JPH01183645A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To improve the sensitivity, the gradation and the graininess of the title emulsion by incorporating silver halide particle contg. a silver halide phase having specified content and distribution of AgI in the emulsion. CONSTITUTION:The silver halide photographic emulsion is composed of a dispersion medium and a silver halide particle A, and the particle A contains a silver halide phase contg. >=3mol.% of AgI, and the distribution of AgI contd. in the phase is completely uniform. The particle A is formed by adding a growing phase to the crystalline nucleus, and the composition of the phase is composed of silver iodobromide, etc. And the position of the phase contg. AgI within the particle A may be the center, the whole or the outside of the particle. And, the phase may be constituted of a single layer or plural layers.

Description

Detailed Description of the Invention (Field of the Invention) The present invention relates to a light-sensitive silver halide emulsion useful in the field of photography, and more particularly to a silver halide emulsion comprising a dispersion medium and silver halide grains containing silver iodide, and a silver halide emulsion comprising silver halide grains containing a dispersion medium and silver iodide. Regarding the manufacturing method.

BACKGROUND OF THE INVENTION Among light-sensitive silver halide emulsions used in the photographic field, emulsions other than silver iodobromide emulsions have only limited use in camera-sensitive photographic elements. As commonly used in the photographic field, silver iodobromide grains contain silver iodide in a silver bromide crystal lattice in an amount below its solubility limit in silver bromide, that is, an iodide content of about 40 mol % or less. . The iodide content in silver iodobromide emulsions has the following advantages (
■) and disadvantages (■).

■Increased latent image formation efficiency, increased light absorption (inherent absorption of silver halide), improved adsorption of additives, and improved graininess.

■ Suppression of development and interference with chemical sensitization.

Up to now, in the development of silver iodobromide photography with camera sensitivity, numerous studies have been conducted in an effort to increase the above-mentioned advantages and further reduce the disadvantages. What is particularly important is that silver halide emulsion grains (hereinafter referred to as grains)
The question was which part (location) of the throat should the silver iodide be placed in?

Duffin Photographic Emulsion Chemistry, Focal Press, 1966,
PI3 states as follows:

"In the case of silver iodobromide emulsions, an important factor to consider is the location of the iodide. The iodide may be present primarily in the center of the crystal, it may be distributed throughout the grain, or it may be primarily It can exist on the outside.

The actual location of the iodide is determined by the preparation conditions, and this location clearly influences the physical and chemical properties of the crystal. First, the entire amount of both iodide and bromide salts is present in the reaction vessel, and then an aqueous silver salt solution is introduced into the reaction vessel to form silver iodobromide particles. In the so-called single-jet method, silver iodide precipitates first, and therefore silver iodide tends to concentrate in the center of the grains. On the other hand, in the double jet method in which both iodide and bromide salts are simultaneously introduced into a reaction vessel together with silver salt, the distribution of silver iodide within the grains can be intentionally controlled. For example, if silver iodide is distributed uniformly throughout the grain, or if the addition of bromide salt is reduced or stopped midway through grain formation and the addition of iodide salt is continued, iodide is formed on the outer surface (outside) of the grain. A silver iodobromide shell with high silver or silver iodide content can be formed. JP-A-58-113927 describes tabular silver iodobromide grains in which at least 50% of the total projected area has a thickness of less than 0.5 μm, a diameter of 0.6 μm or more, and an average aspect ratio of 8:1 or more. , and the tabular grain has first and second opposing parallel major surfaces and a central region extending between the two major surfaces, and the silver iodide content in the central region is also A silver halide emulsion is disclosed which is characterized in that it contains tabular silver iodobromide with a lower iodide content than in at least one laterally displaced region extending between the two major faces. JP-A-59-99433 discloses that 10% (
(number) or more are tabular silver halides with an aspect ratio of 5 or more, and silver iodide is present in the inner part of 80 mol% of the silver amount of the entire grain from the center side in the major axis direction or minor axis direction of the grain. (inner high iodine phase), and the average iodine content of the inner high iodine phase is 5 times or more the average iodine content of silver halide present outside the phase,
And the amount of silver in the inner high iodine phase is 50% of the amount of silver in the entire particle.
Silver halide emulsions containing silver halide grains that are less than or equal to mol % are disclosed. Furthermore, JP-A-60-14772
In 7, in silver halide grains having a multilayer structure and an aspect ratio of 5 or less, the difference in average iodine content between any two adjacent layers each having a homogeneous iodine distribution in the grain is 10 mol% or less; A silver halide photographic emulsion containing silver halide grains having this multilayer structure and having a total silver iodide content of 10 mol % or less is disclosed.

JP-A-60-14331 discloses a core part containing 10 to 45 mol% of silver iodide and a shell part containing 5 mol% or less of silver iodide, and the average silver iodide content is 7 mol% or more. A silver halide photographic emulsion is disclosed that includes silver halide grains having a well-defined layered structure. Furthermore, JP-A-61-245151 has a plurality of layered structures with different silver iodide contents, the outermost shell has a silver iodide content of 10 mol% or less, and the silver iodide content is higher than that of the outermost shell. an intermediate shell having a silver iodide content intermediate between the outermost shell and the high silver iodide content shell; Disclosed is a silver halide emulsion characterized in that it is provided with: The content described in these patents is to vary the silver iodide content in each grain depending on its location (particularly on the inside or outside of the grain), thereby obtaining better photographic properties.

On the other hand, Tan (Y, T, Tan) and Bella Old (R, C
.

Baetzold calculated the energy state of silver halide and proposed at the 5PSE 41st Annual Meeting that iodine in silver iodobromide crystal grains tends to form clusters. The distribution of silver iodide in the tabular silver iodobromide grains described above is a change in silver iodide content at different locations in units of at least 300 to 1000 Å or more, but tan (Y, ↑).

Tan) and Baetzold (R, C, Baetzold)
As expected, a more microscopic and non-uniform distribution of silver iodide is observed in silver iodobromide crystals.

The silver halide grains having a completely uniform silver iodobromide phase disclosed in the present invention are grains in which the microscopic silver iodide distribution described above is completely uniform.

The silver iodide distribution in microscopic silver iodobromide grains can be confirmed by a cooling transmission electron microscope, and the silver halide grains with completely uniform silver iodide disclosed in the present invention have not been produced until now. That's something I couldn't get.

(Objective of the Invention) The object of the present invention is to provide a negative-working silver halide emulsion with low fog, high sensitivity, improved graininess and sharpness covering power, convenient storage stability, and excellent pressure resistance. It's about doing.

(Disclosure of the Invention) An object of the present invention is to provide a silver halide photographic emulsion comprising a dispersion medium and silver halide grains, the silver halide grains having a silver halide phase containing 3 mol% or more of silver iodide. This was achieved by a silver halide photographic emulsion characterized by a completely uniform distribution of silver iodide in the silver halide phase containing the silver iodide.

As an example of the silver halide emulsion grains of the present invention having a completely uniform silver iodide distribution, tabular silver iodobromide grains having a silver iodobromide phase will be described here.

The term "completely uniform silver iodide distribution" as used herein refers to a more microscopic distribution, which is completely different from the silver iodide distribution that has been handled up to now. As a means of measuring silver iodide distribution in silver iodobromide grains, analytical electron microscopy (^nal
ytical Electron Microscope
y) is often used. For example, King (M, A, Kin
g) Loretto (M, l), Mattanahan (T, J).

berry (P, J
, Berry) [analytical electron microscopy (analytical electron microscopy)
tical electron m1croscopy
) Study of Iodide Distribution by Analytical Electron Microscopy
” Probeless in Basic Principles
Of Imaging Systems, International Combres OpPhotography Sciences
Koln, 1986, describes the topographical results of silver iodide content in silver iodobromide tabular grains. The size of the electron beam irradiation probe used in this research was 50 people, but in reality the electron beam spreads due to the elastic scattering of electrons, and the diameter of the electron beam spot irradiated on the sample surface was approximately 300 mm.
I end up in a human position. Therefore, this method cannot measure a finer silver iodide distribution. Japanese Patent Application Publication No. 5
Silver iodide distribution was also measured using the same method in No. 8-113927, but the size of the electron beam tube 7 used was 0.2 μ.

Therefore, depending on these measurement methods, more microscopic (10
It is impossible to clarify the silver iodide distribution (local variations on the order of 0 or less).

This microscopic distribution of silver iodide can be determined, for example, by Hamilton (J.
It can be observed by a direct method using a transmission electron microscope at low temperature as described in 67P, P57 and Takehiro Shiozawa, Photographic Society of Japan, Vol. 35, No. 4, 1972P, P213. In other words, the silver halide grains were taken out under safe light to prevent the emulsion grains from printing out, and placed on a mesh for electron microscopy, and the sample was heated with liquid nitrogen or liquid helium to prevent damage (printout, etc.) caused by the electron beam. Observation is performed using the transmission method in a cooled state.

Here, the higher the accelerating voltage of the electron microscope, the clearer the transmitted image can be obtained, but up to 0.25 μm particle thickness is 200 Kv.
olt, 1000K for larger grain thicknesses
Volt is good. The higher the accelerating voltage, the greater the damage to particles caused by the irradiated electron beam, so it is preferable to cool the sample with liquid helium rather than liquid nitrogen.

(2) The shadow magnification can be changed as appropriate depending on the particle size of the sample, but is from 20,000 times to 40,000 times.

When a transmission electron micrograph of the silver iodobromide tabular grains is photographed in this manner, a very fine annual ring-like striped pattern is observed in the silver iodobromide phase.

An example of this is shown in FIG. The tabular grains shown here are
A silver bromide tabular grain is used as a core, and a silver iodobromide shell containing 10 mol% of silver iodide is formed on the outside of the core, and its structure can be clearly seen in this transmission electron micrograph. . In other words, a part of the core is silver bromide and is naturally uniform, so only a uniform, flat image can be obtained, but on the other hand, the silver iodobromide phase has a very fine ring-like striped pattern. Can be clearly confirmed. It can be seen that the spacing between these striped patterns is very fine, on the order of 100 people or less, indicating extremely microscopic non-uniformity. This very fine striped pattern indicates non-uniformity of silver iodide distribution, which can be revealed by various methods, but more directly, it can be explained by the movement of iodide ions through these tabular grains within the silver halide crystal. Annealing under conditions
This can be clearly concluded from the fact that this striped pattern completely disappears when exposed to heat (for example, at 250° C. for 3 hours).

