JP2001100347A - Silver halide emulsion and silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide emulsion high in sensitivity and superior in graininess and pressure characteristics, fog resistance, reciprocity failure characteristics, performance retaining ability against lapse of time, latent image stability, and resistance to fluctuation of a latent image independent of temperature and humidity and to provide the silver halide color photographic sensitive material using this emulsion. SOLUTION: The silver halide emulsion comprises the silver halide grains and a dispersion medium and it is characterized by having the variation coefficient of the particle riges of silver halide grains contained in this emulsion being <=20%, and containing flat silver halide grains having an aspect ratio of >=5, in an amount of >=50% of the projection areas of the total silver halide grains and having a process for forming grains in an reducing sensitizing atmosphere during formation of the flat silver halide grains, and having dislocation lines in the central regions of the principal planes and the circumferential regions in an amount of >=30 number % of the flat silver halide grains, and having >=10 dislocation lines in the above circumferential region per each flat grain, and the chemically modified gelatin among the gelatin added in the emulsion forming process in an amount of >=15 to; <100 weight % of the total gelatin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide emulsion useful in the field of photography and a silver halide color photographic light-sensitive material using the same. More specifically, a silver halide color photographic material having high sensitivity, granularity, pressure characteristics, low fog, reciprocity failure characteristics and excellent storage stability over time, latent image storage, and temperature and humidity dependence of latent image fluctuation. About.

[0002]

2. Description of the Related Art In recent years, compact cameras and auto-focus cameras 1
With the spread of eye reflex cameras and films with lenses, there is a strong demand for the development of silver halide color photographic materials having high sensitivity and excellent image quality. Therefore, demands for improved performance of photographic silver halide emulsions are becoming more severe, and higher levels of demands are made on photographic performance such as high sensitivity, excellent graininess, and excellent sharpness.

In response to such demands, for example, US Pat. Nos. 4,434,226, 4,439,520, 4,414,310, 4,433,048, and 4,414, No. 306, No. 4,459, 353, etc. disclose techniques using tabular silver halide grains (hereinafter, also simply referred to as "tabular grains"). There are known advantages such as improvement in sensitivity, improvement in sensitivity / granularity, improvement in sharpness due to specific optical properties of tabular grains, and improvement in covering power. However, it is not enough to meet recent high-level demands, and further improvement in performance is desired.

[0004] In connection with the trend toward higher sensitivity and higher image quality, demands for improvement in pressure characteristics of silver halide photographic materials have been increasing more than ever. Although it has been considered to improve the pressure characteristics by various means, a technique for improving the stress resistance of silver halide grains itself is better than a technique using an additive such as adding a plasticizer. The view that it is practically preferable and that the effect is large is promising. In response to these demands, emulsions comprising core / shell type silver halide grains having a silver iodobromide layer having a high silver iodide content have been actively studied. In particular, silver iodobromide emulsions containing core / shell type grains having a high silver iodide phase of 10 mol% or more inside grains have attracted much attention, for example, as emulsions for color negative films.

As a method for increasing the sensitivity of a silver halide emulsion, a technique of introducing dislocation lines into tabular silver halide grains is disclosed in US Pat. No. 4,956,269. 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-3-189642 discloses that tabular silver halide grains having an aspect ratio of 2 or more and having 10 or more dislocation lines in a fringe portion, and the size distribution of the tabular silver halide grains are simple. Dispersed silver halide emulsions are disclosed. However, this technique does not improve the significant desensitization caused by the pressure caused by introducing dislocation lines.

Techniques for improving pressure characteristics with core / shell type particles include, for example, JP-A-59-99433 and JP-A-59-99433.
The techniques disclosed in Japanese Patent Nos. 0-35726 and 60-147727 are known. Also, JP-A-63-220238,
Japanese Patent Application Laid-Open No. Hei 1-2201649 discloses a technique for improving sensitivity, graininess, pressure characteristics, exposure illuminance and the like by introducing dislocations into silver halide grains. Japanese Patent Application Laid-Open No. 6-235988 discloses a technique of improving pressure resistance by using monodisperse tabular grains of a multi-structure type having a high iodine layer in an intermediate shell.

