JP3439563B2 - Silver halide emulsion and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic silver halide emulsion, and more particularly to a tabular silver chlorobromide emulsion or tabular silver chloride emulsion having a high silver chloride content and high sensitivity and excellent suitability for rapid processing. It is about.

[0002]

2. Description of the Related Art At present, in developing a photographic light-sensitive material
There is a demand for shortening the treatment time and reducing the waste liquid accompanying the treatment. Generally, a silver iodobromide emulsion is used for a high-speed negative photographic light-sensitive material, but it is advantageous to use a silver chlorobromide or silver chloride emulsion having a high solubility for the above requirements. On the other hand, it is desirable for those skilled in the art that tabular grains are suitable from the viewpoint of sensitivity, graininess, sharpness, color sensitization efficiency, etc. in order to increase the image density with a small amount of silver in order to reduce waste liquid. well known. Silver halide grains having a high silver chloride content (hereinafter referred to as "high silver chloride grains") generally tend to be cubic grains, and some measures are required to form tabular grains. Two types of tabular grains are known, one having a (111) crystal plane as a parallel main plane and the other having a (100) crystal plane, each of which requires a characteristic device.

A method for producing high silver chloride grains having a (111) main plane is known in the following patents and the like. In the patents cited below, it is common practice to use a morphological stabilizing compound (crystal morphology control agent) for stabilizing the (111) crystal plane in order to form high silver chloride tabular grains having a (111) main plane. It is being appreciated. US Pat. No. 4,399,215
U.S. Pat. No. 4,414,306, U.S. Pat. No. 4,400.
463, U.S. Pat. No. 4,713,323, JP-A-62-
163046, JP-A-59-162540, US Pat. No. 4,942,120, US Pat. No. 5,061,617,
US Patent No. 5185239, US Patent No. 517899
7, US Pat. No. 5,178,998, US Pat. No. 517
6992, US Pat. No. 5,183,732, US Pat. No. 4,804,621, JP-B-55-42737, EP0.
532801A1, EP0481133A1, JP-A-62-218959 and JP-A-63-213836.
JP-A-63-218938, JP-A-63-293
536, JP-A-3-116113, JP-A-2-32
JP-A-3-212639, JP-A-4-28374
No. 2, JP-A-4-335632, JP-A-3-1376.
32, JP-A-3-252649, and JP-A-3-127.
045, JP-A-63-2043, and JP-A-62-29.
9961, JP-A-63-41845, JP-A-3-2
88143, JP-A-4-161947, JP-A-64
-70741, JP-A-64-79744, JP-A-1
-155332, JP-A-1-159646, JP-A-1-250943, JP-A-2-43535, JP-A-4-6546, US Pat. No. 4,783,398, JP-A-63-25643, EP0534325A, and Japanese Patent Publication No. 5-12696, US Pat. No. 5,176,991, US Pat. No. 4,804,621, JP-A-6-11787, US Pat. No. 5,250,408, JP-A-1-102453.
No., etc.

On the other hand, as a method for producing high silver chloride grains having a (100) principal plane, the methods described in European Patent No. 534395 and US Pat. No. 5,264,337 are known. However, silver chlorobromide emulsions are generally liable to have a high fog and are less sensitive to silver iodobromide emulsions, and their use range has been limited to color papers and sensitizers for plate making with relatively high illuminance.

Various techniques have been disclosed in order to overcome the aforementioned drawbacks of a silver halide emulsion having a high silver chloride content (hereinafter referred to as a high silver chloride emulsion). For example, JP-A-58-95736, JP-A-58-108533, and JP-A-58-95733.
Nos. 0-222844 and 60-222845 have various grain structures having a layer having a high silver bromide content in silver halide grains in order to impart high sensitivity to a high silver chloride emulsion. Is disclosed to be effective. However, according to the results of studies conducted by the present inventors, according to these techniques, high sensitivity is certainly obtained, but the effect depends on the type of the spectral sensitizing dye, but the addition amount of the spectral sensitizing dye is compared. In the region where the addition amount is so high that the spectral sensitizing dye covers 60% or more of the total surface area of the particles by adsorption, when these techniques are no longer effective due to so-called intrinsic desensitization. There were many

Since tabular grains have a relatively high surface area per grain volume, it is possible to increase the adsorption amount of the spectral sensitizing dye, which is why tabular grains are advantageous for spectral sensitization. However, due to the above-mentioned intrinsic desensitization,
It was difficult for these technologies to take advantage of the features of the tabular grains. Therefore, it is possible to reduce or eliminate the intrinsic desensitization by the spectral sensitizing dye, and to take advantage of the features of tabular grains that can increase the adsorption amount of the spectral sensitizing dye, and to achieve a high spectral sensitizing sensitivity. Development of technology was desired.

On the other hand, techniques for introducing dislocations into tabular grains are disclosed, for example, in JP-A-63-220238 and JP-A-1-2.
No. 01649, JP-A-3-175440 and the like, it is shown that the photographic characteristics such as sensitivity and exposure illuminance dependency are excellent as compared with tabular grains having no dislocation line. However, all of them are described only for tabular grains mainly containing silver bromide, and nothing is specifically disclosed about introducing dislocations into tabular grains mainly containing silver bromide. Absent. Further, as a result of studies by the present inventors, it was found that none of the methods shown by these techniques can effectively introduce dislocation into tabular silver chloride. For example, JP-A-63-2202
No. 38, a method of providing a specific high iodine layer inside the grain was attempted to introduce dislocations into a silver chloride tabular plate. As a result, a layer having a high silver iodide content was found to be very small. It was found that the grains were unevenly formed, and these grains had an irregular shape that was difficult to call a flat plate. It is considered that the reason why the high iodine layer is formed nonuniformly is that silver iodide is significantly less soluble than silver chloride. That is, because of the low solubility of silver iodide, iodo ions added to the reaction vessel are deposited on the high silver chloride grains in the vicinity at a faster speed than when they are uniformly distributed throughout the reaction vessel by stirring. It is thought that the high iodine layer becomes non-uniform as a result. Therefore, within the range indicated by these techniques, the effect of dislocations on high silver chloride plates was completely unknown.
Naturally, it was impossible to know the effect of dislocation on the above-mentioned defects such as fogging peculiar to silver chloride, and further on the intrinsic desensitization of the high silver chloride tabular emulsion by the spectral sensitizing dye. Furthermore, the introduction of iodine ions into the high silver chloride emulsion is
Naturally, it was expected that the development of the emulsion would be remarkably suppressed, and it was thought that it would be extremely difficult to provide an emulsion excellent in rapid processability, which is a problem to be solved by the present invention. Therefore, it has been desired to develop a technique capable of introducing dislocations into a high silver chloride emulsion by a method without development inhibition.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high silver chloride emulsion having sensitivity comparable to that of silver iodobromide emulsion and excellent in rapid processability.