The tree-ring-like striped pattern indicating the non-uniformity of silver iodide distribution in the tabular silver iodobromide emulsion grains described here is the same as that cited earlier.
It is clearly observed in the transmission electron micrograph attached to JP-A-58-113927, and is also clearly shown in the transmission electron micrograph in the study by King et al. cited above. Due to these facts, silver iodobromide grains that have been prepared with a constant silver iodide content to obtain a uniform silver iodide distribution are completely contrary to the intention of their manufacture.
It has a very microscopic non-uniform distribution of silver iodide, and so far no technique for making it uniform has been disclosed, nor has a method for its production been disclosed. The present invention discloses an emulsion in which the microscopic silver iodide distribution is completely uniform and a method for producing the emulsion.

As mentioned above, the silver halide grains of the present invention having a "completely uniform silver iodide distribution" can be obtained by observing the transmission image of the grains using a cooled transmission electron microscope. It can be clearly distinguished from silver halide grains. That is, the silver halide grains containing silver iodide of the present invention have at most two microscopic lines at an interval of 0.2 μm in a direction perpendicular to the lines due to microscopic non-uniformity of silver iodide. ,
Preferably one, more preferably none. The lines that make up the annual ring-like stripes that indicate this microscopic heterogeneity in silver iodide occur perpendicular to the direction of grain growth, and as a result, these lines extend concentrically from the center of the grain. to be distributed. For example, in the case of the tabular grain shown in Figure 1, the lines constituting the tree-ring-like striped pattern, which indicates the nonuniformity of silver iodide, are perpendicular to the growth direction of the tabular grain, and as a result, they are parallel to the edge of the grain. and the direction perpendicular to them points toward the center of the particle, and is distributed concentrically around the center of the particle.

Of course, if the silver iodide content changes rapidly during grain growth, the boundary line will be observed as a line similar to that described above using the observation method described above. consists of only a single line and can be clearly distinguished from the line composed of multiple lines derived from the microscopic inconsistency of silver iodide. Furthermore, the line resulting from such a change in silver iodide content can be clearly confirmed by measuring the silver iodide content on both sides of this line using the analytical electron microscope described above.

Such a line due to a change in silver iodide content is completely different from a line due to microscopic non-uniformity of silver iodide as referred to in the present invention, and indicates a "macroscopic silver iodide distribution."

In addition, if the silver iodide content is changed substantially continuously during grain growth, there will be no rapid change in the silver iodide content, so the line showing the macroscopic change in the silver iodide content above are not observed, and therefore, if there are at least three or more lines at intervals of 0.1 μm, this means that there is microscopic non-uniformity in the silver iodide content.

Thus, the silver halide grains of the present invention having a completely uniform silver iodide distribution can be seen microscopically at intervals of 0.2 μm in the direction perpendicular to the line in a transmission image of the grains obtained using a cooled transmission electron microscope. It is a silver halide grain having at most two lines showing a typical silver iodide distribution, preferably one line, and preferably no such line, and such a grain accounts for a total of 2 lines. Silver halide grains account for at least 60%, preferably at least 80% and more preferably at least 90%.

Silver halide grains, which have been called silver halide grains containing uniform silver iodide, are grown by a double-jet method using a mixture of silver nitrate and a halide salt of a constant composition (constant iodide content). was simply added to the reaction vessel,
Although the macroscopic silver iodide distribution in such grains is indeed constant, the microscopic silver iodide distribution is not uniform. In the present invention, such particles are referred to as particles having a "fixed halogen composition" and are clearly distinguished from the "completely uniform" particles shown in the present invention.

Next, a method for producing the silver halide grains of the present invention will be described.As will be described in detail later, the production method for obtaining the grains of the present invention relates to a grain growth method, and the present invention does not involve nucleation. . James
The Theory of the Photographic Ink Process, 4th Edition, P, p. 89 states, ``Crystallization is often considered to consist of two main processes: nucleation and growth.

(Two other processes occur under certain conditions, Ostwald ripening and recrystallization.) Nucleation is the process by which entirely new crystals are formed and a rapid increase in the number of crystals occurs. The growth is
It is the addition of a new layer to an already existing crystal. ” is described. The particles of the present invention and their manufacturing method relate to this growth process, and nucleation is performed using a conventionally known method. Therefore, the central part of the particle, which shows the nucleus in a transmission image taken using a cooling transmission electron microscope, is outside the scope of the present invention. After the nucleation is complete, if you use it as a nucleation crystal and cause growth by adding a new layer, the boundary line between the nucleation crystal and the growth phase can be confirmed as a line in the transmission image, especially if the halogen is present in the nucleus and the growth phase. If there is a difference in composition, it can be confirmed more clearly.

In the present invention, the composition of silver halide grains having a completely uniform silver iodide distribution includes silver iodobromide, silver iodochloride,
Although silver iodochlorobromide may be used, silver iodobromide and silver iodochlorobromide are preferable. The phase containing silver iodide may be located in the center of the silver halide grain, over the entire grain, or in the outer part.

Further, the number of phases in which silver iodide is present may be one or more. In general, the phase containing silver iodide often forms a layered structure due to the mechanism of grain growth, but it may also form a specific portion. For example, by utilizing the difference in properties between the edges and corners of tabular grains, it is possible to form a silver iodide phase only at the edges or only at a portion of the corners.

Further, by forming a shell outward from the shell, it is also possible to produce silver halide grains having silver iodide at specific points without a layered structure inside the grain.

Specifically, an example can be given in which, after nucleation, grain growth is performed using the configuration shown below.

First coating layer Second coating layer Third coating layer 18-Ag
Br1 - -2AgBr Uniform -AgBrr -3 Uniform^gBrl
AgBr -4-AgBr1-5 AgBr AgBr
3 AgBr heterogeneous-AgBrI homogeneous-A
gBr17 Average-AgBr1 AgBr
Uniform^gBrT8 Heterogeneous^gBr 1 9 Uniform-AgBr1 AgBr
10 Uniform-AgBr1 Ununiform-AgBr1 *Uniform means "completely uniform" in the present invention.

Furthermore, in the case of silver iodochlorobromide, silver chloride may be contained in the above layer, and the layer containing silver chloride may be any of the first coating layer, the second coating layer, and the third coating layer.

In the present invention, the proportion of the homogeneous AgBr1 phase in the particles is preferably 5 to 95 mol%.

The silver iodide content of the silver iodobromide phase contained in the emulsion grains of the present invention is 3 to 45 mol%, preferably 5 to 35 mol%.
It is. When the silver iodide content is less than 3 mol %, even if microscopic non-uniformity of silver iodide exists, the width of its distribution is substantially small and does not cause much inconvenience. For example, when the outermost layer of a silver halide grain is a silver halide phase containing silver iodide, when the grain is chemically sensitized, if the silver iodide content of the outermost layer is less than 3 mol%, the halide Whether the silver iodide distribution in the silver phase is "perfectly uniform" or not has little bearing on the sensitivity and fog achieved; however, the silver iodide in the outermost silver halide phase containing silver iodide When the content is 3 mol % or more, especially 5 mol % or more, conventional grains with non-uniform silver iodide distribution have extremely low sensitivity and high fog even if chemically sensitized. In other words, conventional grains having a silver halide phase with a "constant silver iodide halide composition" as the outermost layer are prevented from chemical sensitization. This is as stated at the beginning of the description of the prior art of this patent. Therefore, in this case, it was not possible to take advantage of the merits of silver iodide, such as increased latent image forming efficiency, increased light absorption, improved adsorption of additives, and improved graininess. However, if the silver halide phase with the "completely uniform" silver iodide distribution of the present invention is in the outermost layer, there will be no interference with the chemical sensitization described above, and all the advantages of containing silver iodide can be utilized. It is possible to obtain high sensitivity, low fog, good graininess, and high sharpness that have not been achieved before. The reason why a grain surface with a nonuniform iodide root distribution hinders chemical sensitization and a grain surface with a completely uniform silver iodide distribution does not hinder chemical sensitization at all is that the lattice constant of the grain crystal surface is nonuniform. The silver iodide distribution is not constant, and as a result, the composition and size of the chemical sensitizing nuclei formed thereon become non-uniform, making it impossible to obtain optimal chemical sensitization conditions. On the other hand, in the case of a surface with a completely uniform silver iodide distribution, the chemical sensitizing nuclei will have a uniform composition and size, making it possible to perform optimal chemical sensitization. We will have to wait for further consideration.

On the other hand, the silver halide phase containing silver iodide is inside the grain, and the outermost layer has a low silver iodide content, or if no silver iodide is present, the band structure is folded at the interface between the two phases. This is expected, and due to the bending, the regular tag generated by light absorption is directed into the inside of the particle, promoting charge separation between electrons and holes, and the silver iodide inside the grain captures the hole, and the electron It is thought that sensitivity increases by preventing recombination with It has been found that when the silver iodide distribution inside the grain is completely uniform, the achieved sensitivity is high, and when the silver iodide distribution is uneven, the achieved sensitivity is low. This is a surprising effect, and the reason is not yet clear, but if the silver iodide distribution is completely uniform, the internal hole trapping ability is uniform; It is expected that the electron-hole recombination prevention effect will be significantly different between the two.

In this case as well, as mentioned above, if the internal silver iodide content is less than 3 mol%, the sensitivity obtained will not change substantially even if there is a difference in the uniformity of silver iodide distribution, but silver iodide When the content was above 3 mol %, particularly above 5 mol %, the sensitivity of grains with completely uniform silver iodide distribution was clearly higher than that of non-uniform grains.

