JP2664285B2 - Silver halide photographic emulsion and photographic light-sensitive material using the same - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material using the same, and more particularly, to a tabular halide having improved photographic characteristics. The present invention relates to a silver photographic emulsion particle and a photographic light-sensitive material using the same.

(Prior Art) Regarding tabular silver halide grains, U.S. Pat.
4,434,226, 4,439,520, 4,414,310, 4,43
No. 3,048, No. 4,414,306, No. 4,459,353, JP-A-57-2
No. 09002 and the like disclose the production method and use technology, and are known to have advantages such as improvement of color sensitization, improvement of sensitivity / granularity, improvement of sharpness, improvement of covering power, and the like.

Further, JP-A-63-011928 and JP-A-63-151618 disclose techniques for monodispersing the size of tabular grains to increase the ratio of tabular grains.

However, the tabular grains have many problems, such as pressure resistance and latent image preservability, which must be solved in introducing them into photographic light-sensitive materials in terms of their durability, and are described in JP-A-63-220238. Such a technique for improving durability was essential. The method of introducing dislocations into particles described in JP-A-63-220238 is based on sensitivity, pressure, storage,
It can be said that this technology is particularly noteworthy in improving the exposure illuminance dependency.

However, in the above invention, when dislocations are introduced, the grain shape is collapsed, or the distribution of the silver iodide content and the grain size between grains is widened, resulting in soft gradation and a wide development progress width, The demand for photographic materials and emulsions in recent years has been insufficient.

(Problems to be Solved by the Invention) It is an object of the present invention to provide a silver halide photographic emulsion having high sensitivity and improved gradation, and a photographic light-sensitive material using the same.

(Means for Solving the Problems) As a result of intensive studies made by the present inventors, the object of the present invention has been achieved by the following means.

(1) At least 50% of the total projected area has an aspect ratio of 3
The tabular silver halide grains occupy the above, and the relative standard deviation of the grain size distribution of the tabular silver halide grains occupying 50% of the silver halide grains is 25% or less, and accounts for 50% or more of the total number of these silver halide grains. Corresponding silver halide grains have 10 or more dislocations per grain, and 50% of the total projected area of these silver halide grains.
A silver halide photographic emulsion characterized in that the relative standard deviation of the silver iodide content distribution of large tabular silver halide grains occupying 30% or less is 30% or less.

(2) The silver halide photographic emulsion according to the above (1), wherein the tabular silver halide emulsion grains have a portion having a higher silver iodide content than the surface of the grains.

(3) A photographic material having at least one silver halide emulsion layer on a support, characterized in that the silver halide emulsion layer contains the silver halide photographic emulsion described in (1) above. Silver halide photographic material.

(4) A photographic material having at least one silver halide emulsion layer on a support, characterized in that the silver halide emulsion layer contains the silver halide photographic emulsion described in (2) above. Silver halide photographic material.

 Hereinafter, the present invention will be described in more detail.

A tabular silver halide grain (hereinafter, referred to as a "tabular grain") in the present invention is a circle having two opposing parallel main planes and a circle equivalent diameter of the main plane (a circle having the same projected area as the main plane). Is a silver halide grain whose diameter is at least three times larger than the distance of the main plane (that is, the thickness of the grain).

The aspect ratio of the present invention is defined as a value obtained by dividing the equivalent circle diameter of each particle obtained by the method described later by the thickness of the particle.

The average aspect ratio of the emulsion having tabular grains of the present invention is preferably from 3 to 12, particularly preferably from 3 to 8.

Here, the average aspect ratio is obtained by averaging the particle diameter / grain thickness ratio of all tabular grains, but as a simple method, the ratio of the average diameter of all tabular grains to the average thickness of all average grains is given. Can also be sought.

The tabular grains of the present invention have a diameter (equivalent to a circle) of 0.2 to 5.0 μm,
Preferably 0.3 to 4.0 μm, more preferably 0.3 to 3.0 μm
m.

The particle thickness is 0.5 μm or less, preferably 0.05 to 0.5 μm,
More preferably, it is 0.80 to 0.3 μm.

The measurement of the particle diameter and the particle thickness in the present invention can be obtained from an electron micrograph of the particles as in the method described in US Pat. No. 4,434,226.

The standard deviation of the grain size distribution of the tabular grains of the present invention is 25%.
The monodispersion described below is characterized by the relative standard deviation, which is defined as “the variation (standard deviation) of the grain size obtained from the equivalent circle diameter and thickness of the projected area of the tabular grain is calculated as the average grain size. Value divided by size multiplied by 100 "
Is represented by Here, the particle size (R μm) is obtained from the following equation from the circle equivalent diameter (r μm) and the thickness (d μm) of the projected area.

The grain size distribution of the silver halide emulsion composed of a group of grains having a uniform grain morphology and small variation in grain size shows almost a normal distribution, and the standard deviation can be easily obtained. The grain size distribution of the tabular grains of the present invention is not more than 25% in relative standard deviation, preferably not more than 20%.
% Or less, more preferably 15% or less.

Dislocations, for example JFHamilton, Photo.Sci.Eng., 11, 5
7, (1967) and T. Shiozawa, J. Soc. Phot. Sci Japan, 35 , 21
3, (1972) can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, the silver halide grains taken out of the emulsion with care not to apply enough pressure to cause dislocations on the grains are placed on a mesh for electron microscopy observation and on a mesh, and the sample is prepared so as to prevent damage (printout etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 KV or more for a particle having a thickness of 0.25 μm). From the photograph of the particles obtained by such a method, the position and number of dislocations can be obtained for each particle when viewed from a direction perpendicular to the main plane.

The position of the dislocation of the present invention occurs from the distance of x% of the length from the center to the side to the side in the major axis direction of the tabular grain, and the value of x is preferably 10 ≦ x <100.
And more preferably 30 ≦ x <98, and still more preferably 50 ≦ x <95. At this time, the shape formed by connecting the positions where the dislocations start is similar to the grain shape, but may be distorted instead of a perfect similar shape. The direction of the dislocation line is roughly from the center to the side, but often meanders.

Regarding the number of dislocations of the present invention, it is preferred that grains containing 10 or more dislocations are present in 50% (number) or more of all silver halide grains. More preferably, 70% (number) of particles containing 10 or more dislocations are present, and particularly preferably 90% (number) of particles containing 10 or more dislocations are present.

In the tabular grains of the present invention, the relative standard deviation of the silver iodide content distribution of each grain is 30% or less, more preferably 20% or less.

The silver iodide content of each emulsion grain can be measured, for example, by analyzing the composition of each grain using an x-ray microanalyzer. The "relative standard deviation of the silver iodide content of each grain" as used herein means, for example, the silver iodide content when at least 100 emulsion grains were measured for the silver iodide content using an X-ray microanalyzer. This is a value obtained by multiplying the value obtained by dividing the standard deviation of the ratio by the average silver iodide content by 100. A specific method for measuring the silver iodide content of individual emulsion grains is described, for example, in EP 147,868A.