[0009]

[Means for solving the problem] As a result of earnest research,
The object of the present invention can be achieved by the following (1) to ( 4 ). That is, (1) particles occupying 30% or more of the projected area of all particles are
It is a tabular grain containing at least 80 mol% of silver chloride and having an aspect ratio of 2 or more, and 1 per grain.
A silver halide emulsion composed of silver halide grains having zero or more dislocation lines. (2) The dislocation line extends from the center of the tabular grain to the outer periphery.
Starting from the position of 30% or more and less than 99% of the distance,
(1) The silver halide emulsion as described in (1) above. (3) A high silver bromide-containing phase having a silver bromide content higher than the average silver bromide content of the grains is provided on all or part of the surface of the silver halide grain containing at least 80 mol% of silver chloride. And (1) or (2) obtained by coating the high silver bromide-containing phase with a silver halide phase having a higher silver chloride content and a lower silver bromide content than the high silver bromide-containing phase. /> A method for producing the silver halide emulsion described above. (4) The silver bromide content of the high silver bromide-containing phase is 40 mol% or more.
(3) The silver halide emulsion described in (3)
Manufacturing method.

The present invention will be described in detail below. In the present invention, 30% or more of the projected area of all grains in the emulsion layer is
It is a tabular grain containing at least 80 mol% of silver chloride and having an aspect ratio of 2 or more, and has 10 or more dislocation lines per grain. In the present invention, the ratio of the projected area of the particles satisfying the above items to the projected area of all the particles is 30% or more, preferably 50%.
It is above, and more preferably 70% or more. Also,
In the above, the silver chloride content of the grains satisfying the present invention is at least 80 mol%, but preferably 90%.
It is above, and more preferably 95% or more. Also,
In the above, the particles satisfying the present invention have an aspect ratio of 2
The above tabular grains have an aspect ratio of preferably 2 or more and less than 20 and more preferably 3 or more and less than 8.

In the present invention, the tabular grain has two parallel main planes facing each other, and the diameter of a circle equivalent to the main plane (diameter of a circle having the same projected area as the main plane) is between the main planes. A particle that is at least twice as large as the distance (that is, the thickness of the particle). The aspect ratio means a value obtained by dividing the diameter corresponding to the circle (hereinafter referred to as the diameter) by the thickness of each particle. The diameter and thickness of the particles can be measured by electron microscope observation. In particular, the thickness is observed with an electron microscope from a metal evaporated from a diagonal direction of the particles together with a latex for reference,
It can be measured by comparing the particle shadow length with the latex shadow length. In the present invention, the thickness of the tabular grains is preferably 0.02 μm or more and 0.5 μm or less, more preferably 0.5 μm or more and 0.3 μm.
It is the following. In the present invention, the crystal plane of the main plane of the tabular grains may be the (111) plane or the (100) plane.

To form tabular grains having a high silver chloride content (hereinafter referred to as high silver chloride tabular grains), the above-mentioned (prior art) is used.
Any of the methods cited above can be preferably used. As an example of a particularly preferable crystal habit controlling agent, JP-A-1-
General formula (I) described on page 3 of Japanese Patent No. 155332
And the compounds described on pages 3 to 4, the compounds represented by the general formulas (I) and (II) described on pages 3 to 4 of JP-A-2-32, and The compounds described on pages 4 to 6, the applicant is Fuji Photo Film Co., Ltd., and the title of the invention, which was filed on Dec. 19, 1994, serial number 87500758, is "Production of silver halide emulsion for photography. 6-8 of the specification of "Method"
A compound represented by the general formula (I) described on page,
The compounds described on pages 8-9 can be used.
Specific examples of preferable crystal habit controlling agents are shown below.

[0013]

[Chemical 1]

[0014]

[Chemical 2]

[0015]

[Chemical 3]

In particular, the method of using the bispyridinium salt described in JP-A-2-32 as a crystal habit controlling agent is an excellent method in that the particle size distribution is narrow and the sensitivity is high.

Further, in the present invention, the tabular grains have dislocation lines. Dislocation lines of tabular grains are, for example, JF Hamil
ton, Phot. Sci. Eng., 11, 57, (1967)
T. Shiozawa, J. Soc. Phot. Sci. Japan, 35, 21
3, (1972), and can be observed by a direct method using a transmission electron microscope at low temperature. In other words, the silver halide grains taken out carefully so that dislocation lines are not generated on the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beams In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μm). . From the photograph of the grain obtained by such a method, the position and number of dislocation lines for each grain when viewed from the direction perpendicular to the main plane can be obtained.

The average number of dislocation lines is 10 or more per grain. More preferably, the average number of particles per particle is 20 or more and about 1,000 or less. When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count to about 10, 20, or 30 lines, and it is possible to clearly distinguish from the case where there are only a few lines. The average number of dislocation lines per grain is calculated as the number average by counting the number of dislocation lines for 100 grains or more.

Dislocation lines can be introduced, for example, in the vicinity of the outer periphery of tabular grains. In this case, the dislocations are almost perpendicular to the outer circumference, and dislocation lines are generated starting from the position of x% of the length of the distance from the center of the tabular grain to the side (outer circumference) and reaching the outer circumference. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the start positions of the dislocation lines is similar to the particle shape, but it is not a perfect similar shape and may be distorted. This type of dislocation number is not found in the central region of the grain.
The dislocation lines are crystallographically in the (211) direction, but they are often meandering and may intersect with each other.

Further, the dislocation lines may be substantially uniformly distributed over the entire outer circumference of the tabular grains, or may be locally located on the outer circumference. That is, taking hexagonal tabular silver halide grains as an example, the dislocation lines may be limited only in the vicinity of the six vertices, or the dislocation lines may be limited in the vicinity of only one of the vertices. Conversely, the dislocation lines may be limited to only the sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the centers of two parallel main planes of tabular grains. When dislocation lines are formed over the entire main plane, the direction of the dislocation lines may be crystallographically approximately (211) when viewed from a direction perpendicular to the main plane, but (110) or In some cases, they are randomly formed, and the length of each dislocation line is also random. In some cases, they are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer periphery). is there. Dislocation lines are often straight or meandering. Also, they often intersect with each other.