The total silver iodide content of the emulsion grains of the present invention is 2 mol%
The above is the most effective, however, 4 mol% or more is more effective. More preferably, it is 5 mol% or more. The size of the silver halide emulsion grains having a completely uniform silver iodide distribution according to the present invention is not particularly limited, but it is preferably 0.3 μm or more, more preferably 0.8 μm or more, particularly 1.4 μm or more. The effect is greater. The shapes of the silver halide grains according to the present invention are cubic, octahedral, dodecahedron, dodecahedron, icosahedron (3octahedron, tetrahexahedron, rhomboid icosahedron), and 46 It may have a regular crystal shape (normal crystal grain) such as a hedron, it may have an irregular crystal shape such as a spherical shape or a potato shape, and it may also have various shapes having one or more twin planes. particles, especially with two or three parallel twin planes.
Hexagonal tabular grains and triangular tabular grains may exist.

Next, a method for producing silver halide grains of the present invention will be specifically described. The silver halide grain molding method of the present invention consists of nucleation and grain growth, and as mentioned above, the present invention relates to grain growth, and nucleation follows conventional methods.

l Nucleation The silver halide grains that serve as the nucleus of the silver halide of the present invention are P
, Chemie et Phi by Glafkides
siquePhoLographique (Paul
Monte1, 1967) G, F, Durf
in Author Photographic E+mulsion
Chemrstry (The Focal Pres.
s publication, 1966), V, L, Zelikmanet
Making and Coating Ph
otographicEmulsion (The F
ocal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. .

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be used in combination.

When preparing the nuclei of silver halide grains, it is preferable that the halogen composition be constant.

When the inner core is silver iodobromide, it is preferable to use the double jet method or the controlled double jet method.

The pAg when preparing the nucleus varies depending on the reaction temperature and the type of silver halide solvent, but is preferably 7 to 7.
It is 11. Further, it is preferable to use a silver halide solvent because the grain formation time can be shortened. For example, commonly known silver halide solvents such as ammonia and 1,000-onythyl can be used.

The shape of the nucleus may be plate-shaped, spherical, twinned, octahedral, cubic, tetradecahedral, or mixed.

Further, the nuclei may be polydisperse or monodisperse, but it is more preferable that the nuclei be monodisperse. Here, "monodisperse" has the same meaning as described above.

Also, to make the particle size uniform, British patent 1.53
No. 5,016, Special Publication No. 48-36890, No. 52-16
364, etc., a method of changing the addition rate of silver nitrate or alkali halide aqueous solution according to the grain growth rate, and U.S. Pat. As described above, it is preferable to use a method of varying the aqueous solution concentration to grow quickly within a range that does not exceed the critical supersaturation degree. These methods do not cause re-nucleation and each silver halide grain is coated uniformly, so they are preferably used when introducing a coating layer, which will be described later.

In the process of nucleus formation or physical ripening of silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts,
Iron salts or iron complex salts may also be present.

2 After the formation of the growth nucleus, in order to grow the nucleus, water of water-soluble silver salt and alkali halide? 8 solution is newly added to the reaction vessel to prevent nucleation. In the conventional method, an aqueous solution of silver salt and halide salt is added into a reactor under efficient stirring. At this time, when growing silver halide with a single halide composition (for example, silver bromide, silver chloride), the silver halide phase is completely uniform, which can be observed using a transmission electron microscope. However, no microscopic non-uniformity was observed.

If the composition is originally a single halide, nonuniform growth (aside from the unit) will not occur in principle, and therefore,
In the growth of pure silver bromide and pure silver chloride, the non-uniformity referred to in the present invention is impossible regardless of the preparation conditions. However, in the growth of silver halide having a plurality of halide compositions (so-called mixed crystal), non-uniform growth in the halide composition becomes a serious problem. It has already been mentioned that the non-uniform distribution of silver iodide can be clearly confirmed by transmission electron microscopy.

On the other hand, various studies have been made to obtain uniform growth of silver halide. It is known that the growth rate of silver halide grains is greatly influenced by the silver ion concentration and equilibrium solubility in the reaction solution. Therefore, if the concentrations (silver ion concentration, halide ion concentration) in the reaction solution are non-uniform, the growth rate will differ depending on each concentration, and non-uniform growth will occur. Techniques disclosed in US Pat. No. 3,415,650, British Patent No. 1,323,464, and US Pat. No. 3,692,283 are known as methods for improving this local concentration deviation. These methods include a reaction vessel filled with an aqueous colloid solution, a hollow rotating mixer having a slit in the wall of a medium-thick cylinder (the inside is filled with an aqueous colloid solution, and more preferably the mixer is moved up and down by a disk). ) is installed so that its axis of rotation is vertical, and the halogen salt aqueous solution and silver salt aqueous solution are fed from the upper and lower open ends through the supply pipes into the mixer that is rotating at high speed. (If there is an upper and lower separation disc, the halogen salt aqueous solution and silver salt aqueous solution supplied to the upper and lower chambers are diluted by the colloid aqueous solution filled in each chamber, and This is a method in which silver halide particles are grown by rapidly mixing and reacting near the output loss lift), and silver halide particles produced by centrifugal force generated by the rotation of a mixer are discharged into an aqueous colloid solution in a reaction vessel. However, even with this method, the non-uniformity of silver iodide distribution cannot be solved at all, resulting in non-uniform distribution of silver iodide. Tree ring-like striped patterns were clearly observed using a cooled transmission electron microscope.

On the other hand, Japanese Patent Publication No. 55-10545 discloses a technique for preventing uneven growth by locally improving the concentration deviation. In this method, a halogen salt aqueous solution and a silver salt aqueous solution are separately supplied through supply pipes from the lower end of a mixer into which a colloid aqueous solution is dropped into a reactor filled with a colloid aqueous solution, and the reaction takes place. Both reaction solutions are rapidly stirred and mixed by a lower stirring blade (turbine blade) installed in the mixer to grow silver halide, and immediately the grown halogen is removed by an upper stirring blade installed above the stirring blade. This is a technique in which silver oxide particles are discharged from the opening of an upper mixer into an aqueous colloid solution in a reaction vessel. However, even with this method, the non-uniform distribution of silver iodide could not be resolved at all, and tree ring-like striped patterns indicating non-uniform distribution of silver iodide were clearly observed. Moreover, JP-A-57-92
A similar technique is also disclosed in No. 523, but this method also cannot solve the problem of iodide unequal distribution at all.

JP-A No. 62-99751 has an average diameter range of 0.4 to 0.
．． 55μm and aspect ratio of 8 or more.
115435 has an average diameter range of 0.2-0.55 μm
Photographic elements are disclosed containing tabular silver halide grains of silver bromide and silver iodobromide, in which embodiments double aqueous silver nitrate and potassium bromide solutions were used to grow the silver iodobromide tabular grains. Silver iodide (A
gI) Emulsion (particle size approximately 0.05 μm, bone gelatin 4
A technique has been disclosed in which silver iodobromide tabular grains are grown by simultaneously adding and supplying silver iodobromide (0 g/Ag mole).

However, even with this method, the non-uniform distribution of silver iodide was not resolved at all, and tree ring-like striped patterns indicating non-uniform distribution of silver iodide were clearly observed.

Thus, it is clear that completely uniform silver iodide distribution cannot be realized using the techniques disclosed so far. As a result of extensive research, the present inventor has found that in the growth of silver halide grains containing iodide, the silver ions and halide ions (iodine ions, bromide ions, and chloride ions) that form the grains are placed in an aqueous solution in a reaction vessel. By supplying the silver halide particles in the form of fine silver halide particles with the desired halide composition without adding any additives, and allowing the silver halide grains to grow, the ring-like striped pattern completely disappears and completely uniform silver iodide is produced. We found that the distribution of

This is a surprising technique that cannot be achieved using conventional methods. A more specific method is: ① Addition of fine grain emulsion containing silver iodide prepared in advance Fine silver halide grains (i.e. 1 emulsion containing silver bromide, silver chloride iodobromide, silver iodochloride)
Silver halide grains are grown by supplying only this fine grain emulsion to the reaction vessel without supplying any aqueous solution of a water-soluble root salt or aqueous solution of a water-soluble halide to a reaction vessel.

■Method for supplying silver halide fine particles from a mixer outside the reaction vessel As an efficient method for supplying fine particles, a powerful and efficient mixer is installed outside the reaction vessel, and an aqueous solution of water-soluble root salt and water-soluble halide are added to the mixer. and a protective colloid aqueous solution are rapidly mixed to generate extremely fine silver halide particles, which are immediately and continuously fed into a reaction vessel. At this time, as in method (2), the aqueous solution of the water-soluble root salt and the aqueous solution of the water-soluble halogen salt are not supplied to the reaction vessel at all. U.S. Pat. No. 2,146,938 discloses that a coarse grain emulsion is grown by mixing coarse particles that have not adsorbed adsorbed substances with fine particles that have not similarly adsorbed adsorbed substances, or by slowly adding a fine grain emulsion to a coarse grain emulsion. A method is disclosed. The silver iodide content of the fine particles is not specified here, and the silver iodide content in the examples is only 2.6 mol% or less. JP-A-57-23932 discloses that a fine grain emulsion prepared in the presence of a growth inhibitor is washed with water by decantation, redispersed, the emulsion is further melted, and the emulsion is added to the emulsion to be grown to dissolve the fine grains. discloses a method for performing particle growth.

Although it would certainly be advantageous to obtain microparticles of smaller size in this method, redissolution of the microparticles in the reaction vessel would be hindered by the growth inhibitor. Furthermore, this patent does not include any description of the halogen composition of fine grains, and the practical column only describes pure silver bromide fine grains, which is completely different from the present invention, which relates to the growth of silver halide grains containing silver iodide. It is something.

U.S. Pat. Nos. 3,317,322 and 3,206,313 disclose that a silver halide grain emulsion serving as a core is chemically sensitized to have an average grain size of at least 0.8 μm, and is chemically sensitized to have an average grain size of 0.4 μm or less. A method for preparing a silver halide emulsion having a high internal sensitivity by mixing untreated silver halide grain emulsions and ripening to form a shell is disclosed.