In the present invention, the grains for which the silver iodide content is measured and the relative standard deviation of the distribution is determined are arranged in the order of the projected area from all grains of the emulsion, and when the projected areas are added, this sum is Large tabular silver halide grains up to 50% of the total projected area. Here, when actually calculating the relative standard deviation, first, for each of the 500 or more randomly selected grains, it is determined whether or not each grain is a large size tabular silver halide grain to be a control. It is necessary to carry out a test, and to measure the silver iodide content of 50 or more grains randomly extracted from control grains. Therefore, when there are fine grains having extremely different silver iodide contents, the fine particles ignore this silver iodide content when calculating the relative standard deviation.

If the relative standard deviation of the silver iodide content distribution of each grain is large, the appropriate point of chemical sensitization of each grain (condition of chemical sensitization suitable for each grain) differs, and the performance of all emulsion grains It becomes impossible to pull out.

There may or may not be a correlation between the silver iodide content Yi [mol%] of each grain and the grain size Xi [microns] of each grain, but it is desirable that there is no correlation.

Regarding the structure related to the halogen composition of grains, X-ray diffraction, EPMA (also known as XMA) method (a method of detecting silver halide composition by scanning silver halide grains with an electron beam), ESCA (named XPS The method can be confirmed by combining a method (a method of irradiating X-rays and dispersing photoelectrons emitted from the particle surface).

In the present invention, the particle surface refers to a region up to a depth of about 50 ° from the surface. The halogen composition in such a region can usually be measured by the ESCA method. The inside of the particle refers to a region other than the above-described surface region.

 Next, a method for producing the tabular grains of the present invention will be described.

The tabular grains can be produced by appropriately combining methods known in the art.

The silver halide emulsion of the present invention can be produced by any of the following methods: nucleation → ripening nucleation → ripening → growth. Accordingly, each of the basic processes of nucleation, ripening, and growth will be described.

1.Nucleation For nucleation, low molecular weight gelatin is used as a dispersion medium, and pBr 1.0 to 2.
Nucleates under 5 conditions. pBr can be controlled by silver potential at any stage of nucleation, ripening, and growth.

The molecular weight of low molecular weight gelatin during nucleation is 60,000 or less,
Preferably, it is 1,000 to 40,000.

If the average molecular weight is 60,000 or more, the proportion of tabular grains in all silver halide grains is undesirably reduced.

It is preferable that 50% by weight or more, preferably 70% by weight or more of the dispersion medium is low molecular weight gelatin.

The concentration of the dispersion medium can be 0.05 to 10% by weight.

As the type of gelatin, alkali-treated gelatin is usually used, but modified gelatin such as acid-treated gelatin and phthalated gelatin can also be used.

In addition, it is more preferable that one or both of the aqueous AgNO ₃ solution and the aqueous alkali halide solution added during nucleation contain gelatin. As the gelatin used here, the aforementioned low molecular weight gelatin is preferable. Also in this case, it is preferable that 50% by weight or more, preferably 70% by weight or more of the dispersion medium is low molecular weight gelatin.

In this case, the concentration of the dispersion medium is 0.05 to 5% by weight, preferably 0.3 to 2.0% by weight.

Regarding this effect, it is conceivable that the gelatin concentration is not made non-uniform in the vicinity of the addition ports of the aqueous AgNO ₃ solution and the aqueous halide salt solution, thereby preventing the formation of multiple twin grains.

The frequency of twin plane formation during nucleation depends on various supersaturation factors (e.g., temperature during nucleation, gelatin concentration, type of gelatin, molecular weight of gelatin, addition rate of silver salt aqueous solution and alkali halide aqueous solution, Br ^- concentration, stirring rotational speed, I alkali halide aqueous solution to be added ^- content, the silver halide solvent content, pH, (concentration of, for example, KNO _3, NaNO ₃₎ salt concentration
And emulsion stabilizers, antifoggants and sensitizing dye concentrations], and the dependency is described in Japanese Patent Application Laid-Open No. 63-092942 by the present inventors.
No. is shown in the figure.

Usually, in a system in which nucleation is carried out at a low temperature (25 to 30 ° C.), and then high supersaturation growth is carried out at a low temperature without ripening, when these supersaturation factors are increased during nucleation, the main particles produced are a) Octahedral regular particles → b) Particles having a single twin plane → c) Particles having two twin planes (target) → d) Particles having non-parallel twin planes and e) three planes It changes like particles having the above twin planes.

Therefore, in the present invention, nucleation is preferably performed under the condition that the generation probability of c) is as high as possible within the range where the generation ratio of the particles d) and e) does not increase.

Specifically, the proportion of c) in the silver halide emulsion finally obtained by the grain formation method of the present invention is determined by observing the dependence of the diagram in JP-A-63-092942. It regulates these various supersaturation factors to be within. More specifically, the condition of the saturation factor at the time of nucleation may be adjusted while observing the replica image of the finally formed silver halide grains with a transmission electron microscope.

For the nucleation of tabular grains having a silver iodide content at the center of 7 mol% or more, the description in JP-A-63-092942 can be referred to.

By adjusting these various factors and observing the finally obtained tabular grains, the tabular grains obtained by nucleation under the above-mentioned conditions show that photographic gelatin having a normal average molecular weight of 100,000 was used as a dispersion medium. It was found that the mixing ratio of the non-tabular grains was particularly low as compared with the case where it was used. In addition, as the shape
The ratio of hexagonal tabular grains described in JP-A-63-151618 is high.

The grains in the examples of French Patent No. 2534036 have a high ratio of triangular tabular grains (grains having three parallel twin planes), which are thought to be due to nucleation under high supersaturation conditions. Can be

Other preferable conditions at the time of nucleation in the present invention are as follows.

The temperature can be 5 to 60 ° C., but the average particle size is
When producing fine tabular grains having a particle size of 0.5 μm or less, the temperature is preferably 5 to 48 ° C. The I ^- content in the previously charged solution is preferably 0.03 mol / or less. The addition temperature of AgNO ₃ is preferably 0.5 g / min to 30 g / min per one aqueous reaction solution.

The composition of the alkali halide solution to be added is Br
^The I ^- content relative to-is equal to or less than the solid solution limit of the formed AgBr I, preferably equal to or less than 20 mol%.

The concentration of unrelated salts (salts not directly involved in silver halide formation) in the reaction solution is preferably 0 to 1 mol /. Reaction solution p
H can be 2 to 10, but preferably 8.0 to 10 when a reduction sensitized silver nucleus is introduced. The concentration of the silver halide solvent in the reaction solution is preferably from 0 to 3 × 10 ^-1 mol /. As the type of the silver halide solvent, those described below can be used.