Furthermore, there are various inefficiency factors relating to the sensitivity of the emulsion, but from the viewpoint of preventing recombination of free electrons and holes, which is one factor, it is effective to perform reduction sensitization. Has been known for a long time. U.S. Pat. Nos. 2,487,850 and 2,512,925 and British Patent 789,823 disclose reduction sensitization techniques.

However, for example, Journal of Imaging Science (Journal of Imaging Science)
ging Science, Vol. 29, p. 233 (198
As reported in 5), the effect of reduction sensitization is less than that of hydrogen sensitization in which a light-sensitive material is processed in a hydrogen atmosphere. It is believed that further improvements would be possible.

Attempts have also been made to simultaneously improve the sensitivity by reduction sensitization and other performances such as fog, storage stability over time, and latent image storage stability. JP-A-1-196136 and the like disclose that the sensitivity / fogging ratio can be improved by using a reduction sensitization and a thiosulfonic acid compound in combination. JP-A-8-15798 discloses that sensitivity, fog, graininess, and latent image storability can be improved by combining a silver halide emulsion having excellent monodispersibility with reduction sensitization. In JP-A-1-127633, the design of the halide composition of particles is devised, and sulfur, selenium,
It is disclosed that the incorporation of tellurium ions in the grains, and in combination with reduction sensitization, can improve the sensitivity / fogging ratio, pressure and storage characteristics. As described above, the effect of reduction sensitization can be further improved and other characteristics can be synergistically improved by the particle configuration design technique combining the reduction sensitization and other techniques.

[0010] The mechanism of the effect of reduction sensitization has not yet been fully elucidated. Conventionally, Photographic Correspondents (Photograph)
hishe Korrespondenz, Vol. 1, p. 20 (1957) and Photographic Science and Engineering (PhotographicS).
science and Engineering) 19
As reported in Vol. 49, p. 1975, the fine silver nuclei formed by reduction sensitization, ie, reduction sensitization nuclei,
It has been thought that by capturing holes generated by the light absorption of silver halide and emitting electrons, it contributes to higher sensitivity. However, Photographic Science and Engineering (Photographi)
c Science and Engineerine
g) According to Vol. 16, p. 35 (1971) and Vol. 23, p. 113 (1979), the reduction sensitization nucleus has the property of trapping not only holes but also electrons, and has only a hole trapping mechanism. Cannot explain the behavior of reduction sensitization nuclei. That is, the behavior of the reduction sensitization nucleus has not been sufficiently clarified. Furthermore, the behavior of the reduction sensitization nucleus under storage conditions such as high temperature and high humidity, for example, whether or not it causes a reaction such as decomposition or aggregation, is still more unknown.

Further, as a technique for controlling charge carriers (carriers) in silver halide grains such as free electrons and holes, a metal doping technique is known. For example, it has been reported by Leubner that the iridium complex doped with silver halide exhibits an electron trapping property (The Journal of Photo.
graphic Science Vol. 31,93
(1983)). Further, for example, JP-A-3-15040 discloses an iridium ion-containing emulsion in which iridium ions are not present on the grain surface and a method for producing the same. In addition, for example, JP-A-6-175251 discloses that in-plane epitaxy-type grains to which an iridium compound is added during the silver halide grain production step achieve both sensitivity at 1/100 second exposure and reciprocity failure characteristics. Techniques are disclosed. Further, for example, JP-A-7-104406 discloses a technique in which silver halide fine particles are added in the presence of an iridium compound to improve reciprocity failure characteristics.

Japanese Patent Application Laid-Open No. 63-106746 discloses that
Tabular silver halide grains having a substantially layered structure in a direction parallel to two opposite main planes are disclosed in
No. 279237 has a layered structure separated by a plane substantially parallel to two opposite main planes, and the average silver iodide content of the outermost layer is the average silver iodide of the whole silver halide grains. It describes a technique using tabular silver halide grains at least 1 mol% higher than the content.