This method relates to the production of internal latent image-forming grains with a high internal density, and furthermore, there is only a description of a specific example in which the silver iodide content of the shell formation is 2 mol% or less, and the silver iodide content is high. (3 mol % or more) and is completely different from the present invention, which relates to surface latent image-forming silver halide grains. In the specification of JP-A-58-113927 (P
, P, 207) [Silver, bromide and iodide salts can be introduced initially or during the growth stage in the form of finely divided silver halide suspended in a dispersion medium. That is, silver bromide, silver iodide and/or silver iodobromide particles can be introduced." However, in this method, it is not disclosed that silver halide grains are grown only by supplying a fine grain emulsion without supplying any silver salt or halide salt aqueous solution, and a specific method is also not specified. Not yet.

JP-A-62-124500 describes an example in which host particles in a reaction vessel are grown using extremely fine particles (approximately 0.02 μm) prepared in advance, but the fine particles used are bromide particles. It is silver and is completely different from the present invention.

Next, each method will be explained in detail.

■About the method In this method, tabular grains that serve as nuclei or cores are made to exist in a reaction vessel in advance, and then a previously prepared emulsion containing fine-sized grains is added and the fine grains are melted by so-called Ostwald ripening. ,
It accumulates in the nucleus or core, thereby causing particle growth. The halide composition of the fine grain emulsion contains silver iodide that is the same as the silver iodide content of the target tabular grains, which are silver iodobromide, silver chloroiodobromide, and silver iodochloride. The particle size preferably has an average diameter of 0.1 μm or less,
More preferably, it is 0.06 μm or less. In the present invention, the dissolution rate of the fine particles is important, and in order to increase the dissolution rate, it is preferable to use a silver halide solvent. Silver halide solvents include water-soluble bromide, water-soluble chloride,
Examples include thiocyanates, ammonia, thioethers, and thioureas.

For example, thiocyanate (U.S. Pat. No. 2,222°264)
No. 2,448,534, No. 3゜320.06
9), ammonia, 1,000-onythyl compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574,6)
No. 28, No. 3,704.130, No. 4,297,
439, 4.276.347, etc.), 1,000-ion compounds (for example, JP-A-53-144319, JP-A-53-8)
2408, 55-77737, etc.), amine compounds (e.g., JP-A-54-100717, etc.), thiourea derivatives (e.g., JP-A-55-2982), imidazoles (e.g., JP-A-54-100717), Examples include substituted mercaptotetrazoles (for example, JP-A-57-202531).

The temperature at which silver halide grains are grown is 50°C or higher, preferably 60°C or higher, more preferably 70°C or higher. Further, the fine grain emulsion for crystal growth may be added at one time or in portions, but it is preferably supplied at a constant flow rate, and more preferably the addition rate is increased. In this case, how to increase the addition rate depends on the concentration of coexisting colloids, the solubility of silver halide crystals, the size of silver halide fine particles, the degree of agitation in the reaction vessel, the size and concentration of crystals present at each point,
It is determined from the relationship between the hydrogen ion concentration (pH), silver ion concentration (Cp A g), etc. of the aqueous solution in the reaction vessel and the target crystal particle size and its distribution, but it can be easily determined by routine experimental methods. It can be determined by

Regarding (2), the crystal growth method disclosed in the present invention, as described above, involves adding silver ions and halide ions (including iodide ions) necessary for silver halide crystal growth to an aqueous solution as in the conventional method. Rather than supplying silver halide grains, fine silver halide crystals are added and their high solubility is utilized to induce Ostwald ripening, thereby growing silver halide grains. In this case, the rate-determining step in the system is not the growth rate of silver halide grains, but how quickly the fine grains dissolve and supply silver ions and halide ions into the reaction vessel. When an emulsion with fine grains is prepared in advance as in the method, it is desirable to have grains as small as possible, but on the other hand, the smaller the size of silver halide grains, the higher their solubility and the more unstable they become. As a result, Ostwald ripening occurs on its own, resulting in an increase in particle size.

James (T, H, Jan + es), The Theory of the Photographic Process, 4th edition, contains Lippmann emulsions as fine grains.
Emulsion) is cited and its average size is 0.0
It is described as 5 μm. Particle size 0.05μ
Although it is possible to obtain fine particles of less than m, even if they are obtained, they are unstable and the particle size easily increases due to Ostwald ripening. Although this Ostwald ripening can be prevented to some extent by adsorbing the adsorbate, the rate of bone dissolution also decreases, which is contrary to the intention of the present invention.

In the present invention, this problem was solved by the following three techniques.

■After forming the fine particles in the mixer, immediately add them to the reaction vessel.

After forming fine grains in advance to obtain a fine grain emulsion, it is redissolved, and the dissolved fine grain emulsion is added to a reaction vessel that holds silver halide grains serving as the core and in which a silver halide solvent is present to prevent grain growth. What happened was mentioned in ■. However, once the extremely fine particles are generated, they undergo Ostwald ripening during the particle formation process, water washing process, redispersion process, and redissolution process, resulting in an increase in the particle size. In this method, this Ostwald ripening occurs by providing a mixer very close to the reaction vessel and shortening the residence time of the additive liquid in the mixer, thereby immediately adding the generated fine particles to the reaction vessel. I tried not to. Specifically, the residence time t of the liquid added to the mixer is expressed as follows.

In the production method of the present invention, t is 10 minutes or less, preferably 5 minutes or less, more preferably 1 minute or less, even more preferably 20 seconds or less. The fine particles thus obtained in the mixer are immediately added to the reaction vessel without their particle size increasing.

Perform powerful and efficient stirring using an O mixer.

James (T, Hjames) The Theory of the Photographic Ink Process P, P, 93 states, ``Along with Ostwald ripening...
Jfi (coaIessence). During core nocence ripening, the crystals that were previously far apart directly
There is a sudden change in particle size as larger crystals form upon contact and deposition. Both Ostwald ripening and corenocence ripening occur not only after the completion of stacking, but also during stacking. ” The corelenescence ripening described here is
This is especially likely to occur when the particle size is very small, and especially when stirring is insufficient. In extreme cases, coarse particles may even be formed.In the present invention, as shown in Figure 2, a closed mixer is used, so the stirring blades in the reaction chamber are rotated at a high rotation speed. This was not possible with a conventional open-type reaction vessel (with an open type, when the stirring blade is rotated at high speed, the liquid is blown away by centrifugal force, and there is also the problem of foaming, making it difficult to put into practical use). ) Powerful and efficient stirring and mixing can be performed, the above-mentioned coalescence ripening can be prevented, and as a result, fine particles with an extremely small particle size can be obtained. In the present invention, the rotation speed of the stirring blade is 1000 r, p, m or more, preferably 200 or, p, m or more, more preferably 3000 r, p, m or more.
r, p, m or more.

Injection of protective colloid aqueous solution into mixer The aforementioned coalescence ripening can be significantly prevented by protective colloid of silver halide fine particles. In the present invention, the protective colloid aqueous solution is added to the mixer by the following method.

■Inject the protective colloid aqueous solution alone into the mixer.

The concentration of the protective colloid is preferably 1% by weight or more, preferably 2% by weight, and the flow rate is at least 20% of the sum of the flow rates of the silver nitrate solution and the aqueous halide solution, preferably at least 50%, and more preferably 100% or more. .

■Incorporating a protective colloid into the halogen salt aqueous solution.

The concentration of the protective colloid is at least 1% by weight, preferably at least 2% by weight.

■Incorporating a protective colloid into the silver nitrate aqueous solution.

The concentration of the protective colloid is at least 1% by weight, preferably at least 2% by weight. When gelatin is used, it is better to mix the silver nitrate solution and the protective colloid solution immediately before use, since gelatin silver is made from silver ions and gelatin, and silver colloid is produced by photolysis and thermal decomposition.

Further, the above methods (1) to (4) may be used alone or in combination, or three may be used at the same time. As the protective colloid used in the present invention, gelatin is usually used, but other hydrophilic colloids can also be used.
It is described in section ■.

Thus, the particle size of the fine particles obtained by the techniques (1) to (0) can be confirmed by placing the particles on a mesh and using a transmission electron microscope at a magnification of 20,000 times to 40,000 times. The size of the fine particles of the present invention is 0.06 μm or less, preferably 0.06 μm or less, preferably 0.06 μm or less.
．． 0.03 μm or less, more preferably 0.01 μm or less.

In this way, it becomes possible to supply particles of extremely fine size to the reaction vessel, resulting in a higher dissolution rate of fine particles,
Therefore, a higher growth rate of silver halide grains in the reaction vessel can be obtained. Although the method no longer requires the use of silver halide solvents, silver halide solvents may be used if desired to obtain higher growth rates or for other purposes. The silver halide solvent is as described in Method (2). According to this method, the supply rate of silver ions and halide ions to the reaction vessel can be freely controlled. Although a constant feed rate may be used, it is preferable to increase the addition rate. The method is
890, 52-16364. The rest is as stated in ■Law. Furthermore, according to this method, the halogen composition during growth can be freely controlled; for example, it is possible to maintain a constant silver iodide content during the growth of tabular grains, or to continuously increase or decrease the silver iodide content. or change the silver iodide content at some point.

The reaction temperature in the mixer is preferably 60°C or lower, preferably 50°C or lower, more preferably 40°C or lower. At a reaction temperature of 35° C. or lower, ordinary gelatin tends to coagulate (1), so it is preferable to use low molecular weight gelatin (average molecular weight 30,000 or lower).

The emulsions of this invention are typically spectrally sensitized.

Methine dyes are usually used as the spectral enhancing dyes used in the present invention, and these include -anine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Dyes are included. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is,
viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
Imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus , indole nucleus, benzoxadol nucleus, naphthoxadol nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus,
Benzimidazole nuclei, quinoline nuclei, etc. are applicable.

These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

The amount of sensitizing dye added during silver halide emulsion preparation is
Types of additives and halogenated IL! Although it cannot be stated unambiguously in terms of the amount, etc., it can be used in approximately the same amount as that added in the conventional method.

That is, the preferred amount of sensitizing dye added is silver halide 1
The amount of O,OO per mole is 1 to 100 mmoi, more preferably 0.01 to 1Q mmol.

The sensitizing dye is added after or before chemical ripening.For the silver halide grains of the present invention, the sensitizing dye is most preferably added during or before chemical ripening (e.g. during grain formation, during physical ripening). added at the time).

