can be preferably used.

Of these, potassium chloroaurate, potassium aurithiocyanate, auric trichloride, sodium aurithiosulfate, and 2-aurosulfobenzothiazole methchloride are particularly preferred.

The content of the gold sensitizer in the silver halide grain phase is preferably from 10 ^-9 to 10 ^-3 mol, particularly preferably from 10 ^-8 to 10 ^-4 mol, per mol of silver halide.

In the present invention, it is preferable to use not only gold sensitization but also sulfur sensitization.

Examples of the sulfur sensitizer used include thiosulfates, thioureas, thiazoles, rhodanines, and other compounds (specific examples; US Pat. Nos. 1,574,944 and 2,410,689,
No. 2,278,947, No. 2,728,668, No. 3,656,955
Nos. 4,030,928 and 4,067,740), of which thiosulfates, thioureas and rhodanines are particularly preferred.

The amount of sulfur sensitizer depends on the particle size, temperature of chemical sensitization, pA
The optimal amount can be selected according to conditions such as g and pH.
10 ^-9 to 10 ^-3 mol, preferably 5 mol, per mol of silver halide
^{X10 -7} to 10 ^-4 mol, more preferably 5 × 10 ^-7 to 10 ^-5 mol.

The temperature for chemical sensitization is in the range of 30 ° C to 90 ° C, and pAg is 5 or more
The pH can be appropriately selected at 0 or less and at 4 or more.

In the present invention, a sensitization method using a metal such as iridium, platinum, rhodium and palladium (for example, US Pat. No. 2,44
Nos. 8,060, 2,566,245, and 2,566,263) and a selenium sensitization method using a selenium compound can also be used.

Chemical sensitization can also be performed in the presence of a chemical sensitization aid.
Compounds known to suppress fog and increase sensitivity in the course of chemical sensitization, such as azaindene, azapyridazine and azapyrimidine, are used as the chemical sensitization aid. Examples of chemical sensitization aid modifiers are described in U.S. Pat.Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and Duffin, `` Emulsion Chemistry, '' pp. 138-143. ing.

Dye addition in the present invention is used for the purpose of causing a sensitizing dye to act as a control agent for the formation of a photosensitive nucleus during chemical sensitization. Further, such a dye addition method results in adsorption of the dye to the particles at a high temperature of 50 ° C. or higher, and is used for the purpose of promoting the enhancement of the adsorption.

The term “end of post-ripening” as referred to in the present invention refers to the stage at which the progress of chemical sensitization has stopped.

The chemical sensitization in the presence of the spectral sensitizing dye in the present invention can be performed at any stage of emulsion preparation which is known to be useful before chemical ripening is completed and after grain formation. it can. If a spectral sensitizing dye is added during grain formation, dislocation may be introduced by the dye, and a desired grain may not be obtained. U.S. Patent No. 3,
As taught in 628,960 and 4,225,666, spectral sensitization can be performed at the same time as chemical sensitization, or can be performed completely prior to chemical sensitization. US Patent 4,225,666
It is also possible to have some of the spectral sensitizing dyes be present in the step before the completion of the chemical sensitization and the remainder introduced after the chemical sensitization, as taught in US Pat.

That is, the spectral sensitizing dye, after grain formation, during the washing step,
It may be added at any time before chemical sensitization, during chemical sensitization, or immediately before the end of chemical sensitization, but the preferred addition time is after grain formation, during a washing step, and before chemical sensitization.

The spectral sensitizing dye that can be used in the present invention can be selected from common methine dyes, and is not particularly limited.

The dyes used in the present invention include cyanines, merocyanines, complex cyanines and complex merocyanines (ie, tree,
And polymethine dyes including oxol, hemioxonol, styryl, melostyryl and streptocyanin.

Cyanine spectral sensitizing dyes, menolinium, pyridinium, isoquinolinium, 3H-indolium, Benz (e) indolium, oxazolium, oxazolinium, thiazolium, thiazolinium, selenazolium,
Selenazolinium, imidazolium, imidazolinium, benzothiazolinium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, thiazolinium, dihydronaphthia Includes two basic heterocyclic nuclei linked by a methine bond, such as those derived from zolium, sodium and imidazopyrazinium quaternary salts.

Merocyanine spectral sensitizing dyes include barbituric acid, 2
-Thiobarbituric acid, rhodanine, hydantoin, 2
-Thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3-dione, cyclohexane-1,3-dione,
Derived from 1,3-dioxane-4,6-dione, pyrazoline-3,5-dione, pentane-2,4-dione, alkylsulfonylacetonitrile, malononitrile, isoquinolin-4-one and chroman-2,4-dione. Such an acidic nucleus and a basic heterocyclic nucleus of a cyanine dye type are bonded by a methyl bond.

As blue-sensitive sensitizing dyes, for example, US-2493748, JP-B-46-30023, US-3752670, US-3976492, JP-A-58-9144
4, JP-A-61-289,341 and JP-A-59-55,426 can be used. As a green-sensitive sensitizing dye, for example, US-35064
43, JP-B-47-25379, JP-B-43-4936, JP-A-62-139,55
2, JP-A-61-156,046, JP-A-60-128,433, JP-B-49-46
Those described in 50 can be used. Examples of the red-sensitive sensitizing dye include, for example, JP-B-43-4933, JP-B-46-10,473, JP-B-45-32,741, JP-A-59-135,461, JP-A-59-214,030,
JP-A-61-282,831, JP-A-59-166,955, JP-A-59-77,44
3, those described in US-4,326,023 can be used.

