JPH1073896A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve photographic fog and sensitivity, to reduce an increase in the fog or decrease in the sensitivity during storage and to improve pressure resistance by specifying the average aspect ratio, coefft. of changes in the particle size and coefft. of changes in the thickness of silver halide particles. SOLUTION: In this silver halide photographic emulsion containing silver halide particles, the silver halied particles have <=3.0 average aspect ratio and substantially have dislocation lines, <=20.0% coefft. of changes in the particle size and <=20.0% coefft. of changes in the thickness. The silver halide particles are substantially planer silver halide particles and preferably such particles having two parallel twin faces so as to decrease fluctuation in the particle size and thickness of the silver halide particles. The compsn. of the silver halide particles is preferably silver iodide bromide or silver chloride iodide bromide, and especially silver iodide bromide containing >1.0mol% silver iodide is preferable. Moreover, the average silver iodide content is preferably <10.0%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic emulsion which is excellent in sensitivity and fog, and has improved pressure resistance and storage stability. The present invention relates to a silver halide photographic material using the same.

[0002]

2. Description of the Related Art In recent years, demands for performance of silver halide photographic materials (hereinafter, also simply referred to as photographic materials) are becoming more and more severe, and basic photographic properties such as high sensitivity, low fog, and excellent granularity are required. Demands for not only high performance but also improvements in various properties such as pressure resistance and storage stability have become stronger than ever.

In general, a silver halide photographic light-sensitive material is subjected to various pressures. For example, negative films for general photography are subject to great pressure during cutting and perforation in the manufacturing process,
They may bend or rub when transported in the camera. As described above, it is known that when various pressures are applied to a silver halide photographic light-sensitive material, the photographic performance is changed, and a technique for improving the resistance to these pressures is desired. Also, with the spread of photography and the spread of applications with the spread of compact cameras and films with lenses, silver halide photographic materials have been maintained in various environments and used under various conditions. . Along with that, storage stability is also an important performance item.

[0004] Silver halide grains are a dominant factor in the basic performance of silver halide photographic light-sensitive materials, and the development of silver halide grains aimed at improving sensitivity and image quality has been energetically addressed. In general, in order to improve the image quality, it is effective to reduce the particle size of the silver halide grains, increase the number of grains per unit silver amount, and increase the number of coloring points (the number of pixels).

However, reducing the particle size causes a reduction in sensitivity, and there is a limit to satisfying both high sensitivity and high image quality. In order to achieve higher sensitivity and higher image quality, techniques for improving the sensitivity / size ratio per silver halide grain have been studied. One of the techniques is to use tabular silver halide grains. Is disclosed in JP-A-58-111.
No. 935, No. 58-111936, No. 58-1119
37, 58-13927, and 59-99433.

When these tabular silver halide grains are compared with so-called normal crystal silver halide grains such as hexahedral, octahedral, or dodecahedral grains, the surface area per unit volume of the silver halide grains is increased. In the case of the same volume, tabular grains have the advantage that more spectral sensitizing dyes can be adsorbed on the grain surface and that higher sensitivity can be achieved. JP-A-63-92942 discloses a technique for providing a region having a high silver iodide content in tabular silver halide grains, and JP-A-63-151618 discloses a hexagonal tabular silver halide. Techniques using particles have been taken and their effects on sensitivity and granularity have been shown, respectively.

Further, Japanese Patent Application Laid-Open No. 63-106746 discloses that
Japanese Patent Application Laid-Open No. 1-279237 discloses that a tabular silver halide grain having a substantially layered structure in a direction parallel to two opposing main planes is substantially parallel to two opposing main planes. Tabular silver halide grains having a layered structure delimited by planes parallel to each other, wherein the average silver iodide content of the outermost layer is at least 1 mol% or more higher than the average silver iodide content of the whole silver halide grains Are described for each of the techniques used. In addition, in JP-A-1-183644,
A technique using tabular silver halide grains in which the silver iodide distribution of a silver halide phase containing silver iodide is completely uniform is described.

[0008] There have been several reports on techniques focusing on parallel twin planes in tabular silver halide grains (hereinafter also simply referred to as tabular grains). For example, JP-A-63-1
No. 63451, the ratio (b / a) of the longest distance (a) between two or more parallel twin planes and the thickness (b) of a grain
Is a technique using tabular silver halide grains having a value of 5 or more, and JP-A-1-201649 discloses a technique in which the number of dislocation lines present in the tabular silver halide grains is also defined at the same time. Effects on sensitivity, granularity, and sharpness have been reported.

In WO 91/18320, the distance between at least two twin planes is 0.012.
A technique using tabular silver halide grains of less than .mu.m is disclosed in Japanese Patent Application Laid-Open (JP-A) No. 3-353003, in which core / shell type twin silver halide grains having an average distance between the longest twin planes of 10 to 100 DEG are used. Techniques are reported, each describing sensitivity, graininess, or the effect of improving sharpness, pressure characteristics, and graininess.

[0010] Among the efforts in the art for a silver halide emulsion aiming at improving the sensitivity and image quality of a silver halide photographic light-sensitive material, halogen is one of the most basic and important technologies. There is a technique for monodispersing silver halide emulsions. Since the optimum conditions for chemical sensitization are different between large and small silver halide grains, they are optimal for a mixed, ie polydisperse (wide grain size) silver halide emulsion. It is difficult to perform chemical sensitization, and as a result, fog is often increased or sufficient chemical sensitization cannot be performed in many cases.
On the other hand, in the case of a monodispersed silver halide photographic emulsion, optimal chemical sensitization can be easily performed, and a silver halide photographic emulsion having high sensitivity and low fog can be prepared. In addition, a hard gradation (high gamma) characteristic curve can be expected.

As a monodispersion technique for tabular silver halide grains, Japanese Patent Application Laid-Open No. 1-213637 discloses a technique for improving sensitivity, graininess and the like by using monodisperse silver halide grains having two parallel twin planes. Is described. Further, JP-A-5-173268 and JP-A-6-202258 disclose methods for producing tabular silver halide grains having a small grain size distribution. In the monodispersion technique of these tabular grains, the monodisperse silver halide grains mean that the variation in the projected area between individual tabular grains is small. Furthermore, in JP-A-6-258744,
A technique for improving sensitivity, gradation, pressure resistance, and latent image preservability using monodisperse tabular silver halide grains having regions having different silver halide compositions inside the grains has been reported.
Monodispersion as referred to in this technique means that the volume variation between individual particles is small. In other words, the prior art relating to the monodispersion of these tabular silver halide grains focuses only on the variation coefficient of the projected area diameter and the grain volume of the silver halide grains, and the thickness of the silver halide grains is reduced. It is not a technique intended to control the coefficient of variation of the height.

Techniques related to the thickness of tabular silver halide grains are described in JP-A-6-43605 and JP-A-6-436.
No. 06 and Japanese Patent Application Laid-Open No. 7-191425 are known. JP-A-6-43605 and JP-A-6-436
Specifically, the technique disclosed in JP-A-6-2006 focuses on the average value of the thickness of tabular silver halide grains, and the technique disclosed in JP-A-7-191425 discloses a technique disclosed in JP-A-7-191425. It defines a value obtained by taking the ratio of the variation coefficient of the grain thickness to the variation coefficient of the distance between twin planes.

JP-A-6-43605 and JP-A-6-43605
No. 606 and JP-A-6-332090 suggest usefulness in reducing the thickness distribution of tabular silver halide grains in terms of photographic performance or emulsion preparation. Nothing is shown.