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
For example, the emulsion may contain a substance that exhibits hyperchromic enhancement.
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 2,933.390, U.S. Pat. No. 3,635,7)
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615,613, 3.6
No. 15,641, 3.617. No. 295, 3, 6
The combinations described in No. 35,721 are particularly useful.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example H, Friesel (H.

Fr1eser) Wi4, Day Grundlager
Die Grundlagen
derPhotography Prozes
se mit Silberhalogeniden)
(Academische Verlagsgesellschacht 196
8) The method described on pages 675 to 734 can be used.

sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines); reduction aggravation method using noble metal compounds (e.g., gold complex salts,
A noble metal compound using a complex salt of a metal of group (I) of the periodic table such as Pt, Ir, or Pd can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazole M
(especially nitro- or halogen-substituted): heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercapto Pyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; oxadurinthione; azaindenes, such as tetraazaindenes (especially 4-hydroxy direct Many compounds known as antifoggants or stabilizers can be added, such as (3a, 7) tetraazaindenes); benzenethiosulfonic acids; henzenesulfinic acid; etc.

The antifoggant or stabilizer is usually added after chemical sensitization, but more preferably it can be selected during chemical ripening or before the start of chemical ripening. That is, in the process of forming silver halide emulsion grains, during the addition of the silver salt solution, after the addition until the start of chemical ripening, during the chemical ripening (during the chemical ripening time,
(preferably within 50% of the time from the start, more preferably within 20% of the time).

The emulsion of the present invention can be used in photographic window light materials having any layer structure, regardless of whether the emulsion layer is IN or has two or more layers.

A silver halide multilayer color photographic light-sensitive material using the emulsion of the present invention has a multilayer structure in which emulsion layers containing a binder and silver halide grains for separately recording blue, green and red light are superimposed, Each emulsion layer consists of at least two layers: a high-speed layer and a low-speed layer. Particularly practical layer configurations include the following.

(11Bu/BL/Gf-r/GL/RH/RL/S+
2+ BH/BM/BL/GH/GM/GLRH/R
The layer structure of M/RL/S and (31B
H/BL/GH/RH/GL/RL/5RD-2253
4, JP-A-59-177551, JP-A No. 59-177552
It has a layer structure of 4-BH/GH/RH/BL/GL/RL/S as described in et al.

Here, B is the blue-sensitive layer, G is the green-sensitive layer, and R is the red S.
Also, H represents the highest sensitivity layer, M represents the intermediate layer, L represents the low sensitivity layer, and S represents the support. Recording on the optical layer is omitted.

Among these, the preferred layer structure is (l8(2) or (4)).

In addition, +51 B described in JP-A No. 61-34541
H/BL/CL/GH/C, L/RH/RL/S +61 BH/BL/GH, /CL/CL/RH/R
Layer configurations such as L/S are also preferred.

Here, CL is a multilayer effect imparting layer, and the others are as described above.

Further, the high-sensitivity layer and the low-sensitivity layer having the same coloring property may be reversely arranged.

The silver halide emulsion of the present invention can be applied to color light-sensitive materials as described above, but it can also be applied to other light-sensitive materials, whether the emulsion layer is one layer or multilayer, such as X-ray light-sensitive materials, black-and-white light-sensitive materials. It can be similarly applied to materials, photosensitive materials for plate making, photographic paper, etc.

Various additives for the silver halide emulsion of the present invention, such as binders, chemical sensitizers, spectral sensitizers, stabilizers, gelatin hardeners, surfactants, antistatic agents, polymer latex, cloak f+, color couplers, There are no particular restrictions on the support, coating method, exposure method, development method, etc. of the photosensitive material using ultraviolet absorbers, anti-fading agents, dyes, and emulsions of these materials.For example, Research Disclosure 1
Volume 76, Item 17643 (RD-17643)
, same 187S, item 18716 (RD-187
16) and volume 225, item 22534 (RD-
22534) can be referred to.

The descriptions of these research disclosures are shown in the list below.

Additive type RD17643 RD18716
RD225341 Chemical aggravator page 23 6
Page 48 right column Page 24 2 Sensitivity enhancer Same as above 4 Brightening agent Page 24 Ultraviolet absorber 8 Dye image stabilizer Page 25 3
Page 2 9 Hardener Page 26 Page 651 Left MA
Page 28 10 Binder Page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 Right column 1
4 Color coupler 25 pages 649 pages
Page 31 The color coupler used in the present invention preferably has a ballast group or is polymerized to have diffusion resistance, and the coupling active position is a campling-off group rather than a hydrogen atom daily coupler. Substituted two-equivalent couplers are preferable because the amount of silver coated can be reduced, and couplers in which the coloring dye has appropriate diffusivity, colorless couplers, or those that release a development inhibitor upon coupling reaction are preferred. DIR couplers or couplers that release development accelerators can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
No. 7,210, No. 2.875.057 and No. 3
, No. 265, 506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
No. 3,933,501 and No. 4,022゜62
0, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent Box 4,
No. 401,752, No. 4,326.024, RD1
8053 (April 1979), British Patent Box 1,425
, No. 020, West German Application No. 2.219,917, No. 2. 261. No. 361, No. 2,329,587
Typical examples thereof include the nitrogen atom separation type yellow couplers described in No. 1, No. 2, 433.812, and the like. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness;
- Benzoylacetanilide couplers provide high color density.

Examples of magenta couplers that can be used in the present invention include oil-protected couplers of indasilone type or cyanacetyl type, preferably pyrazoloazole type couplers such as 5-pyrazolone type and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is Km with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. Same No. 2゜3
No. 43.703, No. 2,600,788, No. 2.
No. 908,573, same No. 3. 062. No. 653, No. 3,152,896 and No. 3936.015
It is written in the number etc. As a leaving group for two-equivalent 5-pyrazolone couplers, U.S. Patent Box 4,310,619
The nitrogen atom leaving group or U.S. Patent Box 4.3 described in No.
Particularly preferred are the arylthio groups described in No. 51,897.

Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides a simple color density.

As pyrazoloazole couplers, U.S. Patent Box 3,
Pyrazolobenzimidazoles as described in US Pat.・Disclosure 24220
(June 1984) and JP-A No. 60-33552, and pyrazolopyrazoles described in Research Disclosure 24230 (June 1984) and JP-A-60-43659. 9 Imidazo(1,2-b) pyrazoles described in U.S. Pat. No. 4,500.630 are preferable in terms of low yellow side absorption of the coloring dye and light fastness, and U.S. Pat. No. 4,540.654 Pyrazolo (
1,5-b)(L, 2°4) Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, preferably the naphthol-based couplers described in U.S. Pat. No. 2,474°293, and preferably US Pat.
, No. 212, No. 4゜146.396, No. 4,22
Typical examples include the oxygen atom elimination type two-equivalent naphthol couplers described in No. 8,233 and No. 4,296.200. Specific examples of phenolic couplers include U.S. Patent No. 2,369.929 and U.S. Pat.
No. 01,171, No. 2,772.162, No. 2,
No. 895,826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Patent Box 3,772.
, 002, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group in the meta-position of the phenol nucleus, U.S. Pat.
No. 8.308, No. 4,126.396, No. 4.
No. 334,011, No. 4,327゜173, West German Patent Publication No. 3,329,729 and European Patent No. 121
, 365, and U.S. Patent Box 3,446;
No. 622, No. 4.333,999, No. 4,451
, No. 559 and No. 4,427,767, etc., which have a phenylureido group at the 2-position and an acylamino group at the 5-position. Patent application No. 59-93605, No. 59-264277
The cyan cabbler described in No. 59-268135, in which the 5-position of naphthol is substituted with a sulfonamide group, an amide group, etc., also has excellent fastness of the colored image and can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use a colored coupler in combination with a color negative phase for shadowing. U.S. Patent No. 4.163゜670 and Japanese Patent Publication No. 5
7-39413, etc. or U.S. Pat. No. 4,004,929, U.S. Pat.
, 138°258 and British Patent No. 1,146,36
Typical examples include the magenta-colored cyan coupler described in No. 8.

Granularity can be improved by using a coupler in which the coloring dye exhibits appropriate diffusivity. Examples of such blur couplers include magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570.
Also, European Patent No. 96゜570 and West German Application No. 3
, 234,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4,080°211. Specific examples of polymerized magenta couplers include British Patent No. 2,10°2.173 and U.S. Pat. No. 4.367.28.
No. 2, Japanese Patent Application No. 60-75041, and No. 60-11
No. 3596.

The present invention may also include a coupler that releases a development inhibitor upon development, a so-called DIR coupler.

As a DIR coupler, for example, U.S. Pat. No. 3.227
．． Those that release heterocyclic mercapto type development inhibitors as described in Japanese Patent Publication No. 554, etc.: Those that release benzotriazole derivatives as development inhibitors described in Japanese Patent Publication No. 58-9942, etc.; A so-called colorless DIR coupler described in JP-A No. 52-90932 which releases a nitrogen-containing heterocyclic development inhibitor with decomposition of methylol after separation; US Pat. No. 4.248.962
and JP-A No. 57-56837, which release a development inhibitor with an intramolecular nucleophilic reaction; No. 58-98728, No. 58
-209736, 58-209737, 58-
No. 209738, No. 58-209739 and No. 58
209740, etc., which releases a development inhibitor by electron transfer via a conjugated system after separation: JP-A-57-
151944 and 58-217932, which release a diffusible development inhibitor that is deactivated in the developer; Japanese Patent Application Nos. 59-38263 and 59-39
Examples include those that release a reactive compound described in No. 653, and generate a development inhibitor or deactivate the development inhibitor by reaction in the film during development. Among the above-mentioned DIR couplers, those that are more preferable in combination with the present invention are the developer-deactivated type represented by JP-A-57-151944; U.S. Pat. No. 4,248,962;
and the timing type represented by Japanese Patent Application No. 57-154234; and the reaction type represented by Japanese Patent Application No. 59-39653. Particularly preferred among these are the
-151944, 58-217932, patent application No. 1973
No. 9-75474, No. 59-82214, No. 59-8
Developer deactivation type DIR couplers described in No. 2214 and No. 59-90438, etc. and Japanese Patent Application No. 1983-396
This is a reactive DIR coupler described in No. 53 and the like.