For the color sensitization during or in combination with the chemical sensitization in the present invention, various supersensitization techniques can be used. Examples of useful dye combinations, including supersensitizing dye combinations, are described in U.S. Patent Nos. 3,506,443 and 3,672,898. As an example of a supersensitizing combination consisting of a spectral sensitizing dye and a non-light absorbing additive, a thiocyanate is used in the process of spectral sensitization as indicated in U.S. Pat.No. 2,221,805,
U.S. Pat.No. 2,937,390 uses bis-triazinylaminostilbenes as indicated in U.S. Pat.
U.S. Pat.No. 1,413,826 using sulfonated aromatic compounds as shown in U.S. Pat.No. 089, mercapto-substituted heterocyclic compounds as shown in U.S. Pat.
Iodides can be used as indicated on the issue.

As the method of adding the sensitizing dye during the process of producing the emulsion of the present invention, various methods conventionally proposed can be applied. For example, as described in British Patent No. 3,469,987, the method may be carried out by dissolving a sensitizing dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding the dispersion to an emulsion. Furthermore, the sensitizing dyes of the present invention can be individually dissolved in the same or different solvents, and these solutions can be mixed or added separately before adding to the emulsion.

In the present invention, a water-miscible organic solvent such as methyl alcohol, ethyl alcohol or acetone is preferably used as a solvent for the sensitizing dye when the dye is added to the silver halide emulsion.

In the present invention, when the sensitizing dye is added to the silver halide emulsion, the amount of the sensitizing dye added is 1 × 10 5 per mol of silver halide.
⁵ mol to 2.5 × 10 ^-3 mol is preferred, more preferably 1.0 mol
X 10 ^-4 mol to 1.0 x 10 ^-3 mol.

The sensitizing dye can be used in combination with another sensitizing dye or a supersensitizer.

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The emulsion of the present invention may be further subjected to chemical sensitization in the absence of a spectral sensitizing dye (in addition to chemical sensitization in the presence of a spectral sensitizing dye), Spectral sensitization may be performed separately in addition to the spectral sensitization using a sensitizing dye.

The photographic light-sensitive material of the present invention has at least two light-sensitive silver halide emulsion layers having different color sensitivity on a support, and at least one of these emulsion layers contains the emulsion of the present invention and a color developing agent. It contains at least one type of coupler that forms a color by coupling with an oxidant, and can be applied to a multilayer silver halide color photographic material using a color development process.
For example, the present invention can be applied to various photosensitive materials subjected to development processing such as color paper, color reversal paper, color positive film, color negative film, color reversal film, and color direct positive photosensitive material. Particularly, application to color paper and color reversal paper is preferable.

In the multilayer silver halide color photographic light-sensitive material, generally, the arrangement of the color-sensitive layers is, in order from the support side, a red color-sensitive layer,
The layers are arranged in the order of the green color sensitivity layer and the blue color sensitivity, or in the reverse order. However, other color-sensitive layers such as an infrared color-sensitive layer can be used according to the purpose, and the arrangement order can be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

As the non-photosensitive layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer and the like can be used according to the purpose. These layers may contain a light-insensitive emulsion such as a fine grain emulsion.

With respect to the support, a so-called back layer can be provided on the side opposite to the emulsion layer for the purpose of controlling curl, preventing static charge, preventing adhesion, and the like. The back layer may be a single layer or a multilayer.

As a specific example of the layer arrangement, a red photosensitive layer (R) / a green photosensitive layer (C) / a blue photosensitive layer (B) / a support, a B / G / R support and the like can be provided in this order. A layer arrangement having a plurality of layers having the same color sensitivity and different sensitivities is also useful. More specifically, high-sensitivity blue-sensitive layer (BH) / low-sensitivity blue-sensitive layer (BL)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) /
An arrangement in which the high-sensitivity layer and the low-sensitivity layer of the high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) / substrate or any of the color-sensitive layers therein can be used.

Also, as described in Japanese Patent Publication No. 55-34932,
From the farthest side from the support, blue light-sensitive layers / GH / RH / GL / RL can be arranged in this order. JP-A-56-25738, 62
As described in -63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

No. 4,663,271 to improve color reproduction
No. 4,705,744, 4,707,436, JP-A-62-160
A donor layer (CL) with a multilayer effect having a different spectral sensitivity distribution from the main photosensitive layer such as BL, GL, RL described in the specifications of JP-A Nos. 448 and 63-89580 is disposed adjacent to or close to the main photosensitive layer. Is preferred.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The silver halide emulsion used in combination with the emulsion of the present invention in the light-sensitive material of the present invention may be of any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride.

The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the distribution of the halogen composition inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains, and a shell surrounding the core. (Shell) [Layer or plural layers] and a so-called laminated type particle having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (when the particle is on the particle surface, the edge of the particle, Particles having a structure in which portions having different compositions are joined on corners or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, the boundary between different portions in the halogen composition may be a clear boundary or an unclear boundary due to the formation of liquid crystal due to a composition difference. It may be good and may have a continuous structural change positively.

The halogen composition depends on the type of photosensitive material to be applied.For example, a silver chlorobromide emulsion system is mainly used for a printing material such as color paper, and a silver iodobromide emulsion system is mainly used for a photographic material such as a color negative. Used.

Further, a so-called high silver chloride emulsion having a high silver chloride content is preferably used as a photosensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%,
It is more preferably at least 95 mol%.

Such a high silver chloride emulsion preferably has a structure in which a silver bromide localized phase is formed in a layered or non-layered form inside and / or on the surface of silver halide grains as described above.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized phases can be inside the grains, at the edges, corners, or planes of the grain surfaces. One preferred example is a phase grown epitaxy at the corners of the grains.