Japanese Patent Application Laid-Open No. 5-173272 discloses a flat plate having an even number of twin planes parallel to the main plane and having a shape of the main plane which is a hexagon having a maximum adjacent side ratio of 2.0 to 1.0. A silver halide emulsion is disclosed in which the coefficient of variation of the particle size of the silver halide grains is in the range of 21 to 29% and the coefficient of variation of the thickness is 20% or less. In Examples of this publication, silver halide emulsions containing grains having a coefficient of variation of 20% or less in diameter and a coefficient of variation of 20% or less in thickness of tabular grains are mentioned in Comparative Examples. However, the values of these variation coefficients of the emulsion are values measured for tabular silver halide grains whose main plane is hexagonal with a maximum adjacent side ratio of 2.0 to 1.0. The present inventors have conducted additional tests on the Examples. As a result, the emulsion was found to have hexagonal tabular silver halide grains having a principal plane shape having a maximum adjacent side ratio of 2.0 to 1.0 in terms of projected area ratio. Although about 90% or less existed, small particles considered to be normal crystals and coarse particles having a plurality of non-parallel twin planes were also present. With respect to the emulsion, diameter and thickness were again measured for arbitrary grains contained in the emulsion, and the coefficient of variation was determined. The coefficient of variation of both diameter and thickness exceeded 20%.

Therefore, the technique cannot adjust the silver halide emulsion of the present invention.

As a method for increasing the sensitivity of a silver halide emulsion, US Pat. No. 4,956,269 discloses a technique for introducing a transition line into tabular silver halide grains. It is generally known that when pressure is applied to silver halide grains, fogging or desensitization occurs.However, grains having dislocation lines introduced therein have a problem that they are significantly desensitized by application of pressure. Was. JP-A-1-201649 discloses tabular grains having an average aspect ratio of 8 or less, the longest distance (a) between two or more parallel twin planes of the grains and the thickness (b) of the grains. Is 5% or more (number) of all tabular grains, and grains having 10 or more dislocation lines are 50% or less of all tabular grains.
% Or more (number) are disclosed. In this publication, as a preferred embodiment, the coefficient of variation of grain thickness is 20% or less, and the coefficient of variation of projected area is 30% or less. However, when the present inventor re-tested the technique, the silver halide emulsion obtained by the technique contained silver halide grains other than tabular grains defined by the technique, that is, normal crystals and non-parallel twin grains. Were present.

When the particle size of the emulsion was measured with respect to arbitrary particles contained therein, the value was found to be 20%.
Was over.

Therefore, the silver halide emulsion obtained from the technique is different from the silver halide emulsion of the present invention.

In addition, the technique cannot improve remarkable desensitization caused by pressure being caused by introducing dislocation lines. Japanese Patent Application Laid-Open No. Hei 3-189624 discloses a tabular silver halide grain having an aspect ratio of 2 or more and having 10 or more dislocation lines in a fringe portion, and a size distribution of the tabular silver halide grain. Are monodispersed silver halide emulsions. But,
In this publication, there is no mention of the particle thickness distribution.

That is, it is a tabular silver halide grain having dislocation lines, which is a feature of the present invention, and has a feature that both the coefficient of variation of the grain size and the coefficient of variation of the grain thickness are small. Silver halide emulsions have not been obtained before. In addition, it has not been known that the silver halide emulsion improves the desensitization of a silver halide emulsion having dislocation lines when subjected to pressure.

[0021]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic emulsion and a silver halide which are excellent in fog and sensitivity, have little increase in fog and decrease in sensitivity during storage, and have improved pressure resistance. A photographic light-sensitive material is provided.

[0022]

The above objects of the present invention are as follows. In a silver halide photographic emulsion containing silver halide grains, the silver halide grains have an average aspect ratio of at least 3.0, substantially have dislocation lines, and have a coefficient of variation of grain size of 20.0%. Less than and the coefficient of variation of the thickness is 2
1. a silver halide photographic emulsion comprising 0.0% or less; 2. The silver halide photographic emulsion according to the above item 1, wherein the silver halide grains have an average aspect ratio of 6.0 or more; 3. The silver halide photographic emulsion according to the above 1 or 2, wherein the coefficient of variation of the thickness of the silver halide grains is 15.0% or less. 4. A silver halide photographic light-sensitive material comprising at least one silver halide photographic emulsion layer provided on a support, containing the silver halide photographic emulsion described in any one of 1 to 3 above. Material.

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

Tabular silver halide grains are crystallographically classified as twins. Twins are crystals having one or more twin planes in one grain. Classification of twin morphology in silver halide grains is based on a report by Klein and Moiser in "Photographhishhe Korrespon."
denz, Vol. 99, p. 99, and Vol. 100, p. 57.

In the present invention, the silver halide grains are substantially tabular silver halide grains, and the term "tabular silver halide grains" means one or two parallel silver halide grains in the grains.
It has two or more twin planes. However, it is preferable that the grains have two parallel twin planes in order to reduce variation in grain size and thickness between silver halide grains, which is a main constituent requirement of the present invention.

In the present invention, the aspect ratio refers to the ratio of the particle diameter to the thickness of the silver halide grains (aspect ratio = diameter / thickness). In the present invention, the grain size is defined as an area when the grain is projected perpendicularly to a plane having the largest area (also referred to as a main plane) among the planes forming the surface of the silver halide grain (also referred to as a main plane) (Projected area). In the case of tabular grains, the grain thickness is the thickness of the grain in a direction perpendicular to the major plane and generally corresponds to the distance between the two major planes.

The particle size and thickness can be determined by the following method. After preparing a sample coated with silver halide particles so that the main surface and the latex ball of known particle size as an internal standard are oriented in parallel on the support, and shadowed by carbon vapor deposition from a certain angle, A replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area and thickness of each particle are determined using an image processing device or the like. In this case, the projected area of the particle can be calculated from the projected area of the internal standard, and the thickness of the particle can be calculated from the length of the internal standard and the shadow of the particle.

In the present invention, the average value of the aspect ratio, the grain size and the grain thickness is determined by arbitrarily setting the silver halide grains contained in the silver halide emulsion to 10 by the shadowing method.
A value obtained by measuring at least 00 pieces and obtaining an arithmetic average thereof. The average aspect ratio of the tabular silver halide grains of the present invention is 3.0 or more, and particularly preferably 6.0 or more.

In the present invention, the coefficient of variation of the grain size and grain thickness of silver halide grains is a value defined by the following equation using the values obtained from the above measurements.

The coefficient of variation of the grain size of the silver halide grains of the present invention is 20.0% or less, more preferably 10.0% or less. Further, the coefficient of variation of the thickness of the silver halide grains of the present invention is 20.0% or less, more preferably 15.0% or less.

Coefficient of variation (%) of particle size = (standard deviation of particle size /
Average value of particle size) x 100 Variation coefficient of thickness (%) = (standard deviation of thickness / average value of thickness)
× 100 The composition of the silver halide grains in the invention is preferably silver iodobromide or silver chloroiodobromide. In particular, silver iodobromide containing 1.0 mol% or more of silver iodide is preferable. In addition, the average silver iodide content of a silver halide photographic emulsion is 10.0 mol% or less. It is preferably 1.0 mol% or more and 6.0 mol% or less. The composition of the silver halide grains can be determined by a composition analysis method such as an EPMA method and an X-ray diffraction method.

The average silver iodide content of the surface phase of the silver halide grains of the present invention is preferably at least 1 mol%.
It is more preferably from 2 mol% to 20 mol%, and still more preferably from 3 mol% to 15 mol%. Here, the average silver iodide content of the surface phase of the silver halide grains is a value obtained by using the XPS method or the ISS method. For example, the surface silver iodide content by the XPS method can be obtained as follows. The sample was cooled to −155 ° C. or less in an ultra-high vacuum of 1 × 10 ⁻⁴ torr or less, and irradiated with MgKa as an X-ray for a probe at an X-ray source current of 40 mA.
d5 / 2, Br3d and I3d3 / 2 are measured. Correct the integrated intensity of the measured peak with the sensitivity factor,
The composition such as the silver iodide content of the silver halide surface phase is determined from these intensity ratios.