Japanese Patent Application Laid-Open No. 3-121445 discloses a silver halide grain comprising an interface layer having parallel twin planes and regions having different iodine contents from each other.
No. 305343 discloses a tabular silver halide grain having a development start point near the vertex.
Silver halide grains having a (0) plane and a (111) plane are disclosed.

However, these conventional techniques have limitations in achieving both high sensitivity and high image quality, and are insufficient to satisfy recent demands on photosensitive materials. Was rare.

In order to improve the photographic performance, more effective chemical sensitization and color sensitization are applied to silver halide grains. There is a need to develop technologies that allow for composition control, and previous studies in the industry have not adequately responded to this need.

[0016]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide high sensitivity and excellent granularity, pressure characteristics, low fogging, reciprocity failure characteristics and storage performance over time, storage stability of latent images, An object of the present invention is to provide a silver halide emulsion excellent in the temperature and humidity dependence of a latent image variation and a silver halide color photographic light-sensitive material using the same.

[0017]

The above object of the present invention is attained by the following constitutions.

(1) A silver halide emulsion containing silver halide grains and a dispersion medium, wherein the coefficient of variation of the grain size of all silver halide grains contained in the silver halide emulsion is 20% or less, 50% or more of the projected area of the silver halide grain is
Tabular silver halide grains having an aspect ratio of 5 or more;
A step of forming grains in a reduction sensitizing atmosphere during the formation of the tabular silver halide grains, and wherein at least 30% (number ratio) of the tabular silver halide grains is in the central region and the peripheral region of the main plane. A dislocation line, and the dislocation line in the outer peripheral region is 1
10 or more per grain, and chemically modified gelatin among the gelatin added during the silver halide emulsion formation step is 15% by weight to 100% by weight of the total amount of gelatin added.
A silver halide emulsion characterized by being added in an amount less than 1.

(2) A silver halide emulsion containing silver halide grains and a dispersion medium, wherein the coefficient of variation of the grain size of all silver halide grains contained in the silver halide emulsion is 20% or less. 50% or more of the projected area of the silver halide grain is
Tabular silver halide grains having an aspect ratio of 5 or more;
A step of forming grains in a reduction sensitizing atmosphere during the formation of the tabular silver halide grains, and wherein at least 30% (number ratio) of the tabular silver halide grains is in the central region and the peripheral region of the main plane. A dislocation line, and the dislocation line in the outer peripheral region is 1
10 or more per grain, and at least one or more polyvalent metal compounds are contained in the outer periphery of the tabular silver halide grains. A silver halide emulsion, wherein the modified gelatin is added in an amount of 15% by weight or more and less than 100% by weight of the total amount of gelatin.

(3) A silver halide emulsion containing silver halide grains and a dispersion medium, wherein the variation coefficient of the particle size of all silver halide grains contained in the silver halide emulsion is 20% or less, 50% or more of the projected area of the silver halide grain is
Tabular silver halide grains having an aspect ratio of 5 or more;
A step of forming grains under a reduction-sensitized atmosphere during the formation of the tabular silver halide grains, and further forming a grain by appropriately extracting an aqueous solution containing a salt from a reaction solution by ultrafiltration; 30% or more (number ratio) of the silver halide grains have dislocation lines in the central region and the peripheral region of the main plane, and there are 10 or more dislocation lines in the peripheral region per grain. A silver halide emulsion wherein chemically modified gelatin is added in an amount of 15% by weight or more and less than 100% by weight of the total amount of gelatin added during the emulsion formation step.