The position of the number of dislocations may be limited to the outer circumference, the main plane, or a local position as described above, or may be formed by combining these.
That is, they may exist on the outer circumference and the main plane at the same time.

Introduction of dislocation lines into tabular grains can be achieved by providing a specific high silver bromide phase (high silver bromide region) inside the grains. In this case, the high silver bromide phase may have discontinuous high silver bromide regions. Specifically, the high silver bromide phase inside the grain is obtained by preparing a base grain, then providing a high silver bromide phase and covering the outside with a phase having a lower silver bromide content than the high silver bromide phase. The silver bromide content of the base tabular grains is lower than that of the high silver bromide phase, preferably 0 to 20 mol%, more preferably 0 to 15%.

The introduction of dislocations into tabular grains forms high silver chloride tabular grains serving as base grains, forms a high silver bromide phase on the surface of the base grains, and further the high silver bromide phase is converted into a high silver chloride phase ( It can be achieved by coating with a high silver chloride shell). The silver chloride content of the base grains is preferably 80 mol% or more, more preferably 90% mol or more, and further preferably 95% mol or more. The halogen composition other than silver chloride is preferably silver bromide, and is preferably less in silver iodide. The high silver bromide phase formed on the surface of the base grain means a silver halide solid solution containing silver bromide. In this case, silver bromide is preferably silver bromide, silver iodobromide, silver chloroiodobromide or silver chlorobromide, with silver bromide or silver chlorobromide being particularly preferred. The silver bromide content of the high silver bromide phase is preferably 40.
It is at least mol%, more preferably at least 80 mol%. Further, it is essential that the silver bromide content of the high silver bromide phase is higher than the silver bromide content of the base grain and the high silver chloride shell. The difference in silver bromide content between the high silver bromide phase and the base grains and the high silver chloride shell phase is preferably 20 mol% or more,
It is more preferably 40 mol% or more. The silver chloride content of the high silver chloride shell phase is preferably 80 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more. The halogen composition other than silver chloride is preferably silver bromide, and is preferably less in silver iodide.

To form a high silver bromide phase, a method of adding bromide ions to the base grains, a method of simultaneously adding bromide ions and silver nitrate, a method of adding high silver bromide fine particles having a high silver bromide content, and a bromide ion gradual Both can be preferably achieved by a method of adding a release compound. In the case of the method of adding high silver bromide fine particles, it is essential that the size of the high silver bromide fine particles is smaller than that of the base grains. The high silver bromide phase may be formed as a layer over the entire base grain or may be locally formed at a specific site of the grain. It is possible to introduce dislocations at specific sites of the grain by controlling the formation site of the high silver bromide phase. That is, dislocation lines are observed from the high silver bromide phase formation site toward the high silver chloride shell region. In order to selectively form the high silver bromide phase at a specific site of the grain, it is desirable to control the formation conditions of the base grain, the high silver bromide phase, and the phase outside thereof. The control conditions include pAg, temperature, bromide ion addition rate, presence / absence of silver halide solvent, type and amount, presence / absence of adsorbed compound on silver halide containing crystal habit controlling agent, type and amount,
Is an important factor.

Several methods are known for forming a high silver bromide-containing phase at the corner of a high silver chloride plate having a (111) main plane. For example, US Pat. No. 5272052
No. 5,089,009, a bromide ion was slowly added at low temperature to a silver chloride plate having a (111) main plane formed in the presence of 2-hydroaminoazaaines, whereby a high silver bromide-containing phase was added to a corner of the plate. It is stated that can be epitaxially grown. In order to form an epitaxial layer on the outer peripheral portion of a high silver chloride flat plate, as shown in Examples below,
It is possible by adding a KBr aqueous solution to a high silver chloride-containing flat plate having a (111) main plane.

Several methods are known for forming a high silver bromide-containing phase in the corner of a high silver chloride flat plate having a (100) main plane. For example, US Pat. No. 5,275,930.
No. 1, on a plate containing high silver chloride with (100) main plane,
It has been shown that high bromide content epitaxial can be formed at the corners of the plate by adding bromide ions while controlling the temperature and addition rate.

The introduction of dislocations into the grains is made possible by covering the high silver bromide phase with a high silver chloride shell phase. This is considered to indicate that the high silver bromide phase undergoes recrystallization between the high silver chloride phase of the base and the shell and forms a solid solution containing silver chlorobromide to cause dislocation. . That is, in the vicinity of the boundary between the high-silver bromide phase and the high-silver chloride phase, the strain caused by the difference in lattice constant between the two phases is relaxed by solid solution formation by recrystallization, and as a result, dislocation occurs. The formation of the high silver chloride shell is
It is thought that this recrystallization process is promoted, and if it is possible to promote recrystallization by some means, it may be possible to introduce dislocations without forming a high silver chloride shell phase. . However, for that purpose, after the high silver bromide phase is formed, the emulsion is sufficiently ripened under the conditions of high temperature and high pAg at which the solubility of the grains is increased.
It seems that considerable innovation is required. In either case, the high silver bromide phase may disappear by recrystallization.

Therefore, in the final grain, the dislocation line can be easily observed by the above-mentioned method, but the internal silver bromide phase introduced for introducing the dislocation line continuously changes the silver bromide composition at the boundary. Therefore, in many cases it cannot be confirmed as a clear phase. Regarding the halogen composition of each part of the grain, X-ray diffraction, EPMA (also referred to as XMA) method (method for detecting silver halide composition by scanning silver halide grain with electron beam), ESCA (also referred to as XPS)
This can be confirmed by combining the method (a method of irradiating X-rays to disperse photoelectrons emitted from the particle surface) and the like. Further, the halogen composition after introducing dislocations can be arbitrarily selected within the scope of the present invention. Therefore, after forming the high silver chloride shell phase that covers the high silver bromide phase, a phase having a high silver bromide content may be further provided outside thereof.

In general, tabular silver halide grains are tabular having two parallel planes, so that "thickness" in the present invention means two parallel planes constituting the tabular silver halide grain. It is represented by the distance. The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse, but monodisperse is more preferable. The silver halide emulsion of the present invention may be an internal latent image type emulsion or a surface latent image type emulsion.

In the process of silver halide grain formation or physical ripening, even if cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt, etc. are present together. Good. Particularly, an iridium salt or a rhodium salt is preferable. The silver salt solution (eg, AgNO ₃ aqueous solution) and the halide solution (eg, NaCl aqueous solution), which are added to accelerate the grain growth during the production of the silver halide grains of the present invention, the addition rate, the addition amount, and the addition concentration according to the addition time. A method of increasing the temperature is preferably used.