2. Aging In the nucleation described in 1), fine tabular grain nuclei are formed, but a large number of other fine grains (especially octahedral and single twin grains) are formed at the same time. Before the next growth process, it is necessary to eliminate grains other than tabular grain nuclei to obtain nuclei having a shape to be tabular grains and good monodispersity. To enable this, Ostwald ripening is performed following nucleation.

As the ripening method, the items described in JP-A-63-151618 can be used, but the following method is particularly effective.

After nucleation, a part of the emulsion is taken out as a seed crystal, and an aqueous gelatin solution is added, or simply after nucleation, an aqueous gelatin solution is added to adjust pBr and gelatin concentration. The preferred pBr in this case is low pBr (1.4-2.0) and the gelatin concentration is 1-10% by weight. The gelatin used in this case is preferably gelatin having an average molecular weight of 80,000 to 300,000, usually 100,000, which is often used in the photographic industry.

Next, when the temperature is increased and the first aging is performed, tabular grains grow and non-tabular grains disappear. Then, after adjusting the pBr of the solution to a higher pBr (1.7 to 2.6) by adding an aqueous solution of AgNO ₃ ,
A second ripening is performed by adding a silver halide solvent. In this case, the concentration of the silver halide agent is 1 × 10 ^{-4 to} 3 × 10 ^-1 mol /
Is preferred.

Aging is carried out in this manner to make almost 100% tabular grains only.

Basically, in the first ripening of low pBr, Ostwald ripening occurs between twin grains having troughs and grains having no trough, and in the second aging using AgX solvent at the next high pBr, main grains of tabular grains are obtained. Ostwald ripening occurs between the spherical surfaces of the flat and non-tabular grains, and almost 100% of the tabular grains alone.

Further, the second aging has an effect of eliminating non-tabular grains that could not be lost in the first aging and an effect of equalizing the thickness of the seed crystal of the tabular grains. When ripening with a silver halide solvent at a low pAg, tabular grains grow in the thickness direction,
The particles become thicker. If the thickness is not uniform, the growth rate in the lateral direction will be uneven during the next crystal growth. This phenomenon is particularly remarkable during crystal growth in a low pBr (1.4 to 2.0) region, and is not particularly preferable in such a case.

Since the aging is slow at a low temperature, it is carried out at 40 to 80 ° C, preferably 50 to 80 ° C, from a practical viewpoint.

The gelatin concentration is 0.05-10% by weight, preferably 1.0-5.0%.
% By weight is preferred. The emulsion at the stage of completion of the ripening process is tabular grains having two twin planes in which 95% or more of the total projected area of the silver halide grains are parallel. Usually, the tabular grains have hexagonal corners. Hexagonal tabular grains or round tabular grains with a little roundness.

After completion of the ripening process, the emulsion may be washed with a usual washing method, and used as the tabular grains of the present invention.

After the ripening, the crystal growth process is usually started to grow the crystal to a desired size.

After ripening, if the silver halide solvent is unnecessary in the next growth process, the silver halide solvent is removed as follows.

Wash the emulsion with water.

As a method of washing the emulsion, which has been conventionally used,
(I) Nudel washing method, (ii) washing method in which a sedimentation agent is added to settle, (iii) sedimentation method using modified gelatin such as phthalated gelatin, (iv) ultrafiltration method, etc.
GFDuffin, “Photographic Emulsion Chemistry,” Foca
l Press, London. 1966 and references below) can be used.

For such an alkaline silver halide solvent NH _3, HNO
_An acid having a large solubility product with Ag ^{+ such as} ₃ is added to neutralize and neutralize.

In the case of a thioether-based AgX solvent, JP-A-60-136736
Add an oxidizing agent, such as H ₂ O ₂ , to invalidate as described in the item.

3. Growth The pBr during the crystal growth period following the ripening process is preferably maintained at 1.4 to 3.0. In addition, during the crystal growth period, the addition rate of Ag ⁺ and halogen ions was set to be 20 to 100 times the critical crystal growth rate.
%, Preferably 30 to 100%.

That is, as the growth atmosphere during the crystal growth period, the higher the pBr, and the higher the degree of supersaturation, the more monodisperse the tabular grains are with the growth. However, on the high pBr side (pBr2 to 3.0 or a tetrahedral or cubic crystal forming region described later), monodisperse tabular grains having a low aspect ratio can be obtained because of the accompanying growth in the thickness direction.

Although tabular grains with a high aspect ratio can be obtained by growing on a low pBr side (pBr 1.4 to 2.0 or a {111} crystal forming region such as an octahedral crystal described later) and high supersaturation, It gets a little worse.

In this case, the addition rate of silver ions and halogen ions is increased along with the crystal growth. As a method of increasing the addition rate, as described in JP-B-48-36890 and JP-B-52-16364, The addition rate (flow rate) of the silver salt aqueous solution and the halogen salt aqueous solution may be increased, and the concentrations of the silver salt aqueous solution and the halogen salt aqueous solution may be increased. Alternatively, an ultrafine grain emulsion having a size of 0.10 μm or less may be prepared in advance, and the addition speed of the ultrafine grain emulsion may be increased. Also, a combination of these may be used. The addition rates of silver ions and halogen ions may be increased intermittently or continuously.

The details and stirring method are described in JP-A-55-1423.
29, Japanese Patent Application No. 61-299155, U.S. Pat. No. 3,650,757, and British Patent 1,335,925 can be referred to.

In general, the particle size distribution of the obtained particles becomes wider as the growth atmosphere is set to the lower pBr side and the supersaturation is made lower.

The monodispersity and aspect ratio of the tabular grains are as described above.

Basically, the tabular grains of the present invention can be produced through the above-described nucleation, ripening and growth processes. However, if necessary, the following ripening can be carried out.

There is no particular limitation on the halogen composition of the silver halide deposited on the nucleus during the growth period. AgBr.AgBrCl
I (silver iodide content is 0 to solid solubility limit, Cl content is 0 to 50 mol%).

If the iodine distribution in the grains is to be gradually increased or decreased, the composition ratio of iodide in the halide to be added may be gradually increased or decreased along with the crystal growth. The composition ratio of iodide therein may be rapidly increased or sharply increased.

In addition, as a method for supplying iodine ions during the crystal growth period, fine particles of Ag I (prepared with a particle size of 0.1 μm or less,
(Preferably 0.06 μm or less) A method of adding an emulsion may be used, or a method of supplying an aqueous solution of an alkali halide may be used in combination. In this case, particulate Ag I melts with I ^- for the supply, uniform I ^- is supplied, particularly preferred.

In the present invention, the silver halide grains preferably contain a reduction sensitizing nucleus, and from that viewpoint, the pH of the solution during the growth phase is preferably 8.0 to 9.5.

In order to promote the growth during the crystal growth period, a silver halide solvent described below can be used. In this case, the concentration of the silver halide solvent is preferably from ^{0 to} 3.0 × 10 ⁻¹ mol /.