Average grain size of silver halide grains that can be used together in the light-sensitive material of the present invention (expressed as an average based on the projected area based on the grain size, in the case of spherical or nearly spherical grains, and the ridge length in the case of cubic grains. Is also 2 μm or less, preferably 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm or less.
μm or more. The grain size distribution may be either narrow or wide, but the value (variation) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is as follows.
It is preferable to use a so-called monodispersed silver halide emulsion in an amount of 20% or less, particularly preferably 15% or less, together with the light-sensitive material of the present invention. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in an emulsion layer having substantially the same color sensitivity (the monodispersity is defined as (Preferably those having a variation rate) can be mixed in the same layer or multi-layer coated in another layer. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used as a mixture or as a mixture.

The silver halide grains used in combination with the light-sensitive material of the present invention may be those having regular crystals such as cubic, octahedral, rhombodecahedral, and tetradecahedral, or those coexisting therewith. Well, and irregular (ir
It may have a regular) crystal form or a compound form of these crystal forms. Further, tabular grains may be used.

The silver halide photographic emulsion that can be used in combination with the light-sensitive material of the present invention is, for example, Research Disclosure (RD) No. 176
43 (December 1978), pp. 22-23, "I. Emulsion Production (Emulsion
preparation and types) ”and No. 18716 (1979
November), p.648, Grafkid, "Physics and Chemistry of Photography",
Published by Paul Montell (P. Glafkides, Chemie et Phisique
Photograh-ique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffi)
n, Photograhic Emulsion Chemistry (Focal Press, 196
6)), "Manufacture and coating of photographic emulsion" by Zelikman et al., 8V.L. Zelikman et al., Making and published by Focal Press.
Coating Photograhic Emuldion. Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in combination with the publication material of the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (Gutoff, Photographic Science and Engi).
neering), Vol. 14, pp. 248-257 (1970); U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048, 4,4.
It can be easily prepared by the methods described in JP 39,520 and British Patent 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, rhodanic acid and lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

The photographic emulsion of the present invention and the silver halide emulsion used in combination with the emulsion of the present invention are usually those which have been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure Nos. 17643 and 18716, and the relevant portions are summarized in the table below.

Known photographic additives which can be used in combination when using the photographic emulsion of the present invention are described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in (1) to the photosensitive material.

Various color couplers can be used in the light-sensitive material of the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG. .

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,428,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat.
Preferred are 968, 4,314,023 and 4,511,649, and EP 249,473A, particularly those described.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552
No., Research Disclosure No.24230 (June 1984)
Mon), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730
No. 55-118034, No. 60-185951, U.S. Pat.
No. 630, No. 4,540,654, No. 4,556,630, International Publication W
Those described in O88 / 04795 and the like are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453
A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,775,616, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Those described in JP-A-61-42658 are preferred.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643 VII.
-G page, U.S. Pat.No. 4,163,670, JP-A-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,368 are preferred. Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181 and a dye that can form a dye by reacting with a developing agent described in U.S. Pat.No.4,777,120 It is also preferable to use a coupler having a precursor group as a leaving group.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,302; No. 4,576,910; British Patent 2,
No. 102,173, etc.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents described in the paragraph, JP-A-57-151944, 57-154234
And Nos. 60-184248, 63-37346 and 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
Preferred are those described in JP-A-31-188, JP-A-59-157638 and JP-A-59-170840.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618, multi-equivalent couplers described in
No. 185950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, European Patent Nos. 173,302A, 313,
No. 308A, couplers releasing dyes that recolor after release, RD Nos. 11449, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, etc., and ligands described in U.S. Pat.No. 4,553,477 Release couplers, couplers releasing leuco dyes described in JP-A-63-75747, U.S. Pat.
And couplers which release a fluorescent dye described in 4,181.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of high boiling organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like. A step of a latex dispersion method as one of the polymer dispersion methods;
Specific examples of the effects and latexes for impregnation are described in U.S. Pat.
No. 9,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230, etc., the dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO 88/00723.

Examples of the organic solvent used in the above-described oil-in-water dispersion method include alkyl phthalate (eg, dibutyl phthalate, dioctyl phthalate) and phosphate (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl). Phosphate), citrate (eg, tributyl acetyl citrate), benzoate (eg, octyl benzoate), alkyl amide (eg, diethyl lauryl amide), fatty acid esters (eg, dibutoxyethyl succinate, diethyl azelate) , Trimesic acid esters (for example, trimesin tributyl) and the like, or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, Butyl alcohol, methyl isobutyl ketone, beta-ethoxyethyl acetate,
Methyl cellosolve acetate or the like may be used in combination. These dispersions may be washed with water or reduced pressure to remove unnecessary components.

Typical amounts of color coupler used range from 0.001 to 1 mole per mole of photosensitive silver halide,
Preferably 0.01 to 0.5 mol for a yellow coupler,
The amount is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

In the color light-sensitive material of the present invention, JP-A-63-257747
No. 62-272248, and JP-A-1-80941.
2-benzisothiazolin-3-one, n-butyl-p
-Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various preservatives such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole, or a fungicide.

The photographic light-sensitive material used in the present invention is coated on a commonly used plastic film (eg, cellulose nitrate, cellulose acetate, polyethylene terephthalate), a flexible support such as paper, or a rigid support such as glass. For details of the support and the coating method, see Research Disclosure, Vol. 176, Item 17643, item XV (p.27) X
It is described in Section VII (p.28) (December 1978).