Regarding these methods, for example, British Patent No. 1,335,925 and British Patent No. 3,672,900.
No. 3, ibid. 650, 757, ibid. 4, 242, 445
No. 5, JP-A-55-142329 and JP-A-55-15812.
No. 4, No. 58-113927, No. 58-113928.
No. 58-111934, No. 58-111936, etc. can be referred to. The tabular silver halide grain of the present invention may be unchemically sensitized but can be chemically sensitized if necessary.

As the chemical sensitization in the present invention, chalcogen sensitization such as sulfur sensitization, selenium sensitization and tellurium sensitization,
And noble metal sensitization and reduction sensitization are used individually or in combination.

In sulfur sensitization, unstable sulfur compounds were used, and P. Grafkides, Chimie et Physique Photograph.
ique (Paul Momtel, 1987, 5th edition), Resea
Unstable sulfur compounds described in rchDisclosure magazine 307 volume 307105 can be used. Specifically, thiosulfates (for example, hypo), thioureas (for example, 1,3-diphenylthiourea, triethylthiourea, N-ethyl-N ′-(4-methyl-2-thiazolyl) thiourea. , N-carboxymethyl-N, N ', N'
-Trimethylthiourea), thioamides (e.g. thioacetamide), rhodanines (e.g. 3,5-diethylrhodine, 5-benzylidene-N-ethylrhodonine), phosphine sulfides (e.g. trimethylphosphine sulfide) ), Thiohydantoins, 4
-Known oxo compounds such as oxo-oxazolidine-2-thiones, disulfides or polysulfides (for example, dimorpholine disulfide, cystine, lenthionine), mercapto compounds (for example, cysteine), polythionate, elemental sulfur and Activated gelatin and the like can also be used.

In the sensitization of selenium, an unstable selenium compound is used, and JP-B Nos. 43-13489 and 44-157 are used.
48, JP-A-4-25832 and 4-109340.
No. 4, No. 4-271341, No. 5-40324, No. 5
-11385, Japanese Patent Application Nos. 4-202415 and 4-3.
No. 30495, No. 4-333030, No. 5-4203
No. 5, No. 5-4204, No. 5-106977, No. 5-
No. 236538, No. 5-241642, No. 5-286
The selenium compounds described in No. 916 and the like can be used. Specifically, colloidal selenium, selenoureas (eg, N, N-dimethylselenourea, N-trifluoroacetyl-N, N ', N'-trimethylselenourea, N-acetyl-N, N', N'-trimethylselenourea), selenoamides (eg, N, N-dimethylselenobenzamide, N, N-diethylselenobenzamide), phosphine selenides (eg, triphenylphosphine selenide, (pentafluorophenyl)) −
Diphenylphosphine selenide), selenoketones,
(For example, 4,4′-dimethoxyselenobenzophenone), isoselenocyanates, selenocarboxylates, selenoesters, diacylselenides, etc. may be used. Furthermore, Japanese Patent Publication Nos. 46-4553 and 5
A non-unstable selenium compound described in JP-A No. 2-34492,
For example, sodium selenite, potassium selenocyanate, selenazoles, selenides and the like can also be used.

In tellurium sensitization, an unstable tellurium compound is used, and JP-A-4-224595 and JP-A-4-2713 are used.
No. 41, No. 4-333043, No. 5-303157.
Japanese Patent Application No. 4-185004 and No. 4-330495.
No. 4, No. 4-333030, No. 5-4203, No. 5-
No. 4204, No. 5-106977, No. 5-28691.
Unstable tellurium compounds described in No. 6 can be used. Specifically, phosphine tellurides (for example, normal butyl-diisopropyl phosphine telluride, triisobutyl phosphine telluride, trinormal butoxy phosphine telluride, triisopropyl phosphine telluride), diacyl (di) telluride. (Eg, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (N-phenyl-N-benzylcarbimimol) Telluride, bis (ethoxycarbonyl) telluride, telluroureas (for example, N, N′-dimethylethylene tellurourea) telluroamides, telluroesters and the like may be used.

In sensitizing precious metals, P. Grafkides,
Chimie et Physique Photographique (Paul Momtel, 1987, 5th edition), Research Disclosure magazine 3
07, 307105, etc., gold, platinum,
Noble metal salts such as paradium and iridium can be used, and gold sensitization is particularly preferable. In particular,
In addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide, US Pat. Nos. 2,642,361, 5,049,484, and 50,
No. 49485, No. 5169751, No. 5252455
Gold compounds described in, for example, No. 6891857 of Belgium are also usable.

In reduction sensitization, P. Grafkides, Ch.
imie et Physique Photographique (published by Paul Momtel,
1987, 5th edition), Research Disclosure 307
The reducing compounds described in Volume 307105 and the like can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compound (eg, dimethylamineborane), hydrazine compound (eg, hydrazine, p-tolylhydrazine), polyamine compound (eg, diethylenetriamine, triethylene). Tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sodium sulfite, aldehyde compounds, hydrogen gas and the like may be used. Further, reduction sensitization may be performed in an atmosphere of high pH or excess silver ions (so-called silver ripening).

These chemical sensitizations may be used alone or in combination of two or more. When combined, a combination of chalcogen sensitization and gold sensitization, for example, gold sulfur sensitization, gold sulfur selenium sensitization, gold sulfur tellurium sensitization, and gold sulfur selenium tellurium sensitization is preferable. Further, reduction sensitization is preferably performed at the time of forming silver halide grains.

The amount of the chemical sensitizer used in the present invention varies depending on the silver halide grains used and the chemical sensitization conditions, but it is 10 ^-8 to 10 ^-2 per mol of silver halide.
A molar amount, preferably about 10 ⁻⁷ to 10 ⁻³ mol, can be used.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention may contain ordinary silver halide grains in addition to the silver halide grains of the present invention. In the photographic emulsion of the present invention containing the high silver chloride grains according to the present invention, the high silver chloride grains account for 50% or more, preferably 70% or more of the projected area of all silver halide grains in the emulsion. It is preferably 90% or more. When the photographic emulsion of the present invention and other photographic emulsions are used in combination, it is preferable to use the high silver chloride grains of the present invention in an amount of 50% or more in the mixed emulsion.

When the photographic emulsion of the present invention is mixed with another photographic emulsion, the emulsion to be mixed is more preferably a high silver chloride emulsion containing 50 mol% or more of silver chloride. The emulsion of the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a tinazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these After the aromatic hydrocarbon ring is fused to the nucleus of, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benz Imidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine as a nucleus having a ketomethylene structure. 5 such as nucleus and thiobarbituric acid nucleus
~ 6-membered heterocyclic nuclei can be applied. For example, Research Disclosure item. 17643, page 23, item IV (December 1978) or the compounds described in the cited documents can be used.

The dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,9.
No. 69 and No. 4,225,666, the spectral sensitization can be performed simultaneously with the chemical sensitization by adding the chemical sensitizer at the same time as described in JP-A-58-113,92.
It can be carried out prior to chemical sensitization as described in No. 8 or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. Furthermore, it is possible to add these said compounds separately, as taught in US Pat. No. 4,225,666, ie to add some of these compounds prior to chemical sensitization and the balance to the chemical It can also be added after sensitization and at any time during the formation of the halogen compound grains, including the method taught in US Pat. No. 4,183,756.

The addition amount is 5 × per mol of silver halide.
It can be used in an amount of 10 ⁻³ to 15 × 10 ⁻² mol, but about 5 × 10 ^{−4 to} 5 × 10 ⁻² mol is more effective for a more preferable silver halide grain size of 0.2 to 3 μm .
The silver halide emulsion prepared according to the present invention can be used in both color photographic light-sensitive materials and black-and-white photographic light-sensitive materials. Examples of the color photographic light-sensitive material include color paper, color photographic film, color reversal film, and black-and-white photographic light-sensitive material include X-ray film, general photographic film, print film, and the like. It can be preferably used for color paper.

There are no particular restrictions on other additives to the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, Research Disclosure 17
Volume 6, Item 17643 (RD17643) and 1
87, item 18716 (RD18716) can be referred to. RD17643 and RD1
The description points of various additives in 8716 are listed below.

[0048]       Additive type RD17643 RD18716   1 Chemical sensitizer Page 23 Page 648 Right column   2 Sensitivity enhancer Same as above   3 Spectral sensitizer, pages 23-24, page 648, right column-       Supersensitizer, page 649, right column   4 Whitening agents Page 24   5 Antifoggant, pages 24 to 25, page 649, right column       And stabilizers   6 Light absorber, page 25-26, page 649, right column-       Filter Dye 650, left column       UV absorber   7 Anti-Staining Agent, page 25, right column, page 650, left to right column   8 Dye image stabilizer, page 25   9 Hardener, page 26, page 651, left column   10 Binder page 26 Same as above   11 Plasticizers and lubricants Page 27 Page 650 Right column   12 Coating aid, pages 26-27 Ibid.       Surfactant   13 Antistatic agent Page 27 Same as above

Of the above additives, antifoggants and stabilizers are azoles {eg, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, Benzotriazoles, aminotriazoles, etc .; mercapto compounds {eg mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-
Phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinethione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1, 3,3a, 7) Tetraazaindenes), pentaazaindenes, etc.};
Benzenethiosulfones, benzenesulfinic acid, benzenesulfonic acid amide and the like can be preferably used.

The color coupler is preferably a non-diffusible one having a hydrophobic group called a ballast group in the molecule, or a polymerized one. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions.
Further, a colored coupler having a color correcting effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be contained. Further, the product of the coupling reaction may be colorless and may include a colorless DIR coupling compound which releases a development inhibitor.

Examples of magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, and open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers. (For example, benzoylacetanilides, pivaloylacetanilides), and the like, and cyan couplers include naphthol couplers and phenol couplers.

As a cyan coupler, US Pat. No. 377 is used.
No. 2002, No. 2772162, No. 375830
No. 4126396, No. 4334011, No. 43
No. 27173, No. 3446622, No. 4333999.
Nos. 4,451,559 and 4,427,767, etc., a phenolic coupler having an ethyl group at the meta position of the phenol nucleus, a 2,3-diacylamino-substituted phenolic coupler, a phenylureido group at the 2-position and a 5-position. Phenol couplers having an acylamino group and couplers in which sulfonamide, amide, etc. are substituted at the 5-position of naphthol are preferable because of excellent image fastness.

The above-mentioned couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for a light-sensitive material, and the same compound may be added in two or more different layers, of course. Absent.

As the anti-fading agent, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochroman, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and the phenolic hydroxyl groups of these compounds were silylated and alkylated. Representative examples are ether or ester derivatives.
Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Photographic processing of a light-sensitive material using the present invention includes
Any known method can be used, and a known processing solution can be used. The treatment temperature is usually selected from 18 ° C to 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, either a development process for forming a silver image (black and white photographic process) or a color photographic process including a development process for forming a dye image can be applied.

Known black-and-white developers include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol) and the like. The developing agents can be used alone or in combination.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-amino-N, N-diethylaniline, 3-
Methyl-4-amino-N, N-diethylaniline, 4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used.

In addition, L. F. A. Meson's "Photographic Processing Chemistry", Focal
The materials described in Press, pp. 226-229, U.S. Pat. Nos. 2,193,015, 2,592,364, and JP-A-48-64933 may be used.

The developer may be a pH buffer such as alkali metal sulfite, carbonate, borate, and phosphate, a development inhibitor such as bromide, iodide, and an organic antifoggant, or an antifoggant. Agents and the like can be included.
If necessary, a water softener, a preservative such as hydroxylamine, an organic solvent such as benzyl alcohol or diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development inhibitor such as amines, a dye-forming coupler, a competitive coupler, Fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, US Pat. No. 4,083,723.
Published in Germany (O
LS) 2,622,950 and the like may be added.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. Examples of bleaching agents include iron (III) and cobalt (III)
, Compounds of polyvalent metals such as chromium (VI), copper (II),
Peracids, quinones, nitroso compounds and the like are used. For example, ferricyanide, iron dichromate, iron (III) or cobalt (III) organic complex salts such as ethylenediaminetetracomplex salt, nitrilotriacetic acid, aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid, or Complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates, permanganates; nitrosophenol and the like can be used. Of these, potassium ferricyanide,
The ethylenediaminetetracomplex iron (III) sodium salt and the ethylenediaminetetracomplex iron (III) ammonium salt are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

Bleaching or bleach-fixing solutions are described in US Pat.
042,520, 3,241,966, Japanese Examined Patent Publication No. 4
In addition to the bleaching accelerators described in JP-A No. 5-8506 and JP-B No. 45-8836, the thiol compound described in JP-A No. 53-65732, various additives can be added.
Further, after bleaching or bleaching / fixing treatment, washing treatment may be carried out or only stabilizing bath treatment may be carried out. The present invention is further described below with reference to examples, but the present invention is not limited thereto.