(4) A silver halide emulsion containing silver halide grains and a dispersion medium, wherein the variation coefficient of the particle diameter of all silver halide grains contained in the silver halide emulsion is 20% or less. 50% or more of the projected area of the silver halide grain is
Tabular silver halide grains having an aspect ratio of 5 or more;
A step of forming grains in a reduction sensitizing atmosphere during the formation of the tabular silver halide grains, and wherein at least 30% (number ratio) of the tabular silver halide grains is in the central region and the peripheral region of the main plane. A dislocation line, and the dislocation line in the outer peripheral region is 1
When the average silver iodide content of the outermost layer of the tabular silver halide grains is A mol% in the main plane portion and B mol% in the side surface portions, A> B is present in an amount of 10 or more per grain. Of the gelatin added during the silver halide emulsion forming step, the chemically modified gelatin accounts for 15% by weight or more of the total amount of gelatin added;
A silver halide emulsion characterized by being added in an amount of less than 00% by weight.

(5) A silver halide emulsion containing silver halide grains and a dispersion medium, wherein all silver halide grains contained in the silver halide emulsion have a variation coefficient of particle size of 20% or less, 50% or more of the projected area of the silver halide grain is
Tabular silver halide grains having an aspect ratio of 5 or more;
A step of forming grains under a reduction-sensitized atmosphere during the formation of the tabular silver halide grains, and further, performing a grain formation while appropriately extracting an aqueous solution containing a salt from the reaction solution by ultrafiltration; 30% or more (number ratio) of the silver halide grains have dislocation lines in the central region and the peripheral region of the main plane, and there are 10 or more dislocation lines in the peripheral region per grain. The outer periphery of the silver grains contains at least one or more polyvalent metal compounds, and the average silver iodide content of the outermost layer of the tabular silver halide grains is A mol% in the main plane portion and B in the side surface portion. When expressed as mol%, A
> B, wherein chemically modified gelatin is added in an amount of 15% by weight or more and less than 100% by weight of the total amount of gelatin added in the silver halide emulsion forming step.

(6) In a silver halide color photographic light-sensitive material having a silver halide emulsion layer on a support, the silver halide emulsion contained in at least one of the emulsion layers is as defined in the above (1) to (5). A silver halide color photographic light-sensitive material, which is the silver halide emulsion according to any one of the above.

Hereinafter, each invention of the present application will be described in detail.

The silver halide grains contained in the silver halide emulsion of the present invention are tabular grains. Tabular grains are crystallographically classified as twins.

A twin is a silver halide crystal having one or more twin planes in one grain, and a classification of the twin is based on a report by Klein and Moiser in Photographi Corspondents.
(Korrespondenz) Vol. 99, p100, and Vol. 100, p57.

The tabular grains in the present invention have two twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope.

The thickness of the tabular grains of the present invention can be obtained by observing a section using a transmission electron microscope as described above, similarly calculating the thickness of each grain, and performing averaging. Tabular grain thickness is 0.05 μm to 1.5 μm
m is preferable, and 0.07 μm to 0.50 is more preferable.
μm.

The tabular grains of the present invention comprise 50% of the total projected area.
The aspect ratio (particle diameter / grain thickness) is 5 or more, preferably 60% or more of the total projected area is 7 or more, more preferably 70% or more of the total projected area.
% Or more has an aspect ratio of 9 or more.

To determine the aspect ratio, the diameter and thickness of the silver halide grains are first determined by the following method. A latex ball having a known particle size as an internal standard and a sample coated such that the main plane was oriented parallel to the support were prepared on the support, and shadowing was performed by a carbon deposition method from a certain direction. Thereafter, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area diameter and thickness of each silver halide grain are determined using an image processing device or the like. In this case, the thickness of the silver halide grains can be calculated from the internal standard and the length of the shadow of the silver halide grains.

The grain size of the tabular grains in the present invention is represented by the equivalent circle diameter of the projected area of the silver halide grains (the diameter of a circle having the same projected area as the silver halide grains).
0.1 to 5.0 μm is preferable, and more preferably 0.5 to 5.0 μm.
〜3.0 μm.

The particle diameter can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter on the print or the area at the time of projection (measurement). The number of particles shall be 1000 or more indiscriminately).