In the light-sensitive material of the present invention, a compound that releases a nucleating agent, a development accelerator, or a precursor thereof (hereinafter referred to as "development accelerator, etc.") in an image form during development can be used. A typical example of such a compound is British Patent No. 2,0
97,140 and 2,131.188, and is a coupler that releases a development accelerator etc. by a coupling reaction with an oxidized product of an aromatic primary amine developer, that is, a DAR coupler. .

It is preferable that the development accelerator etc. released from the DAR coupler have adsorption properties to silver halide.
No. 638 and No. 59-170840. Particularly preferred are DAR couplers that produce N-acyl-substituted hydrazines having a monocyclic or fused heterocycle as an adsorption group, which is detached from the coupling active site of the photographic coupler with a sulfur atom or a nitrogen atom. Specific examples of couplers are described in JP-A-60-128446.

Specific examples of high boiling point 8g solvents used to disperse color couplers include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, etc.), phosphoric acid or phosphonic acid. Esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptoquine ethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenine) phosphonates, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amide furnaces (diethyldodecaneamide, N-
tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-terL-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline M form (N,N-dibutyl-
2-butoquino-5-tert-octylaniline, etc.)
, hydrocarbons (paraffin, dodecylbenzene, diisopropylnafculene, etc.). In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C.
Any organic solvent having a temperature of about 160°C or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, soclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

Suitable supports that can be used in the silver halide photographic emulsion of the present invention are described, for example, in RD, No. 17643, page 28, and in RD, No. 17643, page 647, right column to page 648, page 648, right column.

The binder used in the silver halide emulsion to which the present invention is applied is preferably gelatin, but in addition to gelatin, derivative gelatin such as phthalated gelatin, dextran, cellulose derivatives, polyvinyl acetate, polyacrylamide, polyvinyl alcohol, etc. used.

Examples of gelatin hardening agents include active halogen compounds (
2,4-dichloro-6-hydroxy-1゜3.5-)riazine and its sodium salt, etc.) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propatol, 1,2-bis( Vinylsulfonylacetamido)ethane or a vinyl polymer having a vinylsulfonyl group in its side chain) is preferred because it quickly hardens hydrophilic colloids such as gelatin and provides stable photographic properties.

N-carbamoylpyridinium salts (1-morpholinocarbonyl-3-pyridinio) methanesulfonate, etc.)
and haloamidinium salts 1 (1-(1-chloro-1-pyridinomethylene)pyrrolidinium 2-naphthalenesulfonate, etc.) are also excellent in their fast curing speed.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can be developed by the usual method described in RD, Ishii 17643, pages 28 to 29, and in 651 left column to right column of Ishibe 18716. Can be done.

A color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 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 their sulfates, hydrochlorides or pt-luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), etc. There are various preservatives, such as ethylene glycol and diethylene glycol. 8 agent, benzyl alcohol, polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifying agents, aminopolycarboxylic acids, aminopolymer Various chelating agents such as phosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, and 1-hydroxyethylidene −
1,■-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (O-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It is also possible to make rR1 or less. When reducing the amount of replenishment, it is preferable to reduce the area of contact with the air in the processing tank to prevent thinning of the liquid and air oxidation. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■), Kobal) (I
II), compounds of polyvalent metals such as chromium (Vl), copper (n), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide dichromate; residual complex salts of iron (I) or cobalt (I), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1. Aminopolycarboxylic acids such as 3-diaminoprobanetetraacetic acid, glycol etheramine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. Can be used. Among these, aminopolycarboxylic acid iron (III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron 1) complex salts, are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron (■) complex salts are particularly useful in both clean liquors and bleach-fix solutions. These iron aminopolycarboxylic acids (
I) The pH of the bleach or bleach-fix solution using complex salts is usually 5.
65-8, but it is also possible to process at an even lower pH for faster processing.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893.858, German Pat.
No. 290.812, JP-A-53-95.630, Research Disclosure Corporation 17,129 (197
Compounds having a mercapto group or a disulfide bond described in JP 50-14.0.129) etc.
Thiazolidine derivatives described in US Pat. No. 3,706
, 561; JP-A-58-16
Iodide salts described in No. 235; West German Patent No. 2,748.
Polyoxyethylene compounds described in Japanese Patent Publication No. 430, polyamine compounds described in Japanese Patent Publication No. 45-8836, bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in US Pat. No. 3,893,858 and Western Patent No. 1. Compounds described in No. 290°812 and JP-A-53-95,630 are preferred. Furthermore, U.S. Patent No. 4,55
Also preferred are the compounds described in No. 2°834. These bleach accelerators may be added to the photosensitive material. These bleaching accelerators are particularly effective when bleaching and fixing color brightening materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiogates are commonly used, and ammonium thiosulfate is the most commonly used. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the publicly available materials (for example, depending on the materials used, such as couplers), the use, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnalof the 5ociety of
Motion Picture and T
elevision Engineers Volume 64, P.
248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will propagate, and the generated suspended matter will adhere to the materials for public sale. The problem arises. As a solution to such problems in the processing of the color optical material of the present invention,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Sterilization of microorganisms" by Sanitary Technology Metals It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents" by Nippon Seedling Prevention and Antifungal Science Kinawa, "Sterilization and Antifungal Technology."

The pH of the washing water in the treatment of publicly available materials of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can be set variously depending on the characteristics of the publicly available materials, their uses, etc., but generally they are 20 seconds to 10 minutes at 15-45'C, preferably 30 seconds to 5 minutes at 25-40°C. A range is selected.

Furthermore, the 8-light material of the present invention can also be directly treated with a stabilizing solution instead of the above-mentioned washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8.543 and 58-14
All known methods described in No. 834, No. 60-220,345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, and an example thereof is a stabilization bath containing formalin and a surfactant, which is used as a final bath for color photogenic materials for photography. can.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color phosphorescent material of the present invention may have a built-in color developing kingdom for the purpose of simplifying and speeding up processing. In order to incorporate it, it is preferable to use various precursors of color developing agents. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35,628.

The silver halide color brightening material of the present invention may contain various types of 1-phenyl-3 for the purpose of promoting color development, if necessary.
- Typical compounds that may contain pyrazolidones are JP-A-56-64,339 and JP-A-57-144,547.
No. 58-115.438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but it is possible to accelerate the processing and shorten the processing time by increasing the temperature to a higher temperature, or conversely by increasing the temperature to a lower temperature to improve both performance and the stability of the processing solution. can be achieved. In addition, in order to save public party materials, West German Patent No. 2.226.770 or U.S. Patent No. 3
, 674.499 may be carried out using cobalt intensification or hydrogen peroxide intensification.

Effects of the present invention The thus obtained silver halide emulsion of the present invention has silver halide grains containing completely uniform silver iodide distribution,
It is possible to provide a negative-working halogenated emulsion having excellent characteristics in sensitivity, gradation, graininess, sharpness, resolution, covering power storage, latent image stability, and pressure resistance.

The present invention will be further explained below with reference to Examples.

Example 1 Silver iodobromide tabular grain silver iodobromide fine grain emulsion! -A 2.0% by weight containing 0.026 M potassium bromide
Add one drop of 1.2M nitric acid to 2.6β gelatin solution using the double jet method while stirring. liquid and 1.08M
A halogen salt aqueous solution containing 0.12M of potassium bromide and 0.12M of potassium iodide was added at 1,200 m each over 15 minutes. During this time, the gelatin solution was kept at 35°C. After this, the emulsion was washed using a conventional flocculation method and gelatin 3
After adding 0 g and dissolving it, the pH was adjusted to 6.5 and the pAg to 8.6. The obtained silver iodobromide fine particles (silver iodide content: 1
0%) had an average particle size of 0.07 μm.

Tabular Silver Bromide Core Emulsion 1-B Add a 0.8% by weight gelatin solution containing 0.09M potassium bromide to a 2.0M silver nitrate solution by double jet method with stirring <2. Add 30 cc of 0M potassium bromide solution. During this time, the gelatin solution in the reaction vessel was maintained at 30°C. After the addition, the temperature was raised to 75°C, and 40g of gelatin was added.

Then 1.0M silver nitrate solution was added to bring the pBr to 2.5.
5, after which 150 g of silver nitrate was added in an accelerated flow of N (end flow rate 10 times that of the start) over the course of 60 minutes;
At the same time, double jet potassium bromide has a pBr of 2.55.
was added so that

Thereafter, the emulsion was cooled to 35° C., washed with water by a conventional flocculation method, 60 g of gelatin was added and dissolved at 40° C., and the pH was adjusted to 6.5 and pAg to 8.6. These tabular silver bromide grains have an average equivalent circle diameter of 1.4 μm, a grain thickness of 0.2 μm, and a coefficient of variation of the equivalent circle diameter of 15 μm.
% monodisperse tabular grains.

Tabular silver iodobromide emulsion ■-C comparative emulsion> Silver nitrate 5
Emulsion ■-B containing silver bromide equivalent to 0 g was added to 1.11 g of water.
The temperature was maintained at 75°C and the pBr at 1°4. Thereafter, immediately after adding 1 g of 3,6-guthioctane-1,8-diol, a potassium bromide solution containing 100 g of silver nitrate and 10 M% of potassium iodide was added at a constant flow rate in equimolar amounts to silver nitrate over a period of 50 minutes. After that, it was washed with water using the usual flocculation method, pH 6.5, pAg 8.6.
Adjusted to. The obtained silver iodobromide tabular grains had silver iodobromide in the center and silver iodobromide containing 10 M% silver iodide in the outer annular part, and had an average circular equivalent grain diameter of 2.3 μm and a grain thickness. was 0.26 μm.

Tabular silver iodobromide emulsion 1-D <This invention> Except for the following,
It was prepared in the same manner as Emulsion 1-C. Instead of adding silver nitrate aqueous solution and halogen salt aqueous washing solution to the reaction vessel, fine grain emulsion I
-A was added to the reaction vessel at a constant flow rate over 50 minutes to give 100 g in terms of silver nitrate. The obtained tabular grains had an average equivalent circular diameter of 2.5 μm and a grain thickness of 0.23 μm.