The generation of dislocations in the tabular grains of the present invention can be controlled by providing a specific high iodine inside the grains.Specifically, a substrate grain is prepared, then a high iodine phase is provided, and the outside thereof is provided. It is obtained by covering with a phase having a lower silver iodide content than the high iodide phase, but in order to make the silver iodide content of each grain uniform, the above-mentioned conditions for forming the high iodide phase are appropriately selected. It is important to.

The internal high iodine phase refers to a silver halide solid solution containing iodine. The silver halide in this case is preferably silver iodide, silver iodobromide, or silver chloroiodobromide, but is preferably silver iodide or silver iodobromide (silver iodide content: 10 to 40 mol%). More preferably, it is particularly preferably silver iodide.

It is important that the internal high iodine phase is not uniformly deposited on the plane of the tabular grains of the substrate, but rather exists locally. Such localization may occur on any of the main plane, side surfaces, sides, and corners of the flat plate. Further, such a site may be selectively epitaxially coordinated. As a method for this, it is preferable to use a so-called conversion method in which an iodide salt is added alone.

At least 50 of the total projected area by the above method
% Is occupied by tabular grains having an aspect ratio of 3 or more, and the standard deviation of the grain size distribution of the grains occupying 50% is 25% or less, and more than 50% of grains have 10 or more dislocations per grain. Such silver halide photographic grains can be formed, but it has been difficult to make the relative standard deviation (hereinafter referred to as intergrain iodine distribution) of the silver iodide content distribution of each grain uniform. In particular, when dislocations are introduced into grains as described in JP-A-63-220238 in order to solve pressure properties and latent image preservability, it is difficult to make the iodine distribution between grains uniform. Was.

In order to make the silver iodide content of each grain of the emulsion uniform, it is important to make the size and shape after Ostwald ripening as uniform as possible. Further, in the growth stage, the aqueous silver nitrate solution and the aqueous alkali halide solution are pAg
While maintaining a constant in the range of 6.0 to 10.0, adding by the double jet method, in order to perform particularly uniform coating, the supersaturation of the solution during the addition is preferably higher, for example, U.S. Pat. It is desirable to add in a relatively high degree of supersaturation such that the crystal growth rate is 30-100% of the critical crystal growth rate in the manner as described.

Further, the intergranular iodine distribution is particularly widened by adding an iodide salt alone when dislocations are formed. At that time, it is necessary to select the following conditions at the time of silver iodide It is effective for making the content uniform. That is, the pAg before adding the iodide salt is preferably in the range of 8.5 to 10.5, more preferably in the range of 9.0 to 10.5. Temperature is 50 ℃
It is preferred to keep it in the range of -30 ° C. The addition of the iodide salt is preferably performed by adding 1 mol% of the iodide salt based on the total silver amount for 30 seconds to 5 minutes under sufficiently stirred conditions.

The silver iodide content of the tabular grains of the substrate is lower than that of the high iodine phase, preferably 0 to 12 mol%, more preferably 0 to 12 mol%.
10 mol%.

The outer phase covering the high iodide phase is lower than the silver iodide content of the high iodide phase, preferably has a silver iodide content of 0 to 12 mol%, more preferably 0 to 10 mol%, and most preferably 0. ~ 3
Mol%.

The internal high iodine phase preferably exists in the range of 5 mol% to 80 mol%, more preferably 10 mol% to 70 mol%, from the center of the grain in terms of silver content of the whole grain in the major axis direction of the tabular grain. %, Especially in the range of 20 mol% to 60 mol%.

Here, the major axis direction of the grains refers to the diameter direction of the tabular grains, and the minor axis direction refers to the thickness direction of the tabular grains.

The iodine content of the internal high iodine phase is higher than the average iodide content of silver bromide, silver iodobromide or silver chloroiodobromide present on the grain surface, preferably 5 times or more, particularly preferably. Is more than 20 times.

Further, the amount of silver halide forming an internal high iodine phase is
The silver content is 50 mol% or less, more preferably 10 mol% or less, and particularly preferably 5 mol% or less, in terms of silver.

As described above, a silver halide solvent is useful for promoting ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. It is therefore clear that ripening can be promoted simply by introducing a halide salt solution into the reactor. Other ripening agents may be used, these ripening agents may be incorporated in their entirety in a dispersion medium in a reactor before adding the silver and halide salts, and one or more ripening agents may be used. And a peptizer may be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

As the ripening agent other than the halogen ion, ammonia or an amine compound, a thiocyanate salt, for example, an alkali metal thiocyanate salt, particularly a sodium and potassium thiocyanate salt, and an ammonium thiocyanate salt can be used. The use of thiocyanate ripening agents is taught in U.S. Pat. Nos. 2,222,264, 2,448,534 and 3,320,069. Also U.S. Pat.
Commonly used thioether ripening agents as described in 71,157, 3,574,628 and 3,737,313 can also be used. Or JP-A-53-82408 and JP-A-53-14431.
A thione compound as described in No. 9 can also be used.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the process of silver halide precipitation. Such compounds may be initially present in the reactor or may be added together with one or more salts according to conventional methods. United States Patent 2,
448,060, 2,628,167, 3,737,313, 3,772,0
Issue 31, Research Disclosure, Volume 134, 1
June 975, copper, iridium, as described in 13452,
The presence of compounds such as lead, bismuth, cadmium, zinc, (chalcogen compounds such as sulfur, selenium, and tellurium), gold and compounds of Group VII noble metals during the precipitation of silver halide precipitates enhances the properties of silver halide. Can control. Japanese Patent Publication No. 58-1410, Moiser
ar) et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27, silver halide emulsions can reduce and sensitize the interior of grains during precipitation.

In the tabular grains used in the present invention, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide, such as, for example, silver rhodan or lead oxide. These emulsion grains are described in U.S. Pat.Nos. 4,094,684 and 4,142,900.
No. 4,459,353, UK Patent No. 2,038,792, U.S. Pat.Nos. 4,349,622, 4,395,478, 4,433,501, 4,4
63,087, 3,656,962, 3,852,067, JP-A-59-
162540, etc.

 The tabular grains of the present invention are usually chemically sensitized.