Here, the average particle diameter r is defined as the particle diameter ri when the product ni × ri ³ of the frequency ni and ri ³ of the particles having the particle diameter ri is maximum (three significant figures, minimum Digits are rounded off to the nearest 5).

The silver halide emulsion of the present invention comprises monodispersed tabular silver halide grains. Here, as the monodispersed silver halide emulsion, the one in which the weight of silver halide contained in a range of ± 20% of the particle size around the average particle size r is 60% or more of the total weight of silver halide particles. It is preferably at least 70%, more preferably at least 80%.

The highly monodispersed emulsion of the present invention has a distribution of not more than 20% as defined by (standard deviation / average particle size) × 100 = coefficient of variation (%) of particle size. Preferably it is 16% or less. Here, the average particle diameter and the standard deviation are determined from the particle diameter ri defined above.

The average silver iodide content of the tabular grains of the present invention is 1
It is at least 1 mol%, preferably from 1 to 20 mol%, more preferably from 2 to 10 mol%.

The tabular grains of the present invention are emulsions mainly containing silver iodobromide as described above, but may contain other compositions of silver halide such as silver chloride as long as the effects of the present invention are not impaired. Can be.

The distribution state of silver iodide in the silver halide grains can be detected by various physical measurement methods, for example, as described in the Abstracts of the Annual Meeting of the Photographic Society of Japan, 1981. It can be measured by low temperature luminescence measurement, EPMA method, or X-ray diffraction method.

In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by an EPMA method (Electron Probe Micro Ana).
(lyzer method). According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, and element analysis of a very small portion can be performed by X-ray analysis by electron beam excitation for irradiating an electron beam. By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the halogen composition of each grain can be determined. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content is determined from the average thereof.

The tabular grains in the present invention preferably have a more uniform silver iodide content between grains. EP
When the distribution of silver iodide content between grains is measured by the MA method, the relative standard deviation is preferably 30% or less, more preferably 20% or less.

In the silver halide grains contained in the silver halide emulsion of the present invention, core / shell type grains can also be preferably used. The core / shell type particles are particles composed of a core and a shell covering the core, and the shell is formed by one or more layers. The silver iodide content of the core and the shell are preferably different from each other.

In the present invention, the outermost layer of the silver halide grains refers to a silver halide phase including the surface of the silver halide grains and extending to a depth of 50 ° from the surface of the silver halide grains.

In the present invention, the average silver iodide content in the outermost layer of the silver halide crystal is defined as the silver iodide content measured at five or more points at equal intervals in the outermost layer of the silver halide grains. Means the average.

In the present invention, the average silver iodide content of the outermost layer of each of the main plane portion and side surface portion of the silver halide grain is measured by the following method.

The tabular silver halide grains in the silver halide emulsion are decomposed by gelatin using a protease, taken out, embedded in methacrylic resin, and continuously cut into sections of about 500 mm in thickness with a diamond cutter. Of these sections, those having a tomographic plane perpendicular to the two parallel principal planes of the tabular silver halide grains appear on the tomographic plane, including the principal plane surface and parallel to the principal plane surface. From 50 ° to a depth of 50 ° is called a main plane portion. Further, a portion other than the main plane portion, which is the outermost layer of the silver halide crystal, is referred to as a side portion. The silver iodide content of the main plane portion and the side surface portion is measured by a point analysis using the EPMA method well known in the art to narrow the spot diameter to 50 ° or less, preferably 20 ° or less.

In the silver halide emulsion of the present invention according to claims 4 and 5, the average silver iodide content of the outermost layer of the silver halide grains is A mol% in the main plane portion and B mol% in the side surface portion. When tabular silver halide grains in which A> B are 50%
It is characterized by the above (number). The relationship between A and B is preferably A / B> 1.3, and A / B>
1.5 is more preferable, and A / B> 2.0 is most preferable. Also, in the present invention, 1
Preferably, mol% <A <20 mol%, and more preferably, 3 mol% <A <15 mol%.