The silver halide photographic emulsion of the present invention has substantially dislocation lines. In the present invention, "having substantially dislocation lines" means that 1000 or more silver halide grains contained in a silver halide photographic emulsion are arbitrarily observed and 50% or more of the total shadow area has dislocation lines. Say. There is no particular limitation on the position where the dislocation line exists, but it is preferable that the dislocation line exists near the outer peripheral portion, near the ridge line, or near the vertex of the tabular silver halide grains. Speaking of the positional relationship of dislocation line introduction in the whole grain, it is preferably introduced at 50% or more of the silver amount of the whole grain, more preferably at 60% or more and 95% or less, more preferably at 70% or more. Most preferably, it is introduced between 90% or less. The number of dislocation lines is preferably 50% or more, more preferably 70% or more, and even more preferably 90% or more of the total projected area of grains containing 5 or more dislocation lines. . In each case, the number of dislocation lines is 1
It is particularly desirable that there be zero or more.

Dislocation lines of silver halide grains are described, for example, in J. Am. F. Hamilton, Photo. Sci. E
ng. 11 (1967) 57 and T.I. Shiozaw
a, J. et al. Soc. Photo. Sci. Japan35
(1972) 213 can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the silver halide photographic emulsion, taking care not to apply enough pressure to generate the dislocations on the silver halide grains, the main planes of which are oriented in parallel on a mesh for an electron microscope. The specimen is cooled and observed by a transmission method so as to prevent damage (such as printout) by an electron beam. At this time, the thicker the silver halide grains, the more difficult it is for an electron beam to pass through, so that a method using a high-pressure electron microscope can be observed more clearly. From the photographs of the silver halide grains obtained by such a method, the position and number of dislocation lines in each silver halide grain can be determined.

Further, in the silver halide photographic emulsion of the present invention, the silver iodide content between silver halide grains is preferably more uniform. That is, the coefficient of variation of the silver iodide content in the silver halide photographic emulsion is preferably 30% or less, and more preferably 20% or less. Here, the coefficient of variation is defined as a value obtained by dividing the standard deviation of the silver iodide content by the average value of the silver iodide content.
And a value obtained by arbitrarily measuring 1000 or more silver halide grains contained in a silver halide emulsion.

The silver halide grains for photography are microcrystals composed of silver chloride, silver bromide, silver iodide, or a solid solution thereof, and two or more phases having different silver halide compositions are contained in the crystal. It is possible to form. As a grain having such a structure, a grain composed of an inner core phase and an outer surface phase having mutually different silver halide compositions is known, and is generally called a core / shell type grain. The silver halide grains of the present invention preferably have a core / shell type grain structure in which the outer surface phase has a higher silver iodide content than the inner core phase.

As a preparation form of the silver halide photographic emulsion of the present invention, a method known in the art can be appropriately applied. For example, p of the reaction solution when forming silver halide grains
A so-called controlled double jet method or controlled triple jet method for controlling Ag can be used. Further, a silver halide solvent can be used if necessary, and as a useful silver halide solvent,
Ammonia, thioethers and thioureas can be mentioned. Regarding thioethers, U.S. Pat.
No. 1,157, No. 3,790,387, No. 3,5
No. 74,628 can be referred to. The method for preparing the silver halide grains of the present invention is not particularly limited, and an ammonia method, a neutral method using no ammonia, an acidic method, or the like can be used, but the fogging during the formation of the silver halide grains is suppressed. From the viewpoint that the silver halide grains can be formed, it is preferable to form tabular silver halide grains in an environment where the pH (the logarithm of the reciprocal of the hydrogen ion concentration) is 5.5 or less, more preferably 4.5 or less.

In order to more precisely control the silver iodide content between and within the silver halide grains of the present invention,
It is desirable that at least a part of the formation of the silver iodide-containing phase of the silver halide grains is carried out in the presence of silver halide grains having a lower solubility than the silver halide grains. It is particularly desirable to use silver iodide. For the same reason, a method of forming at least a part of the silver iodide-containing phase of silver halide grains by supplying only one or more types of silver halide fine grains is also preferable.

The method for introducing dislocation lines into the silver halide grains of the present invention is not particularly limited. For example, a method of adding an aqueous solution of an iodide ion such as potassium iodide and a solution of a water-soluble silver salt by double jet, or A method of adding silver iodide fine grains, a method of adding only an iodine ion solution,
A known method such as a method using an iodide ion releasing agent described in US Pat. No. 11,1781, or the like can be used to form a dislocation which is a source of a dislocation line at a desired position.
Among these methods, a method of adding an aqueous iodide ion solution and a water-soluble silver salt solution by a double jet, a method of adding silver iodide fine particles, and a method of using an iodide ion releasing agent are preferable. The addition method is most preferable.

The silver halide grains of the present invention preferably have a particle size in terms of volume of 0.1 to 1.2 μm, more preferably 0.20 to 0.8 μm.
m is more preferred. If it is less than 0.1 μm, it is difficult to obtain practical sensitivity, while if it is more than 1.2 μm, the granularity is significantly deteriorated due to the large particle diameter. Here, the volume-converted particle size is a value of the length of one side of a cube having the same volume as the silver halide grains.

Generally, tabular silver halide grains are prepared through nucleation, ripening and growth processes. In order to reduce both the coefficient of variation of the grain size and the thickness of the silver halide grains, it is important to note that the respective values are controlled from the nucleation and ripening stages.

The method for preparing the silver halide photographic emulsion of the present invention will be described below.

1. Nucleation The nucleation of tabular grains is generally carried out by simultaneously adding a silver salt aqueous solution and an alkali halide aqueous solution into a reaction vessel holding an aqueous dispersion medium having a protective colloid property, or a double jet method. An aqueous silver salt solution is added to the protective colloid solution containing alkali. Alternatively, a single jet method is used in which an aqueous alkali halide solution is added to a protective colloid solution containing an aqueous silver salt solution.

Also, if necessary, refer to
Nucleation can also be performed using the methods disclosed in US Pat. No. 5,104,786. The nucleation is preferably performed in a protective colloid aqueous solution under the condition of pBr of 1 to 4. Further, the pBr at the time of nucleation is 2.5
The following are preferable, and 1.5 to 2.5 are particularly preferable conditions.

As a dispersion medium having a protective colloid property used at the time of nucleation, there are gelatin and a protective colloid polymer. As a kind of gelatin, alkali-treated gelatin having a molecular weight of about 100,000 is usually used, but low-molecular-weight gelatin (molecular weight of 5,000 to 30,000) or oxidized gelatin is also known. The dispersion medium preferably used in the nucleation of the silver halide photographic emulsion of the present invention is a gelatin having a low content of methionine which suppresses the lateral growth of tabular nuclei grains, and specifically, oxidized gelatin or oxidized gelatin Low molecular weight gelatin (molecular weight 5,000 to 20,000). The concentration of the dispersion medium in the aqueous protective colloid solution during nucleation is generally 5% by weight based on the weight of the aqueous protective colloid solution.
But not more than 1% by weight, preferably 0.5% by weight
The following is more preferred. The temperature at the time of nucleation is preferably 60C or lower, more preferably 5C to 50C, and even more preferably 10C to 40C.