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, organic anti-fading agents for cyan, magenta and / or yellow images mainly include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols and bisphenols. Hindered phenols, gallic acid derivatives, methylenedioxybenzenes,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP 52-152225, etc. UK Patent 2,06
No. 6,975, JP-A-59-10539, JP-B-57-19765, and the like, hindered phenols are described in U.S. Pat.
No., JP-A-52-72224, U.S. Pat.No. 4,228,235, Japanese Patent Publication No. 5
2-6623 and the like, gallic acid derivatives, methylenedioxybenzenes, aminophenols are U.S. Pat.
No. 457,079, No. 4,332,886, JP-B-56-21144, and the like, hindered amines are disclosed in U.S. Pat.
No. 3, No. 1,410,846, JP-B-51-1420, JP-A-58-11
Metal complexes are described in U.S. Pat. Nos. 4,050,938 and 4,241,155 and British Patent 2,027,731 (A), respectively. These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamic acid ester compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
3,700,455) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may be used. These ultraviolet absorbers may be carried in a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

As a binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Weiss, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

The color light-sensitive material of the present invention has at least one layer containing a light-sensitive silver halide emulsion and a coupler on a support. The photosensitive silver halide emulsion is usually spectrally sensitized so as to impart blue sensitivity, green sensitivity, and red sensitivity, but may be provided with infrared sensitivity or intermediate spectral sensitivity according to the purpose. You may. What kind of color sensitivity is given
It depends on the exposure light source such as sunlight, tungsten light, LED, laser and the like. There are no particular restrictions on the number and order of the emulsion layers and the non-photosensitive layers. As an example, the support has at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities.

Generally, a color photographic light-sensitive material is used in combination with the above color-sensitive layers. The relationship between the photosensitivity of the emulsion and the hue of the coloring dye of the coupler is generally such that a yellow coupler is used for the blue-sensitive layer, a magenta coupler is used for the green-sensitive layer, and a cyan coupler is used for the red-sensitive layer. It may be changed according to the purpose.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions are pH buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole, a benzothiazole or a mercapto compound. If necessary, such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine -Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black and white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 l or less per square meter of the light-sensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include iron (III) and cobalt (II
Compounds of polyvalent metals such as I), chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used.
Representative bleaching agents include ferricyan compounds; dichromates; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. . Of these, iron (III) complex salts of aminopolycarboxylic acid, such as iron (III) complex salt of ethylenediaminetetraacetate, and persulfate are preferred from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually
5.5 to 8, but lower p for faster processing
H can also be processed.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-9.
No. 5630, Research Disclosure No. 17,129 (1
A compound having a mercapto group or a disulfide bond described in, for example, Japanese Patent Application Laid-Open No. 50-140129; a thiourea derivative described in US Pat. No. 3,706,561; An iodide salt according to
Polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B-45-8836;
Bromide ions and the like can be used. Of these, compounds having a meltcapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly preferred are compounds described in U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95630. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative of the bleach-fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (stages), a replenishment method such as a counterflow, a forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, a method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., by Hiroshi Horiguchi, "Bactericidal and antifungal chemistry" ( 1986
Year) Sankyo Publishing, Sanitary Technology Association, ed., "Sterilization, sterilization, and fungicide technology of microorganisms" (1982). Can be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in Nos. 57-8543, 58-14834 and 60-220345 can all be used.

In some cases, a stabilization process may be performed after the water washing process. For example, the stabilization process is used as a final bath of a color photographic material for photography. Examples include a stabilizing bath containing formalin and a surfactant. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, 3,342,599, Schiff base-type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, and metals described in U.S. Pat.No.3,719,492 Salt complexes and urethane compounds described in JP-A-53-135628 can be exemplified.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-1154.
No. 38, etc.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing to shorten the processing time, and conversely, lowers the temperature to improve the image quality and improve the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that the light-sensitive material is housed in a cartridge. The most common cartridge is the current 135 format patrone. Other cartridges proposed in the following patents can also be used. (Japanese Utility Model No. 58-67329,
JP-A-58-181035, JP-A-58-182634, Japanese Utility Model SHO 58-195
No. 236, U.S. Pat.No.4,221,479, Japanese Patent Application No. 63-57785, Japanese Patent Application No. 63-183344, Japanese Patent Application No. 63-325638, Japanese Patent Application No. 1-21862
No., Japanese Patent Application No. 1-25362, Japanese Patent Application No. 1-30246, Japanese Patent Application No. 1-2022
No. 2, Japanese Patent Application No. 1-21863, Japanese Patent Application No. 1-37181, Japanese Patent Application No. 1-331
08, Japanese Patent Application No. 1-85198, Japanese Patent Application No. 1-172595, Japanese Patent Application No. 1-1
No. 72594, Japanese Patent Application No. 1-172593, U.S. Pat. No. 4,846,418, U.S. Pat. No. 4,848,693, U.S. Pat. No. 4,832,275) The present invention will be further described below with reference to examples.

Example-1 (1) Preparation of emulsion A. Preparation of base emulsion Preparation of emulsion A-1: A 0.7% aqueous solution of low molecular weight gelatin containing 0.91 mol of potassium bromide was stirred at 30 ° C while stirring with a double jet. 1 at the same constant flow rate
1.01 molar aqueous solution of potassium bromide and silver nitrate over minutes
A 0.94 molar aqueous solution was added (12.7% of the total silver nitrate was consumed). After adding 400 ml of a 16% deionized gelatin solution, the temperature was raised to 75 ° C. Add 0.88 mol aqueous solution of silver nitrate to add pBr
After adjusting to 2.31 (consumption of 18.8% of total silver nitrate), 14.7N
Aqueous ammonia was added to adjust the pH to 8.3, and after physical ripening, 3N nitric acid was added to adjust the pH to 5.5 again. A 1.33 molar aqueous solution of potassium bromide and a 0.88 molar aqueous solution of silver nitrate were added simultaneously over 30 minutes while maintaining the pBr at 3.02 (68.5% of the total silver nitrate was consumed). Next, desalting is performed by the usual flocculation method, and the average aspect ratio is 6.5 and the equivalent circle diameter is 1.0
A AgBr emulsion A-1 having a thickness of μm was prepared. The silver nitrate used was 156 g.