The dislocation lines of the 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 emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for an electron microscope so as to prevent damage by electron beams (such as printout). Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particles, the more difficult it is for an electron beam to pass through, so that a clearer observation can be obtained by using a high-pressure electron microscope. From the grain photograph obtained by such a method, the position and number of dislocation lines in each grain can be determined. The tabular grains of the present invention have dislocation lines in both the central region and the peripheral region of the main plane.

The central region of the main plane of the tabular grains as used herein is defined as the radius of a circle having an area equal to the main plane of the tabular grains of 8
A region having a radius of 0% and a thickness of a tabular grain in a circular portion when the center is shared. The center of the principal plane refers to the midpoint of the distance between the intersection of the circle and the contact point when a perpendicular line is drawn from the contact point of the tangent to the circle when a circle having the same area as the principal plane of the tabular grain is drawn. Further, the peripheral region of the tabular grains refers to a region having an area corresponding to an annular region outside the central region, existing around the tabular grains, and having a thickness of the tabular grains.

The number of dislocation lines present in one particle is measured as follows. A series of particle photographs with different inclination angles with respect to the incident electrons are taken for each particle to confirm the existence of dislocation lines. At this time, if the number of dislocation lines can be counted, the number of dislocation lines is counted. For example, when dislocation lines exist densely or dislocation lines cross each other,
When the number of dislocation lines per particle cannot be counted, it is counted that there are many dislocation lines.

Many of the dislocation lines existing in the central region of the main plane of the tabular grains of the present invention form a so-called dislocation network, and the number thereof may not be clearly counted.

On the other hand, dislocation lines present in the outer peripheral region of the tabular grains of the present invention are observed as lines extending radially from the center of the grains toward the sides, but often meander.

In the tabular grains of the present invention, at least 30% of the number ratio has dislocation lines in both the central region and the peripheral region of the main plane, and the number of dislocation lines in the peripheral region is 1 per particle.
The tabular grains having 0 or more but 50% or more (number ratio) have dislocation lines in both the central region and the peripheral region of the main plane, and the number of dislocation lines in the peripheral region is 1 grain. It is preferable that the number of tabular grains is 20 or more, and 70% or more (number ratio) of tabular grains has dislocation lines in both the central region and the peripheral region of the main plane and the number of dislocation lines in the peripheral region is one It is more preferred to have 30 or more pieces.

As a method for introducing dislocation lines into silver halide grains, for example, a method in which an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution are added by a double jet, or a method including silver iodide. A method of adding a fine grain emulsion,
A method of adding only a solution containing iodide ions;
Known methods such as a method using an iodide ion releasing agent as described in No. 11781 can be used to form dislocations originating dislocation lines at desired positions. Among these methods, a method of adding a fine grain emulsion containing silver iodide and a method of using an iodide ion releasing agent are particularly preferable.

When an iodine ion releasing agent is used, sodium p-iodoacetamidobenzenesulfonate,
Iodoethanol, 2-iodoacetamide and the like can be preferably used.

The tabular grains of the present invention may be either grains whose latent image is mainly formed on the surface or grains mainly formed inside the grain.

The tabular grains of the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium. Here, the aqueous solution containing a dispersion medium refers to an aqueous solution in which a protective colloid is formed in an aqueous solution by gelatin or another substance capable of forming a hydrophilic colloid (a substance capable of serving as a binder), preferably a colloidal protective substance. It is an aqueous solution containing gelatin.

In the practice of the present invention, when gelatin is used as the above protective colloid, the gelatin may be either lime-treated or acid-treated. The details of the method for producing gelatin are described in Arthur Guice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

Examples of hydrophilic colloids other than gelatin that can be used as protective colloids include, for example, gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
There are various kinds of synthetic hydrophilic polymer substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole.

In the case of gelatin, it is preferable to use those having a jelly strength of 200 or more in the puggy method.

In the present invention, the tabular grains are formed during the step of forming and / or growing the grains, including cadmium salts, zinc salts, lead salts, thallium salts, iron salts, rhodium salts, iridium salts, indium salts (including complex salts). ) Can be used to add metal ions to the inside of the particles and / or the surface of the particles to contain these metal elements.