2. Ripening At the end of nucleation, grains that can grow as tabular grains (grains having one twin plane or a plurality of parallel twin planes)
And other particles (normal crystal particles and non-parallel twin particles). In order to obtain tabular silver halide grains having high monodispersibility, grains other than twin twin grains are eliminated,
It is important to make the particle size and thickness uniform.
As a method for achieving this, it is known to perform Ostwald ripening following nucleation. In order to perform Ostwald ripening, a method of increasing the solution temperature, a method of adding a silver halide solvent such as ammonia or thioether, and a method of combining the temperature increase and the addition of the solvent are used.

However, in order to obtain the silver halide photographic emulsion of the present invention, it is preferable not to use a silver halide solvent. This is because the addition of the solvent increases the thickness of the twin parallel twin grains, and at the same time, the distribution thereof is deteriorated. The solution temperature in the aging step is preferably from 40 to 80C, more preferably from 5 to 70C, and the pBr is preferably from 1.0 to 3.0, more preferably from 1.5 to 3.0.
2.5. The concentration of the dispersion medium in the aqueous solution is 0.5 to 1
0% by weight is preferable, and 0.5 to 5% by weight is more preferable.

In order to obtain the silver halide photographic emulsion of the present invention, immediately after the completion of nucleation, the following general formula [I]
Is preferred.

Formula [I] YO (CH ₂ CH ₂ O) m (CH (CH ₃ ) CH ₂ O) p
In (CH ₂ CH ₂ O) nY formula (I), Y represents a hydrogen atom, -SO ₃ M or -COBCOOM. M represents a hydrogen atom, an alkali metal atom, an ammonium group or an alkyl-substituted ammonium group having 5 or less carbon atoms, and B represents a linking group. m and n each represent an integer of 0 to 50, and p represents an integer of 1 to 100. Hereinafter, typical specific examples of the compound represented by the general formula [I] will be shown.

[0050]

Embedded image

Further, instead of the above compounds, US Pat. Nos. 5,147,771, 5,147,772, 5,147,773, 5,171,659, and Compounds such as other polyalkylene oxide block copolymers described in 332090, hydrophilic polyalkylene oxides, and polyethylene oxide derivatives can also be used.

In the technique disclosed in the above patent, the above compound is contained from the time of nucleation. This is because by suppressing the lateral growth of the generated plate nuclei using the above compound, it is possible to suppress the spread of the distribution of the particle size (projected area converted circular diameter value) of the plate nuclei and simultaneously increase the nucleation number. Intended.

However, the presence of the above compound from the nucleation stage is effective for monodispersing the particle size of tabular nuclei, but conversely increases the thickness and distribution of tabular nuclei. It cannot be an effective means for monodispersing the thickness of. It is very difficult to reduce the distribution of grain thickness that has spread during the nucleation stage in subsequent ripening and growth processes. On the other hand, even if the particle size distribution spreads to some extent after nucleation, it is possible to monodisperse the particle size distribution by allowing the compound to exist at the stage of ripening or growth. Therefore, what is essential for preparing the silver halide photographic emulsion of the present invention is: 1. At the time of nucleation, do not use a compound such as the compound or gelatin having a high methionine content, which suppresses lateral growth of tabular silver halide grains, or a protective colloid agent. 2. No ripening with a solvent that increases the thickness of the particles; At the time of ripening and growth, the above compound is used to appropriately suppress the spread of the particle size distribution of tabular grains.

That is, the coefficient of variation of the thickness of tabular silver halide grains is controlled at the stage of nucleation and ripening, and the coefficient of variation of the grain size is controlled at the stage of ripening and grain growth. It becomes possible to prepare a silver halide photographic emulsion.

In the silver halide photographic emulsion of the present invention, Research Disclosure No. 30811
9 (hereinafter abbreviated as RD308119) can be used.

The following shows the places to be described.

[0057]

[Table 1]

The silver halide photographic emulsion of the present invention can be subjected to physical ripening, other chemical ripening and spectral sensitization according to a known method.

The additives used in such a step include Research Disclosure No. 17643,
No. 18716 and no. 308119 (respectively,
RD17643, RD18716, RD30811
9) can be used. The places to be described are shown below.

[0060]

[Table 2]

Known photographic additives which can be used in the present invention are also described in the above-mentioned Research Disclosure.
The places to be described are shown below.

[0062]

[Table 3]

Various couplers can be used in the present invention, and specific examples are described in the above-mentioned Research Disclosure.

The following shows the relevant descriptions.

[0065]

[Table 4]

The additive used in the present invention is RD3081
It can be added by the dispersion method described in 19XIV.

In the present invention, the aforementioned RD17643
28 pages, RD18716 pages 647-8 and RD308
The support described in 119XIX can be used.

The light-sensitive material of the present invention includes the aforementioned RD3081
An auxiliary layer such as a filter layer or an intermediate layer described in the section 19VII-K can be provided.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 08119VII-K can be employed.

The present invention can be applied to various color light-sensitive materials represented by general or movie color negative films, slide or television color reversal films, color papers, color positive films, and color reversal papers. .

The light-sensitive material of the present invention is obtained by using
Pages 28 to 29, RD18716647 and RD30
The development can be carried out by the usual method described in 8119XIX.

[0071]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these embodiments.

(Preparation of Comparative Emulsion Em-100) [Nucleation] The following gelatin solution B-101 was kept at 28 ° C., and the stirring speed was 450 rpm using a mixing and stirring apparatus described in JP-A-62-160128. While stirring in minutes,
The pH was adjusted to 1.95 with 1N sulfuric acid. Thereafter, the S-101 solution and the X-101 solution were added at a constant flow rate for one minute by using the double jet method to form nuclei.

(B-101) Oxidized gelatin (average molecular weight 100,000) 2.100 g Potassium bromide 0.932 g [2.312 ml of a 10% by weight methanol solution of the following (compound A): 837.5 ml of H ₂ O (compound A) _{) HO (CH 2 CH 2 O} ) m (CH (CH 3) CH 2 O) 19.8 (CH 2 CH 2 O) nH (m + n = 9.77) (S-101) silver nitrate 1.624g H ₂ O 18. 747 ml (X-101) 1.138 g of potassium bromide 18.708 ml of H ₂ O [Aging] After completion of the above addition, the G-101 solution was added, and the temperature was raised to 60 ° C. over 30 minutes. Hold at 60 ° C. for another 20 minutes. During this time, the silver potential of the solution (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled at 6 mV using a 0.5 N potassium bromide solution.

(G-101) Alkali-treated inert gelatin (average molecular weight: 100,000) 4.478 g H ₂ O 105.4 ml [Growth] After ripening, p was added using 1N potassium hydroxide.
H was adjusted to 5.8. Subsequently, the S-102 solution and the X-102 solution were added using the double jet method for 41 minutes while accelerating the flow rates (the ratio of the addition flow rates at the end and at the start was about 10 times). After completion of the addition, the G-102 solution is added, and subsequently the S-103 solution and the X-103 solution are accelerated while increasing the flow rates (the ratio of the addition flow rates at the end and at the start is about 8.7 times).
Minutes. During this time, the silver potential of the solution was controlled at 8 mV using a 1.0 N potassium bromide solution.

(S-102) Silver nitrate 20.60 g H ₂ O 92.27 ml (X-102) Potassium bromide 14.43 g H ₂ O 91.77 ml (G-102) Alkali-treated inert gelatin (average molecular weight 100,000) _{) 20.76g H 2 O 170.7ml (S} -103) Silver nitrate _{577.8g H 2 O 834.0g (X-} 103) potassium bromide 396.7g iodide 11.29g H ₂ O 824.2ml said growth After completion, the mixture was subjected to desalting / washing treatment according to a conventional method, and gelatin was added to the mixture, which was dispersed well, and the pH and pAg were adjusted to 5.8 and 8.1.