Preparation of Emulsion A-2: A 0.7% aqueous solution of low molecular weight gelatin containing 0.04 mol of potassium bromide was stirred at 30.degree.
Over a period of 2.3 minutes, a 2.33 molar aqueous solution of potassium bromide and a 1.88 molar aqueous solution of silver nitrate were added (12.7% of the total silver nitrate was consumed). After adding 550 ml of a 6% deionized gelatin solution, the temperature was raised to 75 ° C. Add 1.88 molar aqueous solution of silver nitrate and add pBr
Was adjusted to 2.31 (consumed 18.5% of the total silver nitrate) and 1
A 4.7N ammonia aqueous solution was added to adjust the pH to 8.3, and after physical ripening, 17.5N acetic acid was added to adjust the pH to 5.5 again. A 1.65 molar aqueous solution of potassium bromide, a 0.20 molar aqueous solution of potassium iodide and a 1.92 molar aqueous solution of silver nitrate were simultaneously added over 50 minutes while maintaining the pBr at 2.0 (consuming 68.5% of the total silver nitrate). Next, desalting is performed by a normal flocculation method, and a flat plate A having an average aspect ratio of 7 and a circle equivalent diameter of 1.2 μm is used.
gBr I emulsion A-2 was prepared. The silver nitrate used was 156 g.

B- (a) Preparation of grains having dislocations concentrated near the apex 500 g of base emulsion A-1, A-2, (0.5 mol Ag) and distilled water 3
50 cc was mixed, heated to 40 ° C., and stirred well. While maintaining this state, the following procedure was performed.

A potassium iodide solution (concentration 0.04 mol / l) corresponding to 1.2 mol% with respect to the silver amount of the base emulsion was added over 15 minutes.

A silver nitrate solution (concentration: 1.02 mol / l) and a sodium chloride solution (1.58 mol / l) each corresponding to 4.1 mol% with respect to the silver amount of the base emulsion were added over 1 minute by the double jet method.

A potassium iodide solution (concentration 0.04 mol / l) corresponding to 1.3 mol% with respect to the silver amount of the base emulsion was added over 8 minutes.

Silver nitrate solution (concentration 1.02 mol / l) and potassium bromide solution (concentration 1.02 mol / l) were added in amounts corresponding to 50 mol% with respect to the silver amount of the base emulsion in 49 minutes while maintaining pBr = 1.73. .

 It was desalted by flocculation method.

Emulsion prepared using Emulsion A-1 as a base emulsion (Emulsion B-
1) Emulsion prepared using Emulsion A-2 as a base emulsion (Emulsion B-2) had an average aspect ratio of 6.5 and a circle equivalent diameter.
1.3 μm.

B- (b) Preparation of grains having dislocations concentrated near the apex 500 g of base emulsion A-1, A-2 (0.5 mol Ag) and distilled water 3
50 cc was mixed, heated to 75 ° C., and stirred well. The following procedure was performed while maintaining this state.

 Potassium bromide was added to adjust pBr to 1.3.

A 0.12 mol aqueous solution of potassium iodide was added in an amount of 4 mol% based on the silver amount of the base grains. At this point, the vertices of the particles dissolve.

An aqueous solution of 1.87 mol silver nitrate was added 4.9% to the base particles.

A 1.02 molar silver nitrate solution and a 1.02 molar potassium bromide solution each corresponding to 50 mol% with respect to the silver amount of the base emulsion were added over 49 minutes while maintaining pBr = 1.73.

And desalted by flocculation method.

Emulsion prepared using Emulsion A-1 as a base emulsion (Emulsion B-
3) Emulsion prepared using Emulsion A-2 as a base emulsion (Emulsion B-4), both having a normal aspect ratio of 6.0 and a circle equivalent diameter of 1.2.
μm.

C. Preparation of particles having dislocations that do not localize Among the procedures described in B- (a),
Was performed. The emulsion prepared from the base emulsion A-1 was emulsion C-1 and the emulsion prepared from the base emulsion A-2 was C-2.
And

Also, among the procedures described in B- (b),
The emulsion prepared from the base emulsion A-1 is referred to as emulsion C-3, and the emulsion prepared from the base emulsion A-2 is referred to as C-4.

(2) Observation of dislocation of grains Emulsions B-1 and C-1 were observed using a transmission electron microscope.
Dislocations were directly observed. JEM-2000FX II manufactured by JEOL Ltd. was used for the electron microscope.
Observed at 120 ° C.

FIG. 1 shows a photograph of typical grains obtained by observing the emulsion B-1. It is clear that the dislocations are concentrated only in the vicinity of the vertex.

FIG. 2 shows a photograph of typical grains obtained by observing the emulsion C-1. It can be seen that the dislocations are not concentrated and are uniformly introduced on the sides of the grains.

(3) Spectral sensitization and chemical sensitization Dyes were added to the prepared emulsions B-1 to C-4 and C-1 to C-4 by the following method a or b.

a. Addition at the start of demineralized water washing chemical sensitization. b. Addition after chemical sensitization was completed by lowering the temperature to 40 ° C. The spectral sensitizing dye VIII used in Example 2 was used as the added dye. The amount of addition was determined so that when each emulsion was optimally subjected to gold-sulfur sensitization, the spectral sensitization sensitivity at 1/100 second exposure was the highest. Table 1 shows the thus prepared color sensitized emulsions as 11 to 26.