Chemical sensitization is described in The James of The Theory of Photographic Process, 4th Edition.
Edition, Macmillan, 1977, (THJames The Theory
of the Photographic Process, 4th ed, Macmillan, 197
7) It can be carried out using active gelatin as described on pages 67-76, and can also be carried out using Research Disclosure 120, April 1974, 12008; Research Disclosure 34, June 1975, 13452. U.S. Pat.No. 2,642,3
No. 61, No. 3,297,446, No. 3,772,031, No. 3,857,711
Nos. 3,901,714, 4,266,018, and 3,904,41
No. 5, as well as in British Patent 1,315,755
sulfur at pAg 5-10, pH 5-8 and temperature 30-80 ° C.
It can be carried out using selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers. Chemical sensitization is optimally performed in the presence of a gold compound and a thiocyanate compound, and in U.S. Pat.
The reaction is carried out in the presence of a sulfur-containing compound described in Nos. 66,018 and 4,054,457 or a sulfur-containing compound such as hypo, thiourea-based compound and rhodanine-based compound. Chemical sensitization can also be performed in the presence of a chemical sensitization aid. As the chemical sensitization aid to be used, compounds such as azaindene, azapyridazine and azapyrimidine which are known to suppress capri and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
No. 8, 3,411,941 and 3,554,757, JP-A-58-12652
No. 6 and the aforementioned Duffin's "Emulsion Chemistry", 138-143
Page. In addition to or in lieu of chemical sensitization, reduction sensitization, for example with hydrogen, as described in U.S. Pat.Nos. 3,891,446 and 3,984,249, and U.S. Pat.Nos. 2,518,698, 2,743,182 Using stannous chloride, thiourea dioxide, polyamines and such reducing agents as described in US Pat. Nos. 2,743,183; or low pAg (eg, less than 5) and / or high pAg.
Reduction sensitization can be achieved by H (for example, greater than 8) treatment. U.S. Pat.Nos. 3,917,485 and 3,966,476
The color sensitization can also be improved by the chemical sensitization method described in (1).

A sensitization method using an oxidizing agent described in JP-A-61-3134 or JP-A-61-3136 can also be applied.

The emulsion comprising tabular grains of the present invention can be used in combination with an emulsion comprising ordinary chemically sensitized silver halide grains (hereinafter referred to as "non-tabular grains") in the same silver halide emulsion layer. In the case of a material, a tabular grain emulsion and a non-tabular grain emulsion can be used in different emulsion layers and / or in the same emulsion layer. Here, as non-tabular grains, for example, cubic, octahedral, regular grains having regular crystals such as tetradecahedron and spherical, particles having irregular crystal form such as potato-like and the like. it can. As the silver halide of these non-tabular grains, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing up to 30 mol% of silver iodide. Particularly preferred is silver iodobromide containing from 2 mol% to 25 mol% of silver iodide.

The non-tabular grains used here may be fine grains of 0.1 micron or less or large grains having a projected area diameter of up to 10 microns, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. May be.

Non-tabular grains used in the present invention are described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides,
Chimie et Physique Photographique Paul Montel, 196
7), “Digital Photographic Emulsion Chemistry”, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry)
(Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Published by Focalprene (VLZelikman et
al, Making and Coating Photographic Emulsion Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide is a one-side mixing method, a simultaneous mixing method,
Any of these combinations and the like may be used. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion comprising the regular grains,
It is obtained by controlling pAg and pH during particle formation.
See, for example, Photographic Science and Eng
ineering, Vol. 6, 159-165 (1962); Journal of Photographic Science
graphic Science), 12, 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Monodispersed emulsions are described in JP-A-48-8600 and 51-84.
-39027, 51-83097, 53-137133, 54-48
No. 521, No. 54-99419, No. 58-37635, No. 58-49938
And Japanese Patent Publication No. 47-11386, U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

The crystal structure of these non-tabular grains may be uniform, or the inside and outside may have different halogen compositions.
It may have a layered structure. These emulsion grains are described in GB 1,027,146, U.S. Pat.
4,877 and Japanese Patent Application No. 58-248469.

In the present invention, a non-photosensitive fine grain emulsion having a particle size of 0.6 μm or less, preferably 0.2 μm or less is added to a silver halide emulsion layer, an intermediate layer or a protective layer for the purpose of promoting development, improving storage stability, and effectively utilizing reflected light. May be.

The average particle of the present invention is preferably used for a color photographic light-sensitive material.

The average grain emulsion of the present invention can improve sharpness and granularity at the same time, particularly when used in the same and / or different emulsion layers as non-tabular monodispersed silver halide grain emulsions. .

Here, the monodispersed silver halide emulsion (non-tabular grains) means that the total weight or 95% or more of the silver halide grains contained therein is within ± 40% of the average grain size, more preferably ± 30%. Are defined as The use of a monodispersed silver halide emulsion in a silver halide photographic light-sensitive material can improve the granularity as described in JP-B-47-1138.
6, JP-A-55-142329, JP-A-57-17235, JP-A-59-72440 and the like. Also, the above-mentioned TH James, "The
Theory of Photographic Process ", 58
As described on pages 0 to 585, the 0.3 μ-0.8 μ monodispersed silver halide grains have a large light scattering property for light in a specific wavelength range, but have a large light scattering property for light in other wavelength ranges. It is also known that they have the property of relatively low light scattering.

Therefore, by appropriately arranging a tabular silver halide emulsion having a grain diameter / thickness ratio of 3 or more and a monodispersed silver halide emulsion in consideration of the optical characteristics and graininess of each silver halide emulsion. In some cases, the sharpness and granularity of the silver halide photographic light-sensitive material can be simultaneously improved.

 Some examples of such embodiments are listed.

Example 1) In a light-sensitive material in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side, the silver halide emulsion layer constituting the blue-sensitive layer has an average grain size of silver halide grains contained therein. Is in the range of 0.3 to 0.8 .mu.m, a tabular grain emulsion is used in the emulsion layer, and when the average grain size is not in the above range, a monodispersed silver halide emulsion is used to obtain a green-sensitive layer. Further, it is possible to improve the sharpness of the red-sensitive layer and the granularity of the blue-sensitive layer.

Example 2) In a light-sensitive material having the same layer arrangement as in Example 1, the silver halide emulsion layer constituting the green-sensitive layer has an average silver halide grain size of 0.4 to 0.8 μm.
When the average particle size is in the range of μ, the average grain emulsion is used in the emulsion layer. When the average particle size is not in the above range, a monodisperse emulsion is used to improve the sharpness of the red-sensitive layer and increase the green sensitivity. It is possible to improve the granularity of the layer.

Example 3) In a light-sensitive material having the same layer arrangement as in Example 1, wherein the emulsion layer having the same color sensitivity is composed of two or more layers having different sensitivities, the blue-sensitive layer having the highest sensitivity is 1.0 In the case of monodisperse silver halide of μ or more (especially a double structure grain is preferable), when the light scattering of the light-sensitive blue-sensitive layer is large, use a tabular grain emulsion for the light-sensitive blue-sensitive layer, and The sharpness of the layer and the red-sensitive layer can be improved.

Example 4) In the case of a light-sensitive material having the same layer arrangement as in Example 3, when a plurality of green-sensitive layers all have large light scattering, a tabular grain emulsion is used for all of the green-sensitive layers to improve the sharpness of the red-sensitive layer. ,
It is possible to improve the granularity of the green layer.