[0062]

【Example】

Example 1: Effect of dislocation lines on a high silver chloride tabular plate having a (111) main plane Preparation of base emulsion A (silver chloride tabular plate having a (111) main plane) A base silver chloride tabular grain having a (111) main plane was prepared. Prepared as follows. Solution I- (1) Inert gelatin 30 g Compound Example-1 0.8 g NaCl 4 g H ₂ O 1750 cc Solution I- (2) AgNO ₃ 7.6 g H ₂ O was added to 30 cc Solution I- (3) NaCl 2. 30cc solution I- (4) AgNO ₃ 96cc solution I- (5) was added to 24.5 g H ₂ O 65 cc solution I- (6) AgNO added NaCl 0.3 g H ₂ O was added to 8 g H ₂ O ₃ 400 cc solution I- (7) was added to 101.9 g H ₂ O was added to NaCl 37.6g H ₂ O 400cc

[0063]

[Chemical 4]

Solution I- (2) and solution I- (3) were simultaneously added to solution I- (1) kept at 35 ° C with stirring over 1 minute, and the temperature of the solution was increased to 60 ° C over 15 minutes. Raised to. Next, the solution I- (4) and the solution I- (5) were mixed with 24
Add for 1 minute at the same time, and add solution I- (6) and solution I
-(7) was added simultaneously over 40 minutes to obtain pure silver chloride emulsion A
Got As a result of observation with an electron microscope, Emulsion A was (11
90% or more of the total projected area was occupied by tabular grains having two parallel main planes composed of 1) planes. Emulsion A
The emulsions obtained by further growing Emulsion A by the method described below were designated Emulsion A-1 to Emulsion A-3.

Preparation of Emulsion A-1 (silver chlorobromide tabular emulsion containing dislocations having (111) main planes: the present invention) Solution I- (8) AgNO ₃ 13.8 g H ₂ O was added to prepare a 54 cc solution I-. (9) To the emulsion A added with 5.0 g of H ₂ O at 54 cc and kept at 35 ° C., a 0.84 M aqueous KBr solution 48 was added.
cc was added (at this point, it was separately confirmed by electron microscope observation that tabular grains having epitaxial protrusions were formed on the outer periphery). Then the above solution I-
(8) and Solution I- (9) were simultaneously added over 9 minutes. After adding a precipitating agent and an acid to this and washing with water by flocculation, gelatin and water were added and redispersed.
Emulsion A was prepared by adjusting the pH and the pAg at 40 ° C. to 6.2 and 7.2 with alkali and NaCl solution.
-1 was obtained. As a result of the observation, emulsion A-1 contained at least 80 mol% of silver chloride, and about 60% of the total projected area was obtained by tabular grains having an aspect ratio of 2 or more and having 10 or more dislocation lines per grain. Was occupied. In Emulsion A-1, 95% or more of the total projected area is occupied by tabular grains having an aspect ratio of 2 or more, and the average value in the tabular grains is 0.15 μm in thickness and the circle-equivalent diameter of the main plane is 1. It was 1 μm and the aspect ratio was 8.1. Of the 60% of the projected area, 1 per particle
Zero or more dislocation lines were observed, and almost 100% of grains were 8
The content of silver chloride was 0 mol% or more (average 95.6 mol%). A transmission electron micrograph of emulsion A-1 is shown in FIG.

Preparation of Emulsion A-2 (Dislocation-Free Silver Chloride Emulsion Having (111) Main Plane: Comparative Example) By the same method as Emulsion A-1 except that 0.84M KBr aqueous solution was not added. , Emulsion A-2 was obtained. Emulsion A-2 was a pure silver chloride tabular emulsion having a grain size distribution almost equal to that of emulsion A-1.

Preparation of Emulsion A-3 (silver chlorobromide emulsion without dislocation having (111) main plane: comparative example) A silver chlorobromide emulsion having no dislocation line was prepared as follows. Solution _{I- (10) AgNO 3 13.8g H} 2 O was added added 27cc solution _{I- (12) KBr 4.8g H 2} O 54cc solution I- (11) by adding NaCl 2.5 g H ₂ O and 27 cc and emulsion A kept at 35 ° C. with stirring, Solution I- (10)
Was added at a constant rate over 9 minutes. Solution I- (1
Solution I- (11) was added over 9 minutes so that the addition amount of Solution I- (11) was decreased linearly from 6 cc / minute to 0 over 9 minutes. The amount added per minute was linearly increased from 0 to 6 cc / min. This was washed with water and redispersed in the same manner as Emulsion A-1 to adjust pH and pAg.
Emulsion A-3 having a grain size distribution and an average bromine content almost similar to 1 were obtained. In the observation with a transmission electron microscope, dislocation lines were not observed in most of the grains of emulsion A-2 and emulsion A-3.

Emulsions A-1 to A-3 were optimally chemically sensitized with sodium thiosulfate, potassium thiocyanate and chloroauric acid, and coated to obtain Samples 1 to 3. The coating was performed as follows. That is, any one of Emulsion A-1 to Emulsion A-3 as an emulsion, coupler 1 shown below, and 4-hydroxy-6 as a stabilizer.
An emulsion layer containing methyl-1,3,3a, 7-tetrazaindene, sodium dodecylbenzenesulfonate as a coating aid, tricresyl phosphate as a hardener, and gelatin was added to 2,4-dichloro-6-hydroxy. −
It was coated on a triacetyl cellulose film support provided with an undercoat layer together with a protective layer containing 1,3,5-triazine sodium salt and gelatin.

[0069]

[Chemical 5]

In the emulsion layer, 1 × 10 ^-3 per mol of silver
Samples 4 to 6 were obtained in the same manner as in Samples 1 to 3 except that the dye 1 shown below in a molar amount was added before coating.

[0071]

[Chemical 6]

In order to examine the sensitivity of the silver halide itself in the absorption wavelength region (inherent sensitivity) and the desensitization (inherent desensitization) due to the addition of the spectral sensitizing dye, Samples 1 to 6 were used as optical wedges and Toshiba Glass. V-40 and UVD manufactured by Co., Ltd.
The film was exposed to tungsten light for 1 second through a -36C filter and subjected to the following treatment. Eastman Kodak Co., Ltd. designated D-19 treatment (development at 20 ° C. for 5 minutes) Fuji Photo Film Co., Ltd. designated CN-16 treatment (development at 38 ° C. for 3 minutes 15 seconds) These results are shown in Table 1. Indicated. The photographic sensitivity is the reciprocal of the exposure amount required to give an optical density value higher than the fog value by 0.2, and the sensitivity of Sample 5 is 10
It is shown as a relative value when 0 is set. Here, the sensitivity in CN-16 treatment was determined using the optical density value measured through a green filter.