(4) Preparation of coated sample and its evaluation On the cellulose triacetate film support provided with an undercoat layer, the above-mentioned chemically sensitized emulsion and protective layer were coated at the coating amounts shown in Table 2; Coated samples were prepared for each emulsion.

Table 2 Emulsion coating conditions (1) Emulsion layer · Emulsion ... various emulsion (silver 3.6 × 10 ^-2 mol / m ²⁾ · Coupler (1.5 × 10 ^-3 mol / m ²⁾ ・ Tricresyl phosphate (1.10 g / m ² ) ・ gelatin (2.30 g / m ² ) (2) protective layer ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt (0.08 g / m ² )・ Gelatin (1.80 g / m ² ) After leaving these samples at 40 ° C. and 70% relative humidity for 14 hours, they were passed through a continuous wedge for 1/100 second and 10
Exposure was performed for the same exposure amount for a second, and the next color development processing was performed.

 The density of the treated sample was measured with a green filter.

 Process Processing time Processing temperature Color development 2,000 seconds 40 ° C Bleaching and fixing 3,000 seconds 40 ° C Washing with water (1) 20 seconds 35 ° C Washing with water (2) 20 seconds 35 ° C Stable 20 seconds 35 ° C Drying 50 seconds 65 ° C Next, the composition of the treatment liquid will be described.

(Color developing solution) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-hydroxyethylidene-3.0 Sodium 1,1-diphosphonite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N-β-hydroxyethylamino]
-2-Methylaniline sulfate 4.5 Add water 1.0l pH 10.05 (Bleach-fixing solution) (unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 90.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution 70%) 260.0ml Acetic acid (98%) 5.0ml Bleaching accelerator 0.01mol Add water and add 1.0 l pH 6.0 (washing solution) Tap water is converted to H-type strongly acidic cation exchange resin (Rohm and Haas Amberlite IR-120B) and OH-type anion exchange resin (Amberlite IR-400). Water was passed through the packed mixed-bed column to reduce the concentration of calcium and magnesium ions to 3 mg / l or less, followed by addition of 20 mg / l of sodium diisocyanurate dichloride and 1.5 g / l of sodium sulfate.

 The pH of this solution is in the range 6.5-7.5.

(Stabilizing solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Add water 1.0l pH 5.0-8.0 Sensitivity Is the relative value of the reciprocal of the exposure, expressed in lux-seconds giving a density of 0.2 on fog. The results for the gold-sulfur sensitized samples are shown in Table 3.

As is apparent from Table 3, the emulsion prepared by the method B of the present invention has higher 1 / 100-second sensitivity and 10-second sensitivity than the emulsion prepared by the method C, and the effect of the present invention is remarkable. there were.

Example 2 On the undercoated cellulose triacetate film support, each layer having the composition shown below was applied in a multilayer manner, and the emulsion described in Example 1 was applied to the first blue-sensitive emulsion layer of the multilayer color light-sensitive material. Samples 111-126 containing 11-26 (with the highest gold-sulfur sensitization) were made.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount in g / m ² unit, and indicates the coating amount of silver halide in terms of silver.
However, with respect to the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver silver 0.18 gelatin 1.40 2nd layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (donor layer of multilayer effect on red-sensitive layer) Emulsion J Silver 1.2 Emulsion K Silver 2.0 Sensitizing dye IV 4 × 10 ^-4 EX -10 0.10 HBS-1 0.10 HBS-2 0.10 4th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 gelatin 0.80 5th layer (first red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 sensitizing dye I 1.5 × 10 ^-4 sensitizing dye II 1.8 × 10 ^-5 sensitizing dye III 2.5 × 10 ^-4 EX-2 0.335 EX-10 0.020 U-1 0.07 U-2 0.05 U-3 0.07 HBS-1 0.060 Gelatin 0.87 Sixth layer (second red-sensitive emulsion layer) Emulsion G Silver 1.0 Sensitizing dye I 1.4 × 10 ^-4 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.0 × 10 ^-4 EX-2 0.400 EX-3 0.050 EX-10 0.015 U-1 0. 07 U-2 0.05 U-3 0.07 Gelatin 1.30 7th layer (third red-sensitive emulsion layer) Emulsion D Silver 1.60 Sensitizing dye I 1.0 × 10 ^-4 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.0 × 10 ^-4 EX-3 0.010 EX-4 0.080 EX-2 0.097 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 8th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.80 9th layer (1st green feeling) Emulsion layer) Emulsion A silver 0.15 Emulsion B silver 0.15 sensitizing dye V 3.0 × 10 ^-5 sensitizing dye VI 1.0 × 10 ^-4 sensitizing dye VII 3.8 × 10 ^-4 sensitizing dye IV 5.0 × 10 ^-5 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.005 HBS-1 0.100 HBS-3 0.010 Gelatin 0.63 10th layer (2nd green-sensitive emulsion layer) Emulsion C silver 0.45 sensitizing dye V 2.1 × 10 ^-5 sensitizing dye VI 7.0 × 10 ^-5 sensitizing dye VII 2.6 × 10 ^-4 sensitizing dye IV 5.0 × 10 ^-5 EX-6 0.094 EX-22 0.018 EX-7 0.026 HBS-1 0.160 HBS-3 0.008 Gelatin 0.50 Layer 11 ( third green-sensitive emulsion layer) sensitized emulsion E silver 1.2 sensitizing dye V 3.5 × 10 ^-5 dye VI 8.0 × 10 ^-5 increase Dye VII 3.0 × 10 ^-4 Sensitizing dye ^{IV 0.5 × 10 -5 EX-13} 0.015 EX-11 0.100 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54 12th layer (yellow filter layer) yellow colloidal silver silver 0.05 EX-5 0.08 HBS-1 0.03 Gelatin 0.95 Layer 13 (first blue-sensitive emulsion layer) One of emulsions 11-26 Silver 0.22 EX-9 0.721 EX-8 0.042 HBS-1 0.28 Gelatin 1.10 Layer 14 ( Second blue-sensitive emulsion layer) Emulsion G silver 0.45 sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.154 EX-10 0.007 HBS-1 0.05 gelatin 1.78 15th layer (third blue-sensitive emulsion layer) Emulsion H silver 0.77 sensitized Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 16th layer (first protective layer) Emulsion I Silver 0.20 U-4 0.11 U-5 0.17 HBS-1 0.05 Gelatin 1.00 17th layer ( 2 Protective layer) Polymethyl acrylate particles (about 1.5 μm in diameter) 0.54 S-1 0.20 Gelatin 1.20 In addition to the above components, gelatin hardener H-1 and EX-14 to 21 And a surfactant was added. The contents of emulsions A, B, C, D, E, G, H, I, J and K used in the preparation of
It is as shown in the table. The structural formulas or names of the compounds used for preparing the samples are shown in Table A below.