As in Examples 3 and 4, especially when the blue-sensitive layer, green-sensitive layer and red-sensitive layer are each composed of a plurality of emulsion layers, the emulsion layer having a large light scattering is preferably used to improve the sharpness and granularity. Consideration should be given to using grain emulsions and monodisperse emulsions in the emulsion layer with low light scattering. Further, when a tabular grain emulsion was further used in the red-sensitive layer in Example 4, light scattering between the emulsion layers became large, which sometimes deteriorated the sharpness of the green-sensitive layer on the red-sensitive layer. It may not be preferred to use a tabular grain emulsion in the red-sensitive layer closest to the body.

As described above, the tabular grain emulsion and the non-tabular grain emulsion used in the present invention are usually those subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant locations are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and their locations are shown in the table below.

Various color couplers can be used in the light-sensitive material of the present invention, and specific examples thereof are described in the patents described in the above-mentioned Research Disclosure (RD) No. 17643, VII-CG. I have. As the dye-forming coupler, a coupler which gives the three primary colors of the subtractive color method (that is, yellow, magenta and cyan) by development and development is important. Specific examples of the diffusion-resistant 4-equivalent or 2-equivalent coupler are described in RD17643 and VII. In addition to the couplers described in the patents described in -C and D, the following can be preferably used in the present invention.

Representative examples of yellow couplers that can be used in the light-sensitive material of the present invention include hydrophobic acylacetamide couplers having a ballast group. Specific examples thereof are described in U.S. Pat. Nos. 2,407,210, 2,875,057 and 3,265,506. In the present invention, the use of a two-equivalent yellow coupler is preferable, and U.S. Pat.
Nos. 408,194, 3,447,928, 3,933,501 and 4,022,620, and the like. 1979 4
Mon), UK Patent No. 1,425,020, West German Application Publication No. 2,219,9
No. 17, No. 2,261,361, No. 2,329,587 and No. 2,
A typical example thereof is a nitrogen atom-elimination type yellow coupler described in No. 433,812. The α-pivaloylacetanilide type coupler is excellent in the fastness of a coloring dye, especially in light fastness, while the α-benzoylacetanilide type coupler can obtain a high color density.

Examples of the magenta coupler that can be used in the light-sensitive material of the present invention include hydrophobic isodazolone-based or cyanoacetyl-based couplers having a ballast group, preferably 5-pyrazolone-based and pyrazoloazole-based couplers. A 5-pyrazolone coupler is a coupler in which the 3-position is substituted with an arylamino group or an acylamino group,
Preferred in terms of the hue and color density of the coloring dye, representative examples of which are described in U.S. Patent Nos. 2,311,082, 2,343,703, and
Nos. 2,600,788, 2,908,573, 3,062,653, 3,152,896, and 3,936,015. As the leaving group of the 2-equivalent 5-virazolone coupler, a nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or an arylthio group described in U.S. Pat. No. 4,351,897 is particularly preferred. Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 can obtain a high color density. As the pyrazoloazole-based coupler, pyrazolobenzimidazoles described in U.S. Pat.No. 3,061,432, preferably pyrazolone [5,1-c] (1,2,4) triazoles described in U.S. Pat.No.3,752,067, Research Disclosure 24220 (June 1984
) And Research Disclosure 24230 (1).
Pyrazolopyrazoles described in JP-A-60-43659. The imidazo (1,2-b) pyrazoles described in U.S. Pat.No. 4,500,630 are preferable in terms of low yellow side absorption and light fastness of the coloring dye,
Pyrazolo [1,5-b] described in U.S. Pat.No.4,540,654
[1,2,4] triazole is particularly preferred.

Cyan couplers that can be used in the light-sensitive material of the present invention include hydrophobic and non-diffusible naphthol-based couplers and phenol-based couplers, and the naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.
Representative examples include oxygen atom-eliminating two-equivalent naphthol-based couplers described in 052,212, 4,146,396, 4,228,233 and 4,296,200. Specific examples of phenolic couplers are described in U.S. Pat.
No. 929, No. 2,801,171, No. 2,772,162, No. 2,89
No. 5,826.

Couplers capable of forming cyan dyes that are robust to humidity and temperature are preferably used in the present invention. Typical examples thereof include alkyl groups having an ethyl group or more at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Phenolic cyan coupler having a group, U.S. Pat.No. 2,772,162
No. 3,758,308, No.4,126,396, No.4,334,01
No. 1,327,173, 2,3-diacylamino-substituted phenolic couplers described in West German Patent Publication No. 3,329,729 and European Patent No. 121,365, U.S. Pat.
No. 622, No. 4,333,999, No. 4,451,559 and No.
And phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position described in 4,427,767. A cyan coupler described in European Patent No. 161,626A in which a 5-position of naphthol is substituted with a sulfonamide group, an amide group or the like is also excellent in color image fastness and can be preferably used in the present invention.

In order to correct unnecessary absorption of various coloring elements, it is preferable to carry out masking by using a colored coupler in combination with a color photosensitive material for photography. Typical examples include a yellow-colored magenta coupler described in U.S. Pat.No. 4,163,670 and Japanese Patent Publication No. 57-39413 or a magenta-colored cyan coupler described in U.S. Pat.Nos. 4,004,929, 4,138,258 and British Patent 1,146,368. No. Other colored couplers are described in RD17643, VII-G above.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such couplers are disclosed in U.S. Pat.No. 4,366,237 and British Patent 2,125,570.
No. 1 contains specific examples of magenta couplers, and EP 96,5
No. 70 and West German Application Publication No. 3,234,533 have yellow,
Specific examples of magenta or cyan couplers are described.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,282.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the aforementioned RD17643, VII to F are useful.

Preferred in combination with the present invention is disclosed in
Developer inactivated type represented by 151944; U.S. Pat. No. 4,248,
962 and a timing type represented by JP-A-57-154234; a reaction type represented by Japanese Patent Application No. 59-39653,
Particularly preferred are JP-A-57-151944 and JP-A-58-2179.
No. 32, Japanese Patent Application No. 59-75474, No. 59-82214, No. 59-8221
Developer inactivated DI described in No. 4, No. 59-90438, etc.
R couplers and reactive DIS couplers described in Japanese Patent Application No. 59-39653.

In the light-sensitive material of the present invention, a coupler which releases a nucleating agent or a development accelerator or a precursor thereof in an image-like manner during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. Couplers which release a nucleating agent or the like which has an adsorbing effect on silver halide are particularly preferred, and specific examples thereof are described in JP-A-59-157638 and JP-A-59-170840.

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

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643 and from page 647 of No.18716, right column
It is described in the left column on page 648.

The color photographic light-sensitive material according to the present invention is described in RD.
Developing can be carried out by a conventional method described in 17643, pages 28 to 29 and No. 18716, 651, left column to right column.

The color photographic light-sensitive material of the present invention is usually subjected to a washing treatment or a stabilization treatment after the development, bleach-fixing or fixing treatment.