The emulsion thus obtained is named Em-100.

(Preparation of Comparative Emulsion Em-200) [Nucleation] The following gelatin solution B-201 was kept at 28 ° C., and the stirring speed was 450 rpm using a mixing and stirring apparatus described in JP-A-62-160128. While stirring in minutes,
The pH was adjusted to 1.95 with 1N sulfuric acid. Thereafter, the S-201 solution and the X-201 solution were added at a constant flow rate for one minute by using a double jet method to form nuclei.

(B-201) Oxidized gelatin (average molecular weight 100,000) 2.100 g Potassium bromide 0.932 g H ₂ O 839.9 ml (S-201) Silver nitrate 1.624 g H ₂ O 18.747 ml (X- 201) G-201 was added to the potassium bromide 1.138g H ₂ O 18.708ml [aging] the additive after completion, the temperature was raised to 60 ° C. over a period of 30 minutes. Hold at 60 ° C. for another 20 minutes. During this time, the silver potential of the solution was controlled at 6 mV using a 0.5N potassium bromide solution.

(G-201) Alkali-treated inert gelatin (average molecular weight: 100,000) 4.478 g 10 wt% methanol solution of the above (Compound A) 2.312 ml H ₂ O 103.0 ml [Growth] After ripening, 1N Using potassium hydroxide
H was adjusted to 5.8. Subsequently, the S-202 solution and the X-202 solution were added using the double jet method for 41 minutes while accelerating the flow rates (the ratio of the addition flow rates at the end and at the start was about 10 times). After the addition is completed, the G-202 solution is added, and subsequently the S-203 solution and the X-203 solution are accelerated in flow rate (the ratio of the addition flow rate at the end to the start is about 8.7 times).
Minutes. During this time, the silver potential of the solution was controlled at 8 mV using a 1.0 N potassium bromide solution.

(S-202) Silver nitrate 20.60 g H ₂ O 92.27 ml (X-202) Potassium bromide 14.43 g H ₂ O 91.77 ml (G-202) Alkali-treated inert gelatin (average molecular weight 100,000) 20.76 g H ₂ O 170.7 ml (S-203) silver nitrate 577.8 g H ₂ O 834.0 ml (X-203) potassium bromide 396.7 g potassium iodide 11.29 g H ₂ O 824.2 ml After completion, the mixture was subjected to desalting / washing treatment according to a conventional method, and gelatin was added to the mixture, which was dispersed well, and the pH and pAg were adjusted to 5.8 and 8.1, respectively. The emulsion thus obtained was em-20
Set to 0.

(Preparation of Comparative Emulsion Em-300) [Nucleation] The following gelatin solution B-301 was kept at 28 ° C., and the stirring speed was 450 rpm using a mixing and stirring apparatus described in JP-A-62-160128. While stirring in minutes,
The pH was adjusted to 1.95 with 1N sulfuric acid. Thereafter, the S-301 solution and the X-301 solution were added at a constant flow rate for one minute by using a double jet method to form nuclei.

(B-301) Oxidized gelatin (average molecular weight 100,000) 2.100 g Potassium bromide 0.932 g 10% by weight methanol solution of (Compound A) 2.312 ml H ₂ O 837.5 ml (S-301 ) Silver nitrate 1.624 g H ₂ O 18.747 ml (X-301) Potassium bromide 1.138 g H ₂ O 18.708 ml [Aging] After the addition is completed, add G-301 solution and take 30 minutes to 60 ° C. The temperature rose. Hold at 60 ° C. for another 20 minutes. During this time, the silver potential of the solution was controlled at 6 mV using a 0.5N potassium bromide solution.

(G-301) Alkali-treated inert gelatin (average molecular weight 100,000) 4.478 g H ₂ O 105.4 ml [Growth] After ripening, p was added using 1N potassium hydroxide.
H was adjusted to 5.8. Subsequently, the S-302 solution and the X-302 solution were added by using the double jet method for 41 minutes while accelerating the flow rates (the ratio of the addition flow rates at the end and at the start was about 10 times). After the addition was completed, the G-302 solution was added, and subsequently, 80% equivalents of the S-303 solution and the X-303 solution were added while accelerating the flow rate. During this time, the silver potential of the solution was set to 1.0
It was controlled at 8 mV using a potassium bromide solution of N. The temperature in the reaction vessel was lowered to 40 ° C. over 20 minutes. Thereafter, the silver potential in the reaction vessel was adjusted to -32 mV using a 1.5 N KBr aqueous solution, and Ag having an average particle size of 0.05 µm was used.
After adding 0.058 mol of the I fine grain emulsion, the remaining solution S-303 and solution X-303 were added over 7 minutes.

(S-302) Silver nitrate 20.60 g H ₂ O 92.27 ml (X-302) Potassium bromide 14.43 g H ₂ O 91.77 ml (G-302) Alkali-treated inert gelatin (average molecular weight 100,000) _{) 20.76g H 2 O 170.7ml (S} -303) Silver nitrate _{577.8g H 2 O 834.0g (X-} 303) potassium bromide 396.7g iodide 11.29g H ₂ O 824.2ml said growth After completion, the mixture was subjected to desalting / washing treatment according to a conventional method, and gelatin was added to the mixture, which was dispersed well, and the pH and pAg were adjusted to 5.8 and 8.1, respectively. The emulsion thus obtained was em-30
Set to 0.

(Preparation of Emulsion Em-400 of the Present Invention) [Nucleation] The following gelatin solution B-401 was maintained at 28 ° C., and the number of revolutions was 450 using a mixing and stirring apparatus described in JP-A-62-160128. / Min while stirring
The pH was adjusted to 1.95 with 1N sulfuric acid. Thereafter, the S-401 solution and the X-401 solution were added at a constant flow rate for one minute by using a double jet method to form nuclei.

(B-401) Oxidized gelatin (average molecular weight 100,000) 2.100 g Potassium bromide 0.932 g H ₂ O 839.9 ml (S-401) Silver nitrate 1.624 g H ₂ O 18.747 ml (X- 401) Potassium bromide 1.138 g H ₂ O 18.708 ml [Aging] After the completion of the above addition, G-401 solution was added, and the temperature was raised to 60 ° C. over 30 minutes. Hold at 60 ° C. for another 20 minutes. During this time, the silver potential of the solution was controlled at 6 mV using a 0.5N potassium bromide solution.

(G-401) Alkali-treated inert gelatin (average molecular weight: 100,000) 4.478 g 10 wt% methanol solution of the above (Compound A) 2.312 ml H ₂ O 103.0 ml [Growth] After ripening, 1N Using potassium hydroxide
H was adjusted to 5.8. Subsequently, the S-402 solution and the X-402 solution were added using the double jet method for 41 minutes while accelerating the flow rate (the ratio of the addition flow rate at the end to the start was about 10 times). After completion of the addition, the G-402 solution was added, and subsequently, 80% equivalents of the S-403 solution and the X-403 solution were added while accelerating the flow rate. During this time, the silver potential of the solution was set to 1.0
It was controlled at 8 mV using a potassium bromide solution of N. The temperature in the reaction vessel was lowered to 40 ° C. over 20 minutes. Thereafter, the silver potential in the reaction vessel was adjusted to -32 mV using a 1.5 N KBr aqueous solution, and Ag having an average particle size of 0.05 µm was used.
After adding 0.053 mol equivalent of the I fine grain emulsion, the remaining S-403 solution and X-403 solution were added over 7 minutes.