Flat silver iodobromide hole side 1-E <This invention> Except for the following,
It was prepared in the same manner as Emulsion 1-C1I-D. Here, a mixer with strong and efficient stirring installed near the reaction vessel was used.
A solution containing 100 g of silver nitrate and potassium iodide are mixed in 1 min.
Fine-grained silver iodobromide was prepared by adding a potassium bromide solution containing 0M% at an equimolar constant flow rate. In this case, 300 cc of a 2% by weight gelatin solution was mixed with the aqueous halogen salt solution prior to addition. The ultrafine particles produced in the mixer are immediately and continuously added to the core emulsion T-B.
was introduced into a reaction vessel. During this time, the mixer is 4
It was kept at 0°C. The obtained tabular grains had an average equivalent circular diameter of 2.6 μm and a grain thickness of 0.21 μm.

Tabular silver iodobromide emulsion 1-F <Invention) pBr during grain growth was set to 2.6, and 3.6-guthioctane-1,8
- Emulsion 1-E was made exactly the same as emulsion 1-E except that no diol was added. 86% of the resulting tabular grains are hexagonal tabular grains, and the average equivalent circle diameter is 2.
The coefficient of variation of 1 μm was 17% for the flower-dispersed tabular iodobromide root emulsion. The average particle thickness was 0.23 μm.

Grains of emulsions 1-C1I-D, I-E, and 1-F were each sampled, and their transmission images were observed using a voft i3 transmission electron microscope at 200 degrees Celsius in a state where they were cooled with liquid nitrogen. As a result, emulsion! A clear annual ring-like striped pattern was observed in I-C, but in I-D, I-E, and I-C of the present invention,
In -F, the striped pattern was not observed at all, indicating that a tabular silver iodobromide emulsion having a completely uniform silver iodide distribution was obtained by the present invention. Emulsion 1-C, ID
, 1-E is shown in FIG. 3. In the grains shown in Figure 3, the core is pure silver bromide and does not contain silver iodide, so no striped pattern indicating non-uniformity is observed, and the outer annular part (shell) contains 10% silver iodide. containing a silver iodobromide phase, with a core/shell ratio of 1:2.

These r-c to l-F emulsions (pH 6.5, pAg 8
．． 6) Add sensitizing dye I shown below at 60°C at 250 μ/A.
After 10 minutes, sodium thiosulfate, potassium chloroaurate and potassium thiocyanate were added for optimal chemical enrichment. After completion of chemical sensitization, 100 g of each of emulsions 1-C to IF (containing 0.08 mol of Ag) and sensitizing dye I were dissolved at 40 DEG C., and the following steps 1 to 2 were sequentially added with stirring to prepare solutions.

■ 4-hydroxy-6-methyl-1,3,3a.

7-Chitrazaindene 3% 2CC■ C+ J
3s 0-(CHtCIIO) zs H2% 2
．． 2CC ■ +CHI-C) If, 1 2% 1.
Surface retention 81 on 6S03! Coat the layer coating solution at 40℃ according to the following
The mixture was added one by one while stirring to prepare a solution.

■ 14% gelatin aqueous solution 56.8g■ Polymethyl methacrylate fine particles (average particle size 3.0μm) 3.9g■ Emulsion gelatin 10% 4.24gCHzCOO(
JIzCH(CJs)Cat(q■ Na03S CHCOOCHzCH(CJs)C41
1q10.6 ■ ■ Hzo 68.8cc4
．． 3% 3 cc Together with the emulsion coating solution and the surface protective layer coating solution obtained as above, they were coated on a cellulose triacetate film support by co-extrusion at a volume ratio of 103:
It was applied so that it became 45.

The amount of silver coated is 3.1g/n? It is. 200 lux with a light source with a color temperature of 2854° for these samples.

After applying web exposure for 1/10 seconds, the following developer D-
1 at 20° C. for 7 minutes, then fixed with fixer F-1, washed with water, and dried.

[Developer D-1] Metol 2g Sodium sulfite 100g Hydroquinone
5g Polax・5HzO1, 53g water was added to 11 The results of sensitometry are shown in Table 1.

[Fixer F-1] Ammonium thiosulfate 200.0g Sodium sulfite ($, water) 20.0g Boric acid
8. Og disodium ethylenediaminetetraacetate 0.1g aluminum sulfate 15.0g sulfur #
2.0g glacial acetic acid
Add 22.0g water to make lβ. (The pH is adjusted to 4.2.) Table 1 As shown in Table 1, the emulsion of the present invention has a much higher degree of anger than the comparative emulsion.

Example 2 Silver iodobromide fine grain emulsion 2-A 2.0% by weight containing 0.026 M potassium bromide
gelatin solution? & 2.6p, while stirring, a halogen salt aqueous solution containing 1.2M silver nitrate solution, 0.9M potassium bromide, and 0.3M potassium iodide was added to each solution for 15 minutes at 1200°C while stirring. and added. During this time, the gelatin solution was kept at 35°C. After this, the emulsion was washed using the conventional flocculage method, and 30 g of gelatin was added.
After adding and melting, the pH was adjusted to 6.5 and the pAg to 8.6. The obtained silver iodobromide fine particles (silver iodide content 125%)
) had an average particle size of 0.07 μm.

Tabular silver iodobromide emulsion 2-B <Comparative emulsion> Add 1.31% of gelatin solution containing 0.02 mol of potassium bromide to 2.0 M by double jet method while stirring. of silver nitrate solution and 0.5M potassium iodide and 1
．． Add 20 cc of a halogen salt aqueous solution containing 5M potassium bromide in 30 seconds. During this time, the gelatin solution was kept at 30°C. After the addition, the temperature was raised to 70°C, 30g of gelatin was added, and the mixture was aged for 30 minutes. Thus silver iodide 2
Silver iodobromide core particles containing 5% were obtained and p
After adjusting Br to 2.0, a potassium bromide solution containing 75 g of silver nitrate and 25 mol% potassium iodide was added over 40 minutes at an accelerated flow rate equimolar to that of silver nitrate (the flow rate at the end was 10 times that at the beginning). ) was added.

In another 20 minutes after the end of the addition, 75 g of silver nitrate and an equimolar amount of potassium bromide were added at an accelerated flow rate (the flow rate at the end was twice that at the beginning). After this, the emulsion was cooled to 35°C, washed with water by a conventional flocculation method, 60g of gelatin was added and dissolved at 40°C, and the pH was adjusted to pH 6.5.
Ag was adjusted to 8.6.

This tabular grain has a core/shell (core/shell ratio I)
It has a structure in which the center part is silver iodobromide with a silver iodide content of 25 mol %, and the outer part is pure silver bromide.

The average equivalent circle diameter of the obtained tabular grains was 2.0 μm, and the grain thickness was 0.28 μm.

Tabular silver iodobromide emulsion 2-C (present invention) After forming silver iodobromide tabular grain nuclei containing 25 mol% of silver iodide in the same manner as emulsion 2-B, 40 cc of a 30% potassium bromide aqueous solution was added. 0.8 g of 3.6-cynaoctane-1,8-diol was added, and immediately dissolved fine grain emulsion 2-A was added using a pump.

The addition rate was such that an amount equivalent to 75 g of silver nitrate was added at an accelerated flow rate (the flow rate at the end was 10 times that at the beginning), the pBr was adjusted to 2.0 with a silver nitrate solution, and then 75 g of silver nitrate was added.
5 g and an equimolar amount of potassium bromide were added at an accelerated flow rate (end flow rate twice the start rate). after that,
Washing and redispersion with water was carried out in the same manner as in Emulsion 2-B. These tabular grains are also core/shell type grains with silver iodobromide containing 25 mol % of silver iodide in the center and silver bromide on the outside, and the average equivalent circular diameter of the grains is 2.6 μm and the grain thickness is 0.6 μm. It was 22 μm.

Tabular silver iodobromide emulsion 2-D (present invention) After tabular silver iodobromide nucleation containing 25 mol % of silver iodide was carried out in the same manner as in emulsion 2-B, a strong stirring tube was placed near the reaction vessel. Add 75 g of silver nitrate and potassium bromide containing 25 mol% of potassium iodide to an efficient mixer in 40 minutes at an accelerated flow rate equimolar to silver nitrate (the flow rate at P-7 is 10 times the starting rate). When fine grain silver iodobromide was prepared and added to the reaction vessel, gelatin was previously dissolved in a halide to give a concentration of 1% by weight. After addition of fine particles, 1 nitric acid was added for another 20 minutes.
An accelerated flow of 75g of 1W and the same mole of potassium bromide! It was added to the reaction vessel at (P, flow rate at 7:00 was twice that at the start). Thereafter, water washing and redispersion were performed in the same manner as Emulsion 2-B. This tabular grain also has a silver iodide center of 25
The particles were core/shell type particles with mole % of silver iodobromide and silver bromide on the outside, and the average equivalent circular diameter of the particles was 1.9 μm and the grain thickness was 0.28 μm.

Grains of emulsions 2-B and 2-Cl2-D were each sampled, and their transmission images were observed in the same manner as above.

A tree ring-like striped pattern was clearly observed in the silver iodobromide phase in the center outside the core of emulsion 2-B, but emulsion 2-Cl2
-D had no such pattern at all.

No striped pattern was observed in the outer silver bromide phase.

After optimally sensitizing these 2-B and 1-Cl2-D emulsions at 60°C with sodium thiosulfate, chloroauric acid, and potassium thiocyanate, the following sensitizing dye (■) was added to 250 ■/Ag mole. and then 4-hydroxy-6-methyl-
Add 1,3,3a,7-chitrazaindene (but 2
-C emulsion is a sensitizing dye ■ (CHz) ssO+ (CHI) xsOJa
The amount added was adjusted so that the total amount added was the same as that of the other emulsions. ) Coated onto a polyethylene terephthalate support at a silver content of 2 g/r/.

These samples were then exposed to a 5400”K light source at 50°C.
After exposure for 1/10 second with a filter that cants light with wavelengths shorter than 0 nm (minus blue exposure),
After developing with the following developer D-2 (20° C. for 4 minutes) and fixing with the above-mentioned fixer F-1, the film was washed with water and dried.