In the water washing step, two or more tanks are generally countercurrently washed to save water. As a stabilizing treatment, a multi-stage countercurrent stabilizing treatment as described in JP-A-57-8543 is exemplified as a representative example instead of the washing step. In the case of this step, 2 to 9 countercurrent baths are required. Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (eg, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, etc.) for adjusting the membrane pH (eg, pH 3 to 8) Monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. are used in combination) and formalin. In addition, if necessary, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (benzoisothiazoline, isothiazolone, 4-thiazoline benzimidazole, halogen) Phenol, etc.), surfactants, optical brighteners, hardeners and the like, or two or more of the same or different desired compounds may be used in combination.

Also, ammonium chloride as a membrane pH adjuster after treatment,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. The present invention also relates to Research Disclosure 17123 (July 1978).
The present invention can also be applied to black-and-white light-sensitive materials utilizing a mixture of three-color couplers described in the above.

 Hereinafter, the present invention will be further described with reference to examples.

(Example-1) (1) Preparation of emulsion Preparation of emulsion 1 4.5 g of KBr and 7 g of gelatin having an average molecular weight of (20,000)
AgNO ₃ aqueous solution (32 g of AgNO ₃ and 100,000 gelatin in 100 ml) was stirred into an aqueous solution 1 containing
0.7 g and 0.14 ml of HNO ₃ (1N)) and an aqueous KBr solution (1
(Including 0.7 g of 20,000 gelatin in 00 ml)
While keeping the r value constant, 27.5 cc was added at 25 cc / min. The temperature was 30 ° C. Of this emulsion, 350 ml was used as a seed crystal, and 650 ml of an aqueous gelatin solution (20 g of gelatin, KB
r1.2 g), raise the temperature to 75 ° C., ripen for 40 minutes, add an AgNO ₃ aqueous solution (including 1.7 g of AgNO ₃ ) in 1 minute 30 seconds, and then add NH ₄ NO ₃ (50 wt. %) Aqueous solution 6.2ml and NH
₃ (25% by weight) aqueous solution (6.2 ml) was added and the mixture was aged for 40 minutes. Next, the emulsion was adjusted to pH 7.0, KBr1g was added, and then AgNO ₃
An aqueous solution (containing 10 g of AgNO ₃ in 100 ml) and an aqueous KBr solution were added at a rate of 8 ml / min for the first 10 minutes, and at a rate of 15 ml / min for the next 20 minutes, a CDJ with a silver potential of −20 mV was added. This emulsion was washed with water and redispersed. A replica image of the obtained emulsion grains was obtained by TEM (magnification: 3280).
Times). The average particle size of the particles of the present invention in the emulsion is 1.
The average aspect ratio was 1 μm and the average thickness was 0.16 μm. Table 1 shows other characteristics.

(Preparation of Emulsion 2) When the addition of 80% of the total amount of AgNO ₃ in Emulsion 1 was completed, the addition of the aqueous solution of AgNO ₃ and KBr was interrupted, the temperature was raised to 50 ° C., and 830 ml of KI aqueous solution was added in about 10 seconds. Thus, Emulsion 2 was prepared.

At this time, the KBr aqueous solution was added just before the addition of the KI aqueous solution,
The silver potential was adjusted to -60 mV.

(Preparation of Emulsions 3, 4, 5) Emulsions 3, 4, and 5 were prepared by reducing the amount of the KBr aqueous solution added before the addition of the KI aqueous solution in Emulsion 2, and setting the silver potential to -50 mV, -30 mV, and -20 mV. Prepared.

(Preparation of Emulsions 6, 7, 8) The amount of the KI aqueous solution added in Emulsion 2 was changed from 830 ml to 620 ml.
Emulsions 6, 7, and 8 were prepared by reducing to ml, 410 ml, and 205 ml. (Preparation of Emulsions 9, 10 and 11) In Emulsion 2, the temperature at the time of adding AgNO ₃ for the first time was changed from 30 ° C. to 45 ° C., 60 ° C. and 75 ° C.
0,11 was prepared.

(Preparation of Emulsions 12, 13 and 14) In Emulsion 2, the ripening time and temperature were set at 75 ° C for 40 minutes.
Emulsions 12, 13, and 14 were prepared at 60 ° C for 40 minutes, 50 ° C for 40 minutes, and 50 ° C for 20 minutes.

(2) Preparation of coating sample and evaluation thereof For each of the emulsions obtained in (1), dodecylbenzenesulfonate as a coating aid, p-vinylbenzenesulfonate as a thickener, and vinylsulfone as a hardener An emulsion coating solution was prepared by adding the compound and a polyethylene oxide compound as a photographic property improving agent. Subsequently, these coating liquids were separately and uniformly applied onto a subbed-processed polyester base, and a surface protection tank mainly composed of an aqueous gelatin solution was applied thereon to prepare coating samples 101 to 114. At this time, the coated silver amount of each of Samples -101 to 114 was 4.0 g.
/ m ² , and the gelatin coating amount of the protective layer is 1.3 g / m ² respectively.
The gelatin coating amount of the emulsion layer was 2.7 g / m ² .

The following experiment was performed in order to evaluate the coated product obtained in this manner.

First, the sample pieces of the coating samples 101 to 114 were exposed for 1/100 second exposure time 1
Wedge exposure at 0 CMS exposure dose, with processing solution of the following composition
After developing at 20 ° C. for 4 minutes, fixing, washing, and drying, sensitometry was performed to determine the sensitivity by the reciprocal of the exposure amount giving a density of fog + 0.1, and D = 0.2 and D = 1.0 on the characteristic curve. The gamma was determined from the slope of the straight line connecting the points. Next, two sets of sample pieces of the coated samples 101 to 114 were prepared, exposed to wedges under the same exposure conditions as described above, and immediately after one set of exposures,
One set was stored at 50 ° C, 55% for 3 days, developed with the same processing solution at 20 ° C for 2 minutes, then fixed, washed with water, dried, and then subjected to sensitometry, and the concentration of fog +0.1 in each development The sensitivity was determined from the reciprocal of the amount of exposure that gave, and the storage stability was evaluated.

Treatment solution 1-Phenyl-3-pyrazolidone 0.5 g Hydroquinone 10 g Ethylenediaminetetraacetic acid / sodium sodium 2 g Potassium sulfite 60 g Boric acid 4 g Potassium carbonate 20 g Sodium bromide 5 g Diethylene glycol 20 g Adjusted to pH 10.0 with sodium hydroxide 1 Table 2 shows the obtained results.

Tables 1 and 2 show the following.

In contrast to Emulsion 2, in Emulsions 3, 4, and 5, the number of grains in which dislocations are observed tends to increase in order, but the iodine distribution between grains is widened and the gradation is softened.

In the emulsions 6, 7, and 8, the iodine distribution between grains becomes narrower in order, but the ratio of grains containing dislocations is lowered, and extreme deterioration in latent image preservability is observed.

In the emulsions 9, 10, and 11, the grain size distribution is widened in order and the gradation is soft.

In Emulsions 12, 13, and 14, the proportion of grains having an aspect ratio of 3 or more decreased in order, and softening of gradation was observed.