(S-402) Silver nitrate 20.60 g H ₂ O 92.27 ml (X-402) Potassium bromide 14.43 g H ₂ O 91.77 ml (G-402) Alkali-treated inert gelatin (average molecular weight 100,000) _{) 20.76g H 2 O 170.7ml (S} -403) Silver nitrate _{577.8g H 2 O 834.0ml (X-} 403) potassium bromide 396.7g iodide 11.29g H ₂ O 824.2ml said growth After completion, the mixture was subjected to desalting / washing treatment according to a conventional method, and gelatin was added to the mixture, which was dispersed well, and the pH and pAg were adjusted to 5.8 and 8.1. The emulsion thus obtained was em-40
Set to 0.

(Preparation of Comparative Emulsion Em-500) [Nucleation] The following gelatin solution B-501 was kept at 28 ° C., and the stirring speed was 450 rpm using a mixing stirrer described in JP-A-62-160128. While stirring in minutes,
The pH was adjusted to 1.95 with 1N sulfuric acid. Thereafter, the S-501 solution and the X-501 solution were added at a constant flow rate for one minute by using a double jet method to form nuclei.

(B-501) Oxidized gelatin (average molecular weight 100,000) 2.100 g Potassium bromide 0.932 g 10% by weight methanol solution of (Compound A) 2.312 ml H ₂ O 837.5 ml (S-501) ) nitrate _{1.624g H 2 O 18.747ml (X-} 501) the G-501 was added after potassium bromide 1.138g H ₂ O 18.708ml [aging] the end of the addition, 60 ° C. over a period of 30 minutes The temperature rose. Hold at 60 ° C. for another 20 minutes. During this time, the silver potential of the solution was controlled at 6 mV using a 0.5N potassium bromide solution.

(G-501) Alkali-treated inert gelatin (average molecular weight 100,000) 4.478 g H ₂ O 105.4 ml [Growth] After ripening, p was added using 1N potassium hydroxide.
H was adjusted to 5.8. Subsequently, the S-502 solution and the X-502 solution were added using the double jet method for 41 minutes while accelerating the flow rates (the ratio of the addition flow rates at the end and at the start was about 10 times). After the addition was completed, the G-502 solution was added, and subsequently, 80% equivalents of the S-503 solution and the X-503 solution were added while accelerating the flow rate. During this time, the silver potential of the solution was set to 1.0
It was controlled at 8 mV using a potassium bromide solution of N. The temperature in the reaction vessel was lowered to 40 ° C. over 20 minutes. Thereafter, the silver potential in the reaction vessel was adjusted to -32 mV using a 1.5 N KBr aqueous solution, and Ag having an average particle size of 0.05 µm was used.
After adding 0.058 mol of the I fine grain emulsion, the remaining S-503 solution and X-503 solution were added over 7 minutes.

(S-502) Silver nitrate 20.60 g H ₂ O 92.27 ml (X-502) Potassium bromide 14.43 g H ₂ O 91.77 ml (G-502) Alkali-treated inert gelatin (average molecular weight 100,000) _{) 20.76g H 2 O 170.7ml (S} -503) Silver nitrate _{577.8g H 2 O 834.0g (X-} 503) potassium bromide 396.7g iodide 11.29g H ₂ O 824.2ml said growth After completion, the mixture was subjected to desalting / washing treatment according to a conventional method, and gelatin was added to the mixture, which was dispersed well, and the pH and pAg were adjusted to 5.8 and 8.1. The emulsion thus obtained was em-50
Set to 0.

(Preparation of Comparative Emulsion Em-600) [Nucleation] The following gelatin solution B-601 was kept at 28 ° C., and the stirring speed was 450 rpm using a mixing stirrer described in JP-A-62-160128. While stirring in minutes,
The pH was adjusted to 1.95 with 1N sulfuric acid. Thereafter, the S-601 solution and the X-601 solution were added at a constant flow rate for one minute by using the double jet method to form nuclei.

(B-601) Oxidized gelatin (average molecular weight 100,000) 2.100 g Potassium bromide 0.932 g H ₂ O 839.9 ml (S-601) Silver nitrate 1.624 g H ₂ O 18.747 ml (X- 601) 1.138 g of potassium bromide 18.708 ml of H ₂ O [Aging] After the completion of the addition, the G-601 solution was added, and the temperature was raised to 60 ° C. over 30 minutes. Hold at 60 ° C. for another 20 minutes. During this time, the silver potential of the solution was controlled at 6 mV using a 0.5N potassium bromide solution.

(G-601) Alkali-treated inert gelatin (average molecular weight: 100,000) 4.478 g 10% by weight methanol solution of (Compound A) 2.312 ml H ₂ O 103.0 ml [Growth] After ripening, 1N Using potassium hydroxide
H was adjusted to 5.8. Subsequently, the S-602 solution and the X-602 solution were added using the double jet method in 41 minutes while accelerating the flow rates (the ratio of the addition flow rate at the end to the addition at the start was about 10 times). After the addition was completed, the G-602 solution was added, and subsequently, 80% equivalents of the S-603 solution and the X-603 solution were added while accelerating the flow rate. During this time, the silver potential of the solution was set to 1.0
It was controlled at 8 mV using a potassium bromide solution of N. The temperature in the reaction vessel was lowered to 40 ° C. over 20 minutes. Thereafter, the silver potential in the reaction vessel was adjusted to -32 mV using a 1.5 N KBr aqueous solution, and Ag having an average particle size of 0.05 µm was used.
After adding 0.053 mol of the I fine grain emulsion, the remaining S-603 solution and X-603 solution were added over 7 minutes.

(S-602) Silver nitrate 20.60 g H ₂ O 92.27 ml (X-602) Potassium bromide 14.43 g H ₂ O 91.77 ml (G-602) Alkali-treated inert gelatin (average molecular weight 100,000) _{) 20.76g H 2 O 170.7ml (S} -603) Silver nitrate _{577.8g H 2 O 834.0ml (X-} 603) potassium bromide 396.7g iodide 11.29g H ₂ O 824.2ml said growth After completion, the mixture was subjected to desalting / washing treatment according to a conventional method, and gelatin was added to the mixture, which was dispersed well, and the pH and pAg were adjusted to 5.8 and 8.1. The emulsion thus obtained was em-60
Set to 0.

(Preparation of Comparative Emulsion Em-700) [Nucleation] The following gelatin solution B-701 was kept at 28 ° C., and the mixture was stirred at 450 rpm using a mixing and stirring apparatus described in JP-A-62-160128. While stirring in minutes,
The pH was adjusted to 1.95 with 1N sulfuric acid. Thereafter, the S-701 solution and the X-701 solution were added at a constant flow rate for one minute by using the double jet method to form nuclei.

(B-701) Oxidized gelatin (average molecular weight 100,000) 2.100 g Potassium bromide 0.932 g 10% by weight methanol solution of (Compound A) 1.200 ml H ₂ O 838.7 ml (S-701) ) nitrate _{1.624g H 2 O 18.747ml (X-} 701) the G-701 was added after potassium bromide 1.138g H ₂ O 18.708ml [aging] the end of the addition, 60 ° C. over a period of 30 minutes The temperature rose. Hold at 60 ° C. for another 20 minutes. During this time, the silver potential of the solution was controlled at 6 mV using a 0.5N potassium bromide solution.