In the present invention, it is essential that the tabular grains have been subjected to reduction sensitization (hereinafter simply referred to as reduction sensitization) during grain formation.

Reduction sensitization is carried out by adding a reducing agent to a silver halide emulsion or a mixed solution for growing grains. Alternatively, a silver halide emulsion or a mixed solution for grain growth is prepared under a low pAg of pAg7 or less, or at pH
It is carried out by ripening or growing particles under a high pH condition of 7 or more. Further, these methods can be combined. Preferably, it is performed by adding a reducing agent.

Preferred reducing agents include thiourea dioxide (formamidinesulfinic acid), ascorbic acid and its derivatives, and stannous salts. Other suitable reducing agents include borane compounds, hydrazine derivatives, silane compounds, amines and polyamines, and sulfites. The addition amount is 10 per mole of silver halide.
^-2 to 10 ^-8 mol is preferable, and 10 ^-4 to 10 ^-6 mol is more preferable.

For low pAg ripening, a silver salt can be added, but a water-soluble silver salt is preferred. Silver nitrate is preferred as the water-soluble silver salt. The pAg at ripening is suitably 7 or less, preferably 6 or less, more preferably 1 or less.
３3 (where pAg = −log [Ag ⁺ ]).

High pH ripening is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As the alkaline compound,
For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used. In the method of adding ammoniacal silver nitrate to silver halide formation, an alkaline compound other than ammonia is preferably used because the effect of ammonia is reduced.

As a method for adding the reduction sensitizer, the silver salt and the alkaline compound for the reduction sensitization, rush addition or addition over a certain period of time may be employed. In this case, the addition may be performed at a constant flow rate, or may be performed by changing the flow rate like a function. Further, the required amount may be added several times. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed in a soluble halide solution and added together with the halide. Further, it may be added separately from the soluble silver salt and the soluble halide.

In a preferred constitution of the present invention, a tabular grain has a layer containing a silver chalcogenide nucleus. The silver chalcogenide nucleus containing layer is preferably outside 50% by volume of the whole grain, more preferably outside 70% by volume. The chalcogenide silver nucleus-containing layer may or may not be in contact with the grain surface, but by chemical sensitization, the chemical sensitization nucleus of the formed chalcogenide and the chalcogenide silver nucleus-containing layer referred to here The contained chalcogenide nuclei are clearly distinguished in that they themselves form latent image forming centers. That is, the chalcogenide silver nuclei contained in the chalcogenide silver nucleus containing layer in the present invention are:
It is necessary that the electron capture ability is lower than that of the chemical sensitization nucleus. Silver chalcogenide nuclei satisfying such conditions are formed by a method described later.

The silver chalcogenide nucleus is formed by adding a compound capable of releasing a chalcogen ion. Preferred silver chalcogen nuclei are silver sulfide nuclei, silver selenide nuclei, and silver telluride nuclei, and more preferably silver sulfide nuclei.

As the compound capable of releasing a chalcogen ion, a compound capable of releasing a sulfide ion, a selenide ion or a telluride ion is preferably used.

As compounds capable of releasing sulfide ions, thiosulfonic acid compounds, disulfide compounds, thiosulfates, sulfide salts, thiocarbamide compounds, thioformamide compounds and rhodanine compounds can be preferably used. .

As compounds capable of releasing selenide ions, those known as selenium sensitizers can be preferably used. Specifically, colloidal selenium metal, isoselenocyanates (e.g., allyl isoselenocyanate, etc.), selenoureas (e.g., N, N-dimethylselenourea, N, N, N'-triethylselenourea, N, N N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N '
-Trimethyl-N'-4-nitrophenylcarbonylselenourea, etc.), selenoketones (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), and selenophosphates (eg, tri-p-triselenophosphate, etc.) And selenides (for example, diethyl selenide, diethyl diselenide, triethylphosphine selenide, etc.).