The samples 112 to 126 thus obtained were exposed and processed by the processing method shown in Table 5 using an automatic processor (until the replenishment amount of the bleaching solution became three times the capacity of the mother liquor tank). Processed.

Next, the composition of the treatment liquid will be described.

The sensitivity of the first blue-sensitive layer was evaluated from the exposure amount giving a density 1.5 times higher than the minimum density of yellow density. When using the emulsion of the present invention in which the dislocations are concentrated near the apex, compared with an emulsion in which the dislocations are uniformly present on the sides of the grains, 10 seconds exposure, 1/10
Both 0-second exposures were high in sensitivity and the effect of the present invention was remarkable.

Example 3 A final size of 1.1 according to the formulation of monodisperse octahedral double structure particles described in the examples of US Pat. No. 4,668,614.
μm (emulsion D-1) 1.5 μm (emulsion D-2) and 1.6 μm
A silver iodobromide grain core grain containing 30 mol% of silver iodide of (Emulsion D-3) was prepared. Subsequently, an octahedral emulsion having dislocations at the vertices was prepared by the same procedure as in Example 1, B- (b).

These emulsions were subjected to spectral sensitization and chemical sensitization by the method (a) in Example 1 and then the emulsion of the fifth layer was prepared as Emulsion D.
-1 was replaced by Emulsion D-2, and the emulsion of the twelfth layer was replaced by Emulsion D-3 to prepare the following multilayer color photographic material. When sensitometry was performed in accordance with Example 2, the photographic materials containing emulsions D-1, D-2, and D-3 of the present invention exhibited high sensitivity both in 1/100 second and 10 second, indicating that The effect was significant.

(Composition of photosensitive layer) For silver halide and colloidal silver,
g / m ² units, for couplers, additives and gelatin, the amount is expressed in g / m ² units, and for sensitizing dyes, the number of moles per mole of silver halide in the same layer. Indicated by