(G-701) Alkali-treated inert gelatin (average molecular weight: 100,000) 4.478 g H ₂ O 105.4 ml [Growth] After ripening, p was added using 1N potassium hydroxide.
H was adjusted to 5.8. Subsequently, the S-702 solution and the X-702 solution were added using the double jet method for 38 minutes while accelerating the flow rates (the ratio of the addition flow rate at the end to the addition at the start was about 10 times). After the addition was completed, the G-702 solution was added, and subsequently, 80% equivalents of the S-703 solution and the X-703 solution were added while accelerating the flow rate. During this time, the silver potential of the solution was set to 1.0
It was controlled at 8 mV using a potassium bromide solution of N. The temperature in the reaction vessel was lowered to 40 ° C. over 20 minutes. Thereafter, the silver potential in the reaction vessel was adjusted to −32 mV using a 1.5 N aqueous KBr solution, and Ag having an average particle size of 0.05 μm was used.
After adding 0.058 mol of the I fine grain emulsion, the remaining S-703 solution and X-703 solution were added over 7 minutes.

(S-702) Silver nitrate 20.60 g H ₂ O 92.27 ml (X-702) Potassium bromide 14.43 g H ₂ O 91.77 ml (G-702) Alkali-treated inert gelatin (average molecular weight 100,000) _{) 20.76g H 2 O 170.7ml (S} -703) Silver nitrate _{577.8g H 2 O 834.0ml (X-} 703) potassium bromide 396.7g iodide 11.29g H ₂ O 824.2ml said growth After completion, the mixture was subjected to desalting / washing treatment according to a conventional method, and gelatin was added to the mixture, which was dispersed well, and the pH and pAg were adjusted to 5.8 and 8.1, respectively. The emulsion thus obtained was em-70
Set to 0.

(Preparation of Inventive Example Emulsion Em-800) [Nucleation] The following gelatin solution B-801 was kept at 28 ° C., and the number of rotations was 450 using a mixing and stirring apparatus described in JP-A-62-160128. / Min while stirring
The pH was adjusted to 1.95 with 1N sulfuric acid. Thereafter, the S-801 solution and the X-801 solution were added at a constant flow rate for one minute by using a double jet method to form nuclei.

[0102] (B-801) oxidized gelatin (average molecular weight 100,000) 2.100G Potassium bromide _{0.932g H 2 O 839.9ml (S-} 801) silver nitrate 1.624g H ₂ O 18.747ml (X- 801) 1.138 g of potassium bromide 18.708 ml of H ₂ O [Aging] After the completion of the above addition, the G-801 solution was added, and the temperature was raised to 60 ° C. over 30 minutes. Hold at 60 ° C. for another 20 minutes. During this time, the silver potential of the solution was controlled at 6 mV using a 0.5N potassium bromide solution.

(G-801) Alkali-treated inert gelatin (average molecular weight: 100,000) 4.478 g 10% by weight methanol solution of (Compound A) 1.200 ml H ₂ O 104.2 ml [Growth] After ripening, 1N Using potassium hydroxide
H was adjusted to 5.8. Subsequently, the S-802 solution and the X-802 solution were added using the double jet method for 38 minutes while accelerating the flow rates (the ratio of the addition flow rates at the end and at the start was about 10 times). After the addition was completed, the G-802 solution was added, and subsequently, 80% equivalents of the S-803 solution and the X-803 solution were added while accelerating the flow rate. During this time, the silver potential of the solution was set to 1.0
It was controlled at 8 mV using a potassium bromide solution of N. The temperature in the reaction vessel was lowered to 40 ° C. over 20 minutes. Thereafter, the silver potential in the reaction vessel was adjusted to -32 mV using a 1.5 N KBr aqueous solution, and Ag having an average particle size of 0.05 µm was used.
After adding 0.053 mol of the I fine grain emulsion, the remaining S-803 solution and X-803 solution were added over 7 minutes.

(S-802) Silver nitrate 20.60 g H ₂ O 92.27 ml (X-802) Potassium bromide 14.43 g H ₂ O 91.77 ml (G-802) Alkali-treated inert gelatin (average molecular weight 100,000) _{) 20.76g H 2 O 170.7ml (S} -803) Silver nitrate _{577.8g H 2 O 834.0ml (X-} 803) potassium bromide 396.7g iodide 11.29g H ₂ O 824.2ml said growth After completion, the mixture was subjected to desalting / washing treatment according to a conventional method, and gelatin was added to the mixture, which was dispersed well, and the pH and pAg were adjusted to 5.8 and 8.1, respectively. The emulsion thus obtained was em-80
Set to 0.

(Preparation of Emulsion Em-900 of the Present Invention) [Nucleation] The following gelatin solution B-901 was maintained at 28 ° C., and the number of revolutions was 450 using a mixing and stirring apparatus described in JP-A-62-160128. / Min while stirring
The pH was adjusted to 1.95 with 1N sulfuric acid. Thereafter, the S-901 solution and the X-901 solution were added at a constant flow rate for one minute by using a double jet method to form nuclei.

(B-901) Oxidized gelatin (average molecular weight 100,000) 2.100 g Potassium bromide 0.932 g H ₂ O 839.9 ml (S-901) Silver nitrate 1.624 g H ₂ O 18.747 ml (X- 901) Potassium bromide 1.138 g H ₂ O 18.708 ml [Aging] After completion of the above addition, G-901 solution was added, and the temperature was raised to 60 ° C. over 30 minutes. Hold at 60 ° C. for another 20 minutes. During this time, the silver potential of the solution was controlled at 6 mV using a 0.5N potassium bromide solution.

(G-901) Alkali-treated inert gelatin (average molecular weight 100,000) 4.478 g 10% by weight methanol solution of (Compound A) 0.600 ml H ₂ O 104.8 ml [Growth] After ripening, 1N Using potassium hydroxide
H was adjusted to 5.8. Subsequently, the S-902 solution and the X-902 solution were added using the double jet method for 38 minutes while accelerating the flow rates (the ratio of the addition flow rate at the end to the addition at the start was about 10 times). After the completion of the addition, the G-902 solution was added, and subsequently, 80% equivalents of the S-903 solution and the X-903 solution were added while accelerating the flow rate. During this time, the silver potential of the solution was set to 1.0
It was controlled at 8 mV using a potassium bromide solution of N. The temperature in the reaction vessel was lowered to 40 ° C. over 20 minutes. Thereafter, the silver potential in the reaction vessel was adjusted to −32 mV using a 1.5 N aqueous KBr solution, and Ag having an average particle size of 0.05 μm was used.
After adding 0.053 mol of the I fine grain emulsion, the remaining S-903 solution and X-903 solution were added over 7 minutes.

When the characteristics of Em-900 were examined, the average silver iodide content of the surface phase was 7.2 mol%, and the area ratio of silver halide grains having 10 or more dislocation lines was determined by the ratio of the total projected area to the total projected area. It was found that the coefficient of variation of the silver iodide content was 91% and the variation coefficient of the silver iodide content was 14%.

(S-902) Silver nitrate 20.60 g H ₂ O 92.27 ml (X-902) Potassium bromide 14.43 g H ₂ O 91.77 ml (G-902) Alkali-treated inert gelatin (average molecular weight 100,000) 20.76 g 10% by weight methanol solution of (Compound A) 0.60 ml H ₂ O 170.1 ml (S-903) silver nitrate 577.8 g H ₂ O 834.0 ml (X-903) potassium bromide 396.7 g Potassium iodide 11.29 g H ₂ O 824.2 ml After completion of the above growth, desalting and washing were carried out according to a conventional method, gelatin was added to the mixture, and the mixture was dispersed well. The pH was adjusted to 5.8, and the pAg was adjusted to 8.1. The emulsion thus obtained was em-90
Set to 0.

Table 5 shows the characteristics of the silver halide photographic emulsions prepared as described above.

[0111]

[Table 5]

Incidentally, the area ratio of dislocation line particles in the table is as follows.
(Sum of projected areas of silver halide grains having dislocation lines / total projected area of silver halide grains) × 100 (%).