Emulsions in which dislocations are scarcely observed are not favorable in terms of gradation softening and latent image preservability.

(Example 2) Preparation of Sample 201 A multilayer color photosensitive material composed of each layer having the following composition was prepared on an undercoated cellulose triacetate film support having a thickness of 127 µm to prepare Sample 201. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: Anti-halation layer Black colloid 0.25 g Gelatin 1.9 g UV absorber U-1 0.004 g UV absorber U-3 0.1 g UV absorber U-4 0.1 g UV absorber U-6 0.1 g High boiling organic solvent Oil-1 0.1 g Second layer: Intermediate layer Gelatin 0.4 g Dye D-4 0.4 mg Compound Dpd-D 4 mg High boiling organic solvent Oil-2 0.04 g Ultraviolet absorber U-2 0.1 g Third layer: Intermediate layer Fine-grained silver iodobromide emulsion fogged inside (average particle size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) Silver amount 0.05 g gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver Amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-9 0.05 g Fifth layer: Medium-sensitivity red-sensitive emulsion layer Emulsion C Silver amount 0.5 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling organic solvent Oil-2 0.1 g Layer: High sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-3 0.7 g Coupler C-1 0.3 g Additive P-1 0.1 g Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3g Color mixture prevention agent Cpd-K 2.6mg UV absorber U-1 0.1g UV absorber U-6 0.1g Compound Cpd-D 2.0mg High boiling organic solvent Oil-2 0.04g Eighth layer: Intermediate layer Surface and interior Silver iodobromide emulsion (average grain size 0.06
μm, variation coefficient 16%, Ag I content 0.3 mol%) silver amount 0.02 g gelatin 1.0 g additive P-1 0.2 g color mixture inhibitor Cpd-J 0.1 g color mixture inhibitor Cpd-A 0.1 g 9th layer: low sensitivity Green-sensitive emulsion layer Emulsion E Silver content 0.25 g Emulsion F Silver content 0.15 g Gelatin 0.5 g Coupler C-4 0.2 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High-boiling organic solvent Oil-1 0.1 g High-boiling organic solvent Oil-2 0.1 g 10th layer: Medium-sensitive green-sensitive emulsion layer Emulsion G Silver amount 0.4 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.05 g Compound Cpd-H 0.05 g High boiling organic solvent Oil-2 0.01 g 11th layer: High sensitivity green-sensitive emulsion layer Emulsion H Silver amount 0.5 g Gelatin 1.0 g Coupler C-8 0.1 g Coupler C-4 0.3 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling organic solvent Oil-1 0.02 g High boiling organic solvent Oil -2 0.02g 12th layer: Intermediate layer Gelatin 0.6 g Dye D-2 0.05g Dye D-1 0.02g Dye D-3 0.01g 13th layer: Yellow filter layer Yellow colloidal silver Silver 0.1 g Gelatin 1.1 g Prevent color mixing Agent Cpd-A 0.01 g High boiling organic solvent Oil-1 0.01 g 14th layer: intermediate layer gelatin 0.6 g 15th layer: low-sensitivity blue-sensitive emulsion layer Emulsion I Silver amount 0.4 g Emulsion J Silver amount 0.2 g Gelatin 0.8 g Coupler C-5 0.6g 16th layer: Medium speed blue-sensitive emulsion layer Emulsion K Silver amount 0.5g Gelatin 0.9g Coupler C-5 0.3g Coupler C-6 0.3g 17th layer: High speed blue-sensitive emulsion layer Emulsion L Silver amount 0.4g gelatin 1.2g coupler C-6 0.7g 18th layer: 1st protective layer gelatin 0.3g UV absorber U-1 0.04g UV absorption Agent U-2 0.01g UV absorber U-3 0.03g UV absorber U-4 0.03g UV absorber U-5 0.05g UV absorber U-6 0.05g High boiling organic solvent Oil-1 0.02g Formalin scavenger Cpd -C 0.2 g Cpd-I 0.4 g Cpd-L 2.3 mg Dye D-3 0.05 g 19th layer: 2nd protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content Silver content 0.1g Gelatin 0.4g 20th layer: 3rd protective layer Gelatin 0.2g Polymethyl methacrylate (average particle size 1.5μ) 0.1g Copolymer of methyl methacrylate and acrylic acid 4: 6 (average particle size) Diameter 1.5μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g Phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol , And phenethyl alcohol were added.

Further, additives F-1 to F-7 were added in addition to the above composition. Furthermore, in addition to the above composition, gelatin hardener H-1 and surfactants W-3 to 6 for coating and emulsification were added to each layer.

The silver iodobromide emulsions A to L used in Sample 201 are shown in Tables 3 and 4.
It is as follows. The names or chemical structural formulas of the compounds used for preparing Sample 201 are as shown in Table A below.

(Preparation of Samples 202 to 214) Except for using Emulsion-2 to 14 in place of Emulsion L (Emulsion 1 of Example 1) used in the high-sensitivity blue-sensitive emulsion layer of the 17th layer in the preparation of Sample 201, Sample 202 in the same procedure as Sample 201
To 214 were prepared.

(Evaluation of Coated Sample) After subjecting the sample pieces of the coated samples 201 to 214 obtained as described above to white light wedge exposure with an exposure time of 1/100 second and an exposure amount of 20 CMS, the following development processing is performed. And sensitometry.

The overflow liquid of the second washing (2) is washed with the second washing (1).
Led to the bath.

 The composition of each processing solution was as follows.

The gradation of the seventeenth layer (high-sensitivity blue-sensitive emulsion layer) was estimated based on the relative exposures that were 2.5 and 1.5 larger than the minimum yellow density. As a result, the sample containing the emulsion of the present invention had a hard gradation, and the effect of the present invention was confirmed.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-220238 (JP, A) JP-A-60-254032 (JP, A) JP-A-63-151618 (JP, A) JP-A-1- 201649 (JP, A) JP-A-2-256043 (JP, A)

Claims (4)

(57) [Claims] (1) Tabular silver halide grains having an aspect ratio of 3 or more occupy at least 50% of the total projected area, and the relative standard deviation of the grain size distribution of the tabular silver halide grains occupying 50% is 25% or less. The silver halide grains corresponding to 50% or more of the total number of silver halide grains have 10 or more dislocations per grain, and 50% of the total projected area of these silver halide grains. A silver halide photographic emulsion characterized in that the relative standard deviation of the silver iodide content distribution of large tabular silver halide grains occupying 30% or less is 30% or less. 2. The silver halide photographic emulsion according to claim 1, wherein the tabular silver halide emulsion grains have a portion having a higher silver iodide content than the surface of the grains. 3. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein said silver halide emulsion layer contains the silver halide photographic emulsion according to claim (1). Characteristic silver halide photographic material. 4. A photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains the silver halide photographic emulsion according to claim (2). Characteristic silver halide photographic material.