[Developer D-2] 1-phenyl-3-pyrazolidone 0.5g Hydroquinone 20.0g Disodium ethylenediaminetetraacetate 2.0g Potassium sulfite 60.0g Boric acid
4.0g potassium carbonate
20.0g sodium bromide 5.
0g diethylene glycol Add 30.0g water to make 11. (The pH was adjusted to 10.0.) The results of sensitometry are shown in Table 3.

Table 3 Example 3 Silver iodobromide octahedral grain emulsion 3-A Comparative emulsion> 0.0% by weight of gelatin solution containing 0.05M potassium bromide was added to 1.21% of gelatin solution while stirring. .1%
3.80% methanol solution of 4-dimethyl-4-thiazoline-2-thione was added to a reaction vessel kept at 75°C.
50 cc of 3M silver nitrate solution and 59 cc of a halogen salt aqueous solution containing 0.063M potassium iodide and 0.19M potassium bromide were added over 3 minutes by a double jet method. Thereby, nucleation was performed by obtaining silver iodobromide grains having a projection surface ellipse equivalent diameter of 0.3 μm and a silver iodide content of 25 mol %. Subsequently, at 75°C, 1
．． 5M nitric acid 11Y800+++7! and a halogen salt solution containing 0.375M potassium iodide and 1.13M potassium bromide were simultaneously added over 100 minutes by a double jet method. Thereafter, the emulsion was cooled to 35°C, washed with water by a conventional flocculation method, and gelatin 70%
g was added to adjust the pH to 6.2 and pAg to 8.8 to form a first coating layer. The obtained emulsion grains were octahedral silver iodobromide emulsions with an equivalent diameter for average projected area of 1.7 μm. (Iodide content: 25 mol %) Subsequently, this emulsion was used as a core emulsion to form a silver bromide shell (second coating layer). The silver bromide second coating layer had a molar ratio of first coating layer/second coating layer of 1:1. The obtained emulsion grains had an average circular equivalent diameter of 2.2 μm and contained 25 silver iodide particles inside.
core/shell monodisperse octahedral particles containing mol %.

Emulsion 3-B (Invention)> Nucleation was carried out in the same manner as in Emulsion 3-A to obtain silver iodobromide core grains of 0.3 μm. A first coating layer was formed by adding 1.2 mol of silver (containing 25 mol %) using a pump over 100 minutes. After this, the emulsion was cooled and washed with water, and then I)H,
I) Ag was adjusted as in Emulsion 3-A. Furthermore, using this emulsion grain as a core, nitric acid i1W? The fI solution and the potassium bromide solution were simultaneously added to the reaction vessel by a double jet method to form a silver bromide shell (second coating layer) at a first coating layer/second coating layer ratio of 1:1. The obtained particles had an average equivalent circular diameter of 2.2 μm and contained 25 mol% of silver iodide inside.
core/shell monodisperse octahedral particles containing

Emulsion 3-C (present invention) After nucleation was performed in the same manner as Emulsion 3-A, 1.5M was added to a mixer with strong and efficient stirring installed near the reaction vessel.
800 d of silver nitrate and 0.375M potassium iodide and 1.
Halogen salt solution containing 13M potassium bromide? &, 5oo-
and 500 ml of a 2% by weight aqueous gelatin solution were added over 100 minutes using the triple jet method. The temperature of the mixer was maintained at 30°C.

The ultrafine particles generated in the mixer are immediately and continuously heated to 75°C.
A first coating layer was formed by introducing the mixture into a reaction vessel maintained at

Thereafter, a 1.5M silver nitrate solution, a 1.5M potassium iodide solution, and a 2% by weight gelatin solution were further added to the mixer to form a silver bromide shell (second coating layer), thereby forming a first coating layer. Particles were obtained with a second coating layer ratio of 1:1. The obtained grains were octahedral monodisperse core/shell emulsion grains with an equivalent circle diameter of 2.2 μm.

After optimally chemically sensitizing emulsions 3-A, 3-B, and 3-C with sodium thiosulfate, potassium chloroaurate, and potassium thiocyanate, the following compounds were added to form a triacetyl cellulose film support with lower=i. applied on the body.

il+ Emulsion layer/emulsion... Emulsion G coupler shown in Table 4 (J propyl) oxacarbocyanine sodium/stabilizer 4-hydroxy-6-methyl-1゜3.3a
,? -Tetrazaindene/Coating aid Sodium dodecylbenzenesulfonate (2) Protective layer/2,4-dichloro-6-hydroxy-S-triazine sodium salt Q gelatin These samples were subjected to sensitometric exposure, and the following Color development processing was performed.

The concentration of the treated sample was measured using a green filter.

The photographic performance results obtained are shown in Table 4.

The development process used here was carried out at 38°C under the following conditions.

1. Color development...2 minutes 45 seconds 2. Drifting
White... Old... 6 minutes 30 seconds 3, Washed...
...3 minutes 15 seconds 4, established...6
Minute 30 seconds 5, Wash with water...3 minutes 15 seconds 6
, Stability...3 minutes and 15 seconds The composition of the processing solution used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate
30.0g potassium bromide ・
1.4g hydroxylamine sulfate 2
．． 4g4-(N-Ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate 4.5g water added 11 Bleach Ammonium Bromide 160.0g Aqueous ammonia (28%>25.0d Ethylenediamine-4 Sodium acetate salt 130g glacial acetic acid
14- Add water
1z Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0+d Sodium bisulfite 4.6g Add water
17! Stabilized liquid formalin 8. (Addition of ld water) The results of 1β photographic performance are shown in Table 4.

Table 4 Emulsion 3-B of the present invention, 3. -C exhibits very favorable characteristics in terms of sensitivity and fog. Furthermore, when we investigated the pressure characteristics (folding test of emulsion-coated film) of the above samples, we found that emulsion 3-A showed extremely extreme pressure desensitization, but emulsions 3-B and 3-C showed the same pressure desensitization. is rarely seen,
markedly improved.

Example 4 Silver iodobromide octahedral emulsion Emulsion 4-A Comparative emulsion> Add 5% 3% by weight to 1.21% of a 3.0% by weight gelatin aqueous solution containing 0.03M potassium bromide while stirring.
．． 80 d of 6-guthioctane-1,8-diol was added, and an aqueous solution containing 100 g of silver nitrate and an aqueous solution containing 70 g of potassium bromide were simultaneously added at 75°C by a double jet method to obtain monodispersed silver bromide octahedrons of 1.7 μm. Particles were obtained. Next, using this particle as a core, 400. d and 0.15M potassium iodide and 1.3
An aqueous solution of 400 ml of a halide salt containing 5 M potassium bromide was simultaneously added over 50 minutes using a double jet method to form a silver iodobromide shell having a silver iodide content of 10 mol %. Thereafter, the emulsion was cooled to 35°C, washed with water by a conventional flocculation method, added with 85 g of gelatin, and adjusted to pH 6.2 and p.
Ag was adjusted to 8.8. The resulting grains were monodisperse octahedral emulsions with an average projected area equivalent diameter of 2.2 μm, containing 10 mol % of silver iodide on the outside, and a core/shell ratio of 1:1.

Emulsion 4-B <This invention> After preparing a core with an average equivalent circle diameter of 1.7 μm in the same manner as Emulsion 4-8, 20 CC of 30% potassium bromide was added,
Fine grain emulsion 1- of Example-1 containing 10 mol% silver iodide
At 75°C, add A to 0.6 mol of silver by 50
The mixture was added using a pump at a constant speed over a period of minutes, and core/shell emulsion grains were completed in the same manner as in Emulsion 4-A. The resulting grains were monodisperse octahedral emulsions with an average equivalent circular diameter of 2.2 μm and a core/shell ratio of 1:1, containing 10 mol % of silver iodide on the outside.

Emulsion 4-C <This invention> Silver bromide cores with an average equivalent circular diameter of 1.7 μm were prepared in the same manner as Emulsion 4-A, and then placed in a mixer with strong and efficient stirring installed near the reaction vessel. .5M silver nitrate aqueous solution 40
Q ml and 0.15M potassium iodide and 1,35
4QOml of a halogen salt aqueous solution containing M potassium bromide and 200 ml of a 1% by weight gelatin aqueous solution were simultaneously added over 50 minutes by a triple jet method. The temperature of the mixer was maintained at 35°C. The ultrafine particles produced in the mixer were immediately introduced into a reaction vessel continuously maintained at 75°C. The obtained particles had a core of silver bromide, a shell of silver iodobromide with a silver iodide content of 10 mol%, and a core/shell ratio of 1.
:1 monodisperse octahedral particles had an average equivalent circular diameter of 2.2 μm.

After optimally chemically sensitizing emulsions 11A, 4-B, and 4-C with sodium thiosulfate, potassium chloroaurate, and potassium thiocyanate, samples were prepared as shown in Example 3, and the same procedure as in Example 3 was carried out. Sensitometry was performed as follows. Table 5 shows a comparison of the photographic performance obtained.

Table 5 Emulsions 4-B and 4-C of the present invention have a much higher degree of irritability than 4-A.

[Brief explanation of the drawing]

FIG. 1 is a transmission electron micrograph showing the crystal structure of conventional silver halide grains in which the iodide distribution of the silver iodobromide phase is not completely uniform, and the magnification is 50.000 times. FIG. 2 schematically shows one of the emulsion manufacturing methods according to the present invention, in which silver halide grains are supplied from a mixer outside the reaction vessel. FIG. 3 is a transmission electron micrograph showing the crystal structure of typical silver halide grains in emulsions 1-C11-D and 1-E prepared in Example-1, and the magnification is 50,000.
It is 0 times. Patent applicant Fuji Photo Film Co., Ltd. Figure 3 f-C-E-D

Claims (1)

[Claims] A silver halide photographic emulsion comprising a dispersion medium and silver halide grains, the silver halide grains containing a silver halide phase containing 3 mol% or more of silver iodide, and a silver halide containing the silver iodide. A silver halide photographic emulsion characterized in that the distribution of silver iodide in the phase is completely uniform.