[Photosensitive material sample No. 100-No. 90
0] The above silver halide photographic emulsions Em-100 to
While maintaining Em-900 at 52 ° C., the following sensitizing dye S
SD-1, SSD-2 and SSD-3 were added. After aging for 20 minutes, sodium thiosulfate was added, and chloroauric acid and potassium thiocyanate were further added. After ripening each silver halide photographic emulsion to obtain optimum sensitivity and fog, 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1,3,3a, 7
-Stabilized by adding tetraazaindene. The amount of sensitizing dye, sensitizer, and stabilizer added to each silver halide photographic emulsion and the ripening time were set so that the sensitivity and fogging relationship at the time of 1/200 second exposure were optimized.

Em-100 to Em-9 after sensitization
The following coupler MCP was added to each silver halide photographic emulsion
-1 is dissolved in ethyl acetate, tricresyl phosphate, and a dispersion obtained by emulsifying and dispersing in an aqueous solution containing gelatin, a spreading agent, and a general photographic additive such as a hardening agent are added to prepare a coating solution. It is coated on an undercoated cellulose triacetate film support according to a conventional method, dried and dried.
100-No. 900 were produced.

[0115]

Embedded image

Immediately after the preparation of these samples,
Wedge exposure was performed through a Toshiba glass filter (Y-48) using a light source having a color temperature of 5400K, and development was performed according to the following processing steps. In order to evaluate the pressure resistance, each sample was held for 24 hours in an atmosphere at 23 ° C. and a relative humidity of 55%, and then subjected to a tip test using a scratch strength tester (manufactured by Shinto Kagaku) under the same conditions. Radius of curvature of 0.025
The same process was performed by scanning the surface of the sample at a constant speed while applying a load of 5 g to the needle having a diameter of 5 mm. Further, in order to evaluate the storage stability, each sample was subjected to a forced deterioration test (40 ° C., relative humidity 8).
After storage for 14 days in an environment of 0%), the same treatment was performed.

(Processing step) Processing step Processing time Processing temperature Replenishment amount Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2.0 ° C. 830 ml Stable 1 minute 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C. The replenishment amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developing solution and color developing replenishing solution Developer replenishing solution Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium bicarbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g iodide Potassium 1.2 mg-Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g-4-Amino-3-methyl-N-ethyl-N-([beta] -hydroxylethyl) aniline sulfate 4.5 g 6.3 g Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Water was added to make 1 liter. The color developing solution was adjusted to pH 10.06 using potassium hydroxide or 20% sulfuric acid, and the replenisher was adjusted to pH 1.
Adjust to 0.18.

Bleach and bleach replenisher Bleach replenisher replenisher water 700 ml 700 ml 1,3-diaminopropanetetraacetic acid ammonium iron (III) 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g water And adjust the pH of the bleaching solution to 4.4 and the pH of the replenishing solution to 4.0 using ammonia water or glacial acetic acid.

Fixer Solution and Fixer Replenisher Fixer Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Aqueous solution using ammonia water or glacial acetic acid, pH 6.2
Then, the pH of the replenisher is adjusted to 6.5, and water is added to make 1 l.

Stabilizing solution and stabilizing replenishing solution water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylol urea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (UCC 0.1 g ammonia water 0.5 ml After adding water to make 1 l, the pH is adjusted to 8.5 using ammonia water or 50% sulfuric acid.

The sensitivity and fog of each of the obtained samples were measured using green light. The sensitivity and fog of each sample after the forced deterioration test were also measured, and compared with each performance immediately after the sample was prepared. The measuring method and conditions are shown below.

The relative sensitivity was determined by calculating the reciprocal of the exposure amount that gives the minimum density (Dmin) +0.2 in each sample. The relative value is defined as a relative value with the sensitivity of 100 being 100 (the larger the value, the higher the sensitivity).

The relative fog was measured by measuring the density (= Dmin) of the unexposed portion of each sample. 100 D
The relative value was set to a minimum value of 100 (the smaller the value, the lower the fog).

The fog increase due to the pressure was measured by measuring the amount of increase in the density of the unexposed portion where the load was applied.
o. A relative value (ΔDp
1) (the smaller the value, the smaller the fog increase due to the pressure being applied).

The decrease in sensitivity due to the pressure being applied is (Dmax−Dm
in) / 2), the amount of decrease in the density of the portion where the load was applied was measured, and the sample No. 100 changes in density
The relative value (ΔDp2) was set to 00 (the smaller the value, the smaller the decrease in sensitivity due to the pressure being applied).

The Δ sensitivity was represented by the ratio of the sensitivity immediately after sample preparation to the sensitivity after forced degradation test (Δ sensitivity = sensitivity after forced degradation test / sensitivity immediately after sample fabrication) × 100 in each sample (this value). Is closer to 100 means that the change in sensitivity due to storage is smaller).

The Δ fog of each sample was represented by the ratio of Dmin immediately after sample preparation to Dmin after forced deterioration test (Δfog = Dmin after forced deterioration test / Dmin immediately after sample preparation) × 100 (this value). Is closer to 100 means that fog change due to storage is smaller).

Table 6 shows the results obtained for each sample.

[0131]

[Table 6]

From the characteristics of each silver halide photographic emulsion shown in Table 5 and the evaluation results shown in Table 6, the following can be understood.

The sample No. By comparing 100 to 300, 1) by introducing dislocation lines into tabular silver halide grains, it is possible to achieve high sensitivity and improvement of fog increase due to pressure, but at the same time, decrease sensitivity significantly due to pressure. 2) Sample No. By comparing 100-400,
High sensitivity, low fog and improved storage stability can be achieved by setting both the coefficient of variation of the particle size and the thickness of the tabular silver halide grains to 20.0% or less. By setting the variation coefficient of the thickness of the tabular silver halide grains of 300 and 400 to 20.0% or less, the desensitization of silver halide grains having dislocation lines due to pressure can be greatly improved.

The sample No. By comparing 300 to 600, 4) In the tabular silver halide grains having an average aspect ratio of less than 3.0, the improvement effects of the above 2) and 3) are not remarkable.

Accordingly, it is an object of the present invention to provide a silver halide photographic emulsion and a silver halide photographic light-sensitive material which are excellent in sensitivity and fog, and further have improved storage stability and pressure resistance. This is achieved by the silver halide emulsion of the present invention, which is a tabular silver halide grain having a dislocation line of 0 or more, and both of the variation coefficients of the grain size and the thickness of the silver halide grain are 20.0% or less. You can see that

The sample No. 300-400, and N
o. By comparing 700 to 900, the problem of the present invention is that the silver halide grains of the present invention have an average aspect ratio of 6.0 or more and a variation coefficient of the thickness of the grains of 1 or more.
It can be seen that it is more remarkably achieved when the content is 5.0% or less.

[0137]

As demonstrated in the Examples, the silver halide photographic emulsion and the silver halide photographic light-sensitive material of the present invention are excellent in fog and sensitivity, and have little increase in fog and decrease in sensitivity during storage. It has an excellent effect of improved pressure resistance.

Claims (4)

[Claims] 1. A silver halide photographic emulsion containing silver halide grains, wherein the silver halide grains have an average aspect ratio of at least 3.0, substantially have dislocation lines, and have a coefficient of variation in grain size. Is 20.0% or less, and the coefficient of variation of thickness is 20.0% or less. 2. The silver halide photographic emulsion according to claim 1, wherein the average aspect ratio of the silver halide grains is 6.0 or more. 3. The variation coefficient of the thickness of silver halide grains is 1
3. The silver halide photographic emulsion according to claim 1, wherein the content is not more than 5.0%. 4. A silver halide photographic emulsion according to claim 1, which is contained in at least one silver halide photographic emulsion layer provided on a support. Silver halide photographic light-sensitive material.