[0073]

[Table 1]

To examine the absorption wavelength region sensitivity (spectral sensitization sensitivity) of the spectral sensitizing dye, Samples 4 to 6 were exposed to tungsten light through an optical wedge and an SC-50 filter manufactured by Fuji Photo Film Co., Ltd. After exposure for 1 second, the photographic sensitivity was evaluated in the same manner as described above. Here, in order to compare the development progress of these samples, the photographic properties were evaluated at a plurality of development times. Development time is 1 in CN-16 processing
3 minutes 15 minutes, 2 minutes 15 seconds, 3 minutes 15 seconds (development temperature is 38 ° C.), and the photographic sensitivity is a relative value when the sensitivity when developing Sample 5 for 3 minutes 15 seconds is 100. did. The results are shown in Table 2.

[0075]

[Table 2]

As shown in Table 1, the emulsion having dislocation lines obtained by the present invention has high sensitivity and less desensitization by the spectral sensitizing dye. As a result, Table 2
As shown in (1), the emulsion having a dislocation line obtained by the present invention has higher spectral sensitization sensitivity than the silver chloride and silver chlorobromide emulsions having no dislocation line. Further, the emulsion having a dislocation line obtained by the present invention achieves high sensitivity in a short development time region as compared with an emulsion having no dislocation line, and thus the development progress is extremely good. Is shown in. The superiority of the emulsion of the present invention in the progress of development can be seen not only for an emulsion having no dislocation having the same silver bromide content but also for a pure silver chloride emulsion having no dislocation having no silver bromide. To be This is contrary to the well-known development inhibitory effect of silver bromide on silver chloride emulsions, which is an unexpected and surprising result. In fact, in comparison between emulsions having no dislocations, it can be seen from Table 2 that the developability of an emulsion having a high silver bromide content is poor.
Is shown in.

Example 2: Effect of dislocation lines on a high silver chloride tabular plate having a (100) main plane Preparation of base emulsion B (silver chloride tabular plate having a (100) main plane) Base silver chloride having a (100) main plane Tabular grains were prepared as follows. Solution II- (1) inert gelatin 20g NaCl 1.3g H ₂ O 1600cc solution II- (2) 15.6cc solution II- (3) by adding _{AgNO 3 7.96g H 2 O NaCl 2.73g} H 2 15.6cc added O solution _{II- (4) AgNO 3 1.46g H} 2 O was added 28.6Cc solution II- (5) 28.6cc solution was added KBr 1.02g H ₂ O II- ( 6) the AgNO ₃ 23.87g H ₂ O was added 46.8Cc solution II- (7) 46.8cc solution II- (8 by addition of _{NaCl 8.21g H 2 O) AgNO 3} 92.82g H 2 O In addition 182cc

Nitric acid was added to the solution II- (1) kept at 40 ° C. to adjust the pH to 4.1. In this, solution II-
(2) and Solution II- (3) were simultaneously added with stirring at a constant flow rate over 15 seconds. Next, Solution II- (4)
And solution II- (5) were added in the same manner over 20 seconds, and solution II- (6) and solution II- (7) were added in the same manner as above.
Added over seconds. After 1 minute, 13 g of gelatin and 2 g of NaCl were added and aged for 5 minutes, and then the temperature of the solution was raised to 75 ° C. over 12 minutes. After heating, NaCl
And NaOH were added, the silver potential was 90 mV, and the pH was 5.
Each was adjusted to 9 and aged for 14 minutes. Solution after aging
II- (8) was added with stirring at a constant flow rate over 20 minutes. Simultaneously with the addition of the solution II- (8), a 3M NaCl aqueous solution was added by the controlled double jet method so that the silver potential of the solution was kept at +90 mV. Thus, a base silver chlorobromide emulsion B having an average bromine content of about 1 mol% with respect to silver was obtained.

Preparation of Emulsion B-1 (silver chlorobromide flat plate containing (100) principal planes: the present invention) Emulsion B held at 60 ° C. was added with silver bromide fine grains formed by the method described below. 4 mol% was added to the number of moles of silver and ripened for 10 minutes. 1M AgNO ₃ and NaCl
73.4 cc of each aqueous solution was simultaneously added at a constant flow rate over 3 minutes. After adding a precipitating agent and an acid to this and washing with water by flocculation, gelatin and water, and NaOH at 40 ° C. to a pH of 6.2 and a pAg of 7.2.
And an aqueous NaCl solution were added and redispersed to obtain Emulsion B-1. As a result of observation, Emulsion B-1 contained at least 80 mol% of silver chloride and contained 10 grains per grain.
About 60% of the total projected area was occupied by tabular grains having two or more dislocation lines and an aspect ratio of 2 or more.
In the emulsion B-1, 80% or more of the total projected area is occupied by tabular grains having an aspect ratio of 2 or more, and the average value in the tabular grains is 0.22 μm in thickness and the circle-equivalent diameter of the main plane is 1. It was 2 μm and the aspect ratio was 6. Of the 80% of the projected area particles, 1 per particle
Zero or more dislocation lines were observed, and almost 100% of grains were 8
The content of silver chloride was 0 mol% or more (average 95.6 mol%).

Preparation of Emulsion B-2 (silver chlorobromide emulsion without dislocation having (100) principal plane: comparative example) In the preparation process of Emulsion B-1, instead of silver bromide fine grains, the method described below was used. Emulsion B-2 having substantially the same grain shape and grain size distribution as Emulsion B-1 was obtained by a different preparation process except that the formed silver chloride fine grains were added in an amount of 4 mol% based on the number of moles of silver in Emulsion B. Emulsion B-2 was a silver chlorobromide emulsion containing about 1 mol% Br with respect to silver.

Preparation of Emulsion B-3 (silver chlorobromide emulsion without dislocation having (100) principal planes: Comparative Example) Emulsion B held at 60 ° C. was stirred with 102.8 cc.
Of 1M AgNO ₃ of it was added simultaneously over 20 min an aqueous KBr solution, and 73.4cc of 1M of NaCl aqueous solution of 1M of 29.4Cc. The addition rate of each aqueous solution was controlled as follows. That is, the AgNO ₃ aqueous solution is kept constant for 20 minutes, the KBr aqueous solution is changed from an initial speed of 0 cc / min to a final speed of 5.14 cc / min, and the NaCl aqueous solution is changed from an initial speed of 5.14 cc to a final speed of 0 cc / min. In addition, the addition rate was controlled so that the addition rate changed linearly in 20 minutes. This was washed and redispersed in the same manner as Emulsion B-1 to obtain Emulsion B-3 having substantially the same grain shape and grain size distribution as Emulsion B-1. Emulsion B-3 was a silver chlorobromide emulsion containing 4.4 mol% Br with respect to silver. The presence or absence of dislocations in the obtained emulsion was examined by observing it with a transmission electron microscope at a temperature of 120K. Emulsion B-2
Almost no grains having dislocations were observed in Emulsion B-3.