First layer (anti-halation layer) Black colloidal silver ... 0.2 Gelatin ... 1.3 UV-1 ... 0.05 UV-2 ... 0.05 UV-3 ... 0.10 UV-4 ... 0.10 Oil-1 ... 0.10 Oil-2 ... 0.10 Second layer ( Intermediate layer) Gelatin... 1.0 Third layer (First red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 7.1 mol%, octahedral multiple structure grains,
Volume equivalent spherical diameter 0.4 .mu.m, a variation coefficient of 15% equivalent spherical diameter) silver coverage ... 1.0 Gelatin ... 2.0 S-1 ... 2.8 × 10 -4 S-2 ... 2.0 × 10 -4 S-3 ... 1.0 × 10 - ⁵ Cp-1 ... 0.40 Cp-2 ... 0.040 Cp-3 ... 0.020 Cp-4 ... 0.0020 Oil-1 ... 0.15 Oil-2 ... 0.15 Fourth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 7.7) Mol%, octahedral multi-structure particles,
Volume equivalent sphere diameter 0.8 μm, variation coefficient of sphere equivalent diameter 10%) Silver coating amount 1.20 Gelatin 0.8 S-1 2.0 × 10 ^-4 S-2 1.5 × 10 ^-4 S-3 8.0 × 10 ^{− 6} Cp-1 ... 0.30 Cp-2 ... 0.03 Cp-3 ... 0.03 Cp-4 ... 0.002 Oil-1 ... 0.12 Oil-2 ... 0.12 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (AgI8 Mol%, octahedral multi-structure particles, volume equivalent sphere diameter 1.1 μm, coefficient of variation of sphere equivalent diameter 13%) Silver coating amount: 1.0 gelatin: 1.50 S-1: 1.5 × 10 ^-4 S-2: 1.5 × 10 ^{− 4} S-3 ... 8.0 × 10 ^-6 Cp-1 ... 0.10 Cp-2 ... 0.10 Oil-1 ... 0.05 Oil-2 ... 0.05 6th layer (intermediate layer) Gelatin ... 0.70 Cpd-11 ... 0.03 Oil-1 ... 0.05 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 7 mol%, octahedral multi-structured grains, volume equivalent sphere diameter 0.4 μm, sphere equivalent diameter variation coefficient 15%) Silver coating amount 1.10 gelatin … 2.50 S-4… 2.4 × 10 ^-4 S-5… 2.4 × 10 ^-4 S-6… 1.2 × 10 ^-4 S-7 ... 5.0 × 10 ^-5 Cp-5 ... 0.15 Cp-6 ... 0.10 Cp-7 ... 0.03 Cp-8 ... 0.02 Oil-1 ... 0.30 Oil-2 ... 0.30 Layer 8 (second green) Sensitive emulsion layer) Silver iodobromide emulsion (AgI 7.3 mol%, octahedral multiple structure grains,
Volume equivalent sphere diameter 0.7 μm, variation coefficient of sphere equivalent diameter 9%) Silver coating amount 1.10 Gelatin 0.80 S-4 2.0 × 10 ^-4 S-5 1.9 × 10 ^-4 S-6 1.1 × 10 ^{− 4} S-7 ... 4.0 x 10 ^-5 Cp-5 ... 0.10 Cp-6 ... 0.070 Cp-7 ... 0.030 Cp-8 ... 0.025 Oil-1 ... 0.20 Oil-2 ... 0.20 Ninth layer (third green sensitive emulsion layer) ) Silver iodobromide emulsion (AgI 7.5mol%, thick plate aspect ratio 2,
Volume equivalent sphere diameter 1.5 μm, variation coefficient of sphere equivalent diameter 14%) Silver coating amount 1.20 Gelatin 1.80 S-4 1.3 × 10 ^-4 S-5 1.3 × 10 ^-4 S-6 9.0 × 10 ^{− 5} S-7 3.0 × 10 ^-5 Cp-6 0.20 Cp-7 0.03 Oil-1 0.20 Oil-2 0.05 Layer 10 (yellow filter layer) Gelatin 1.2 Yellow colloidal silver 0.08 Cpd-12 0.1 Oil-1 ... 0.3 11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6.5 mol%, octahedral multi-structure grain,
Volume equivalent sphere diameter 0.4 μm, coefficient of variation of sphere equivalent diameter 9%) Silver coating amount: 0.20 Silver iodobromide emulsion (AgI 7 mol%, octahedral multi-structure grains, volume equivalent sphere diameter 0.8 μm, variation of sphere equivalent diameter) Coefficient of silver: 0.45 Gelatin: 0.45 Gelatin: 1.75 S-7: 1.0 × 10 ^-4 S-8: 2.0 × 10 ^-4 Cp-9: 0.45 Cp-10: 0.50 Oil-1: 0.20 Oil-2: 0.10 12th layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 9.7 mol%, thick plate aspect ratio 2,
Volume equivalent sphere diameter 1.6μm, Coefficient of variation of sphere equivalent diameter 12%) Silver coating amount 1.10 Gelatin 1.20 S-7 1.0 × 10 ^-4 S-8 1.0 × 10 ^-4 Cp-9 0.25 Oil-1 ... 0.060 Oil-2 ... 0.030 13th layer (first protective layer) Fine grain silver iodobromide (average particle size 0.08 µm, Agl 2 mol%) 0.40 Gelatin ... 1.30 UV-1 ... 0.05 UV-2 ... 0.05 UV-3 ... 0.10 UV-4 ... 0.10 UV-5 ... 0.03 Oil-1 ... 0.1 Oil-2 ... 0.1 14th layer (second protective layer) Gelatin ... 0.50 Surfactant (W-11) polymethyl methacrylate particles ... 0.2 Sliding agent (B-11) ... 0.03 H-1 ... 0.4 In addition to the above components, coating aid W-12, dispersion aid W-13, hardener H-11, H-12, formalin scavenger Cpd-13, C
pd-14, Cpd-15 and Cpd-16 as preservatives, and stabilizer Cpd1
7. Antifoggants, Cpd-18 and Cpd19 were added. The structural formulas or names of the compounds used for preparing the samples are shown in Table B below.

[Brief description of the drawings]

FIG. 1 is an electron micrograph showing the crystal structure of silver halide grains in which dislocations are concentrated near the vertices in the emulsion 11 according to the present invention in Example 1, and the magnification is 65,000 times. FIG. 2 is an electron micrograph showing the crystal structure of silver halide grains having dislocations on the sides in Emulsion 19 of Comparative Example of Example 1, and the magnification is 50,000 times.

Claims (7)

(57) [Claims] 1. A tabular silver halide grain having an aspect ratio of 2 or more and dislocations concentrated near the apex of the grain, the silver halide chemically sensitized in the presence of a spectral sensitizing dye. A silver halide photographic emulsion comprising grains. 2. A tabular silver halide grain having a grain thickness of less than 0.5 μm, a grain diameter of at least 0.3 μm and an average aspect ratio of at least 2 accounts for at least 50% of the projected area of all silver halide grains. 3. The silver halide photographic emulsion according to claim 1, wherein 3. A silver halide photographic emulsion according to claim 2, wherein the support has at least two light-sensitive silver halide emulsion layers having different color sensitivities, and at least one of these emulsion layers is at least one layer. And a photographic material containing at least one coupler that forms a color by coupling with an oxidized form of a color developing agent. 4. Normal grain silver halide grains in which dislocations are concentrated near the vertices of the grains, characterized by containing the silver halide grains chemically sensitized in the presence of a spectral sensitizing dye. Silver halide photographic emulsion. 5. The silver halide photographic emulsion according to claim 4, wherein the grains are normal crystal grains in which at least 60% of the grain surface area is the (111) plane. 6. A silver halide photographic emulsion according to claim 4, which is a normal crystal grain substantially consisting of silver iodobromide. 7. A silver halide photographic emulsion according to claim 4, wherein at least two light-sensitive silver halide emulsion layers having different color sensitivity are provided on a support. A photographic light-sensitive material containing at least one coupler that forms a color by coupling with an oxidized form of a color developing agent.