Emulsions B-1 to B-3 were optimally chemically sensitized with sodium thiosulfate, potassium thiocyanate and chloroauric acid, and the above dye 1 was added to silver in an amount of 0.7 × 10. After adding ^-3 mol, samples 7 to 9 were obtained by coating. The coating was performed as follows. That is, any of Emulsion B-1 to Emulsion B-3 as the emulsion, the above-mentioned coupler 1, 4-hydroxy-6methyl-1,3,3a, 7-tetrazaindene as the stabilizer, and dodecylbenzenesulfone as the coating aid. An emulsion layer containing sodium acidate, tricresyl phosphate as a hardener, and gelatin was added to 2,4-dichloro-6-hydroxy-1,
It was coated on a triacetyl cellulose film support provided with an undercoat layer together with a protective layer containing 3,5-triazine sodium salt and gelatin. In order to examine the photographic performance, Samples 7 to 9 were exposed to tungsten light for 1 second through an optical wedge and an SC50 filter manufactured by Fuji Photo Film Co., Ltd., and the following treatments were performed. Eastman Kodak Co., Ltd. designated D-19 processing (development at 20 ° C for 1, 3, 5 minutes) Fuji Photo Film Co., Ltd. designated CN-16 treatment (development at 38 ° C for 1 minute 15 seconds, 2 minutes 15 seconds) 3 minutes 15 seconds) The characteristics of Samples 7 to 9 are shown in Table 3, and the evaluation results of photographic properties are shown in Table 3.
Each is shown in Table 4. The photographic sensitivity is shown as a relative value of the reciprocal of the exposure amount required to give an optical density value 0.2 higher than the fog value for each sample.
For each of the -16 processes, the sensitivity of Sample 8 was set to 100 when the development time was 5 minutes and 3 minutes 15 seconds, respectively. Here, the sensitivity in CN-16 treatment was determined using the optical density value measured through a green filter.

[0083]

[Table 3]

[0084]

[Table 4]

Table 4 shows that the emulsion having dislocation lines obtained by the present invention has high sensitivity and low fog. Further, it can be seen that the development progresses not only for emulsions having no dislocation lines and having the same silver bromide content, but also for comparison with emulsions having no dislocation lines and having a low silver bromide content. As described above, it was revealed that the present invention is effective for a high silver chloride tabular emulsion whose main plane is (100) plane. In the high silver chloride emulsion having a dislocation line of the present invention, the progress of development is rapid even though the content of silver bromide is high. Is considered to have occurred.
It is considered that this development accelerating effect may be due to the fact that the dislocation lines facilitate the formation of a latent image which is advantageous for the progress of development. It is considered that such a development accelerating effect of the dislocation lines was first revealed by introducing the dislocation lines into the high silver chloride emulsion. That is, the reason why dislocations can be introduced by silver bromide, which has a relatively small development inhibiting effect as compared with silver iodide, is because a high silver chloride emulsion is used as a base, and therefore, a high dislocation line having a dislocation line according to the present invention. It can be said that the silver chloride emulsion has an effect which cannot be expected from the known emulsion having silver bromide-based dislocations.

Preparation of silver bromide fine grain emulsion In a reaction vessel, 1200 ml of an aqueous gelatin solution (gelatin having an average molecular weight of 30,000 (hereinafter referred to as M3 gelatin), KBr0.0) was used.
9 g, pH 3.0) was added, and while stirring at a temperature of 23 ° C., 240.0 ml of AgNO ₃ aqueous solution (AgNO ₃ 6
0.0 g, M3 gelatin 2.0 g, 1M HNO ₃ 1.
00.0 ml) and KBr aqueous solution 240.0 ml (KBr4
2.0 g, M3 gelatin 2.0 g, 1M KOH1.0
(including ml) was simultaneously mixed and added at 90 cc / min for 2 minutes and 40 seconds. After stirring for 30 seconds, the pH was adjusted to 4.0 and pBr3.2. The obtained silver bromide fine grain emulsion had an average equivalent spherical diameter of 0.04 μm.

Preparation of silver chloride fine grain emulsion In a reaction vessel, 1200 ml of gelatin aqueous solution (M3 gelatin 2
4g, containing 0.5g NaCl, pH 3.0),
While stirring at a temperature of 23 ° C., AgNO ₃ aqueous solution 900.
0 ml (AgNO ₃ 225.0 g, M3 gelatin 9.0)
g, containing 2.3 ml of 1M HNO ₃ ) and 900.0 ml of aqueous NaCl solution (77.4 g of NaCl, M3 gelatin 9.
0 g, containing 2.3 ml 1M KOH) at 90 cc / min
Simultaneous mixed addition for 0 minutes. After stirring for 30 seconds, pH
It was adjusted to 4.0 and pCl 1.7. The obtained silver chloride fine grain emulsion had an average equivalent spherical diameter of 0.06 μm.

[Brief description of drawings]

FIG. 1 is an electron micrograph (magnification: about 20,000 times) showing a crystal structure of silver halide grains of emulsion A-1.

Claims (4)

(57) [Claims] 1. Grains occupying 30% or more of the projected area of all grains contain at least 80 mol% of silver chloride,
A silver halide emulsion comprising silver halide grains which are tabular grains having an aspect ratio of 2 or more and have 10 or more dislocation lines per grain. 2. The dislocation line extends from the center of the tabular grain to the outer periphery.
Starting from the position of 30% or more and less than 99% of the distance to
The halogenation according to claim 1, which reaches the outer circumference.
Silver emulsion. 3. A high silver bromide-containing phase having a silver bromide content higher than the average silver bromide content of the silver halide grains on all or a part of the surface thereof, which contains at least 80 mol% of silver chloride. the provided, according to claim 1 or 2 obtained by coating a high-silver bromide-containing phase further than the high silver bromide-containing phase at a lower silver halide phase having high and silver bromide content: silver chloride content is
The method for producing a silver halide emulsion according to 1. 4. The silver bromide content of the high silver bromide-containing phase is 40 mol.
% Or more, the halogen according to claim 3.
Method for producing silver halide emulsion.