Compounds capable of releasing telluride ions include telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea), phosphine and the like. Tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, etc.), telluroamides (eg, telluroacetamide, N, N-dimethyltellurobenzamide, etc.), telluroketones, telluroesters, Isotellocyanates and the like.

Particularly preferred as a compound capable of releasing a chalcogen ion is a thiosulfonic acid compound,
It is represented by the following general formulas [1] to [3].

General formula [1] R-SO ₂ SM General formula [2] R-SO ₂ S-R ₁ General formula [3] RSO ₂ SL _m -SSO ₂ -R ₂ R ₁ and R ₂ may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group, M represents a cation, L represents a divalent linking group, and m represents 0 or 1. .

The compounds represented by the general formulas [1] to [3] may be a polymer containing a divalent group derived from these structures as a repeating unit.
R ₁ , R ₂ and L may combine with each other to form a ring.

The thiosulfonic acid compounds represented by the general formulas [1] to [3] will be described in more detail. R, R ₁ , R ₂
Is an aliphatic group, a saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, Hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, t-butyl, etc.),
Examples thereof include an alkenyl group having 2 to 22 carbon atoms (such as allyl and butenyl) and an alkynyl group (such as propargyl and butynyl), which may have a substituent.

When R, R ₁ and R ₂ are aromatic groups, they contain a monocyclic or condensed ring aromatic group, and preferably have 6 to 6 carbon atoms.
20 and, for example, phenyl, naphthyl and the like. These may have a substituent.

When R, R ₁ and R ₂ are heterocyclic groups, nitrogen,
3 having at least one element selected from oxygen, sulfur, selenium and tellurium and having at least one carbon atom
A to 15-membered ring, preferably a 3 to 6-membered ring, for example, pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tetrazole, Triazole, benzotriazole, oxadiazole, thiadiazole ring.

Examples of the substituent for R, R ₁ and R ₂ include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyloxy),
Aryl groups (eg, phenyl, naphthyl, tolyl),
Hydroxy group, halogen atom (for example, fluorine, chlorine,
Bromine, iodine), aryloxy group (eg, phenoxy), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, butyryl, valeryl), sulfonyl group (eg, Methylsulfonyl,
Phenylsulfonyl), acylamino group (eg, acetylamino, benzoylamino), sulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino), acyloxy group (eg, acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, Examples include an amino group, a —SO ₂ SM group (M represents a monovalent cation), and a —SO ₂ R ₁ group.

As the divalent linking group represented by L, C,
An atom or an atomic group containing at least one selected from N, S and O can be mentioned. Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group,
-O -, - S -, - NH -, - CO -, - SO 2 - is made of a single or a combination of these, and the like.

L is preferably a divalent aliphatic group or a divalent aromatic group. As the divalent aliphatic group, for example,

[0082]

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A xylylene group and the like can be mentioned. Examples of the divalent aromatic group include a phenylene group and a naphthylene group.

These substituents may be further substituted with the substituents described above.

[0085] M is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include an ammonium ion (eg, ammonium, tetramethylammonium, tetrabutylammonium), a phosphonium ion (eg, tetraphenylphosphonium), and a guanidyl group.

When the compounds represented by the above general formulas [1] to [3] are polymers, their repeating units include
For example, the following are mentioned. These polymers are
It may be a homopolymer or a copolymer with another copolymerized monomer.

[0087]

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Specific examples of the compounds represented by the general formulas [1] to [3] are described in, for example, JP-A-54-1019, British Patent No. 972,211 and Journal of Or.
ganic Chemistry vol. 53, p.
396 (1988).

The amount of the compound capable of releasing a chalcogen ion for forming a silver chalcogenide nucleus is preferably 10 ⁻² to 10 ⁻⁸ mol per mol of silver halide.
^-3 to 10 ^-6 is more preferable.

As a method of adding a compound capable of releasing a chalcogen ion for forming a silver chalcogenide nucleus,
Rush may be added, or may be added over a certain period of time. In this case, the addition may be performed at a constant flow rate, or may be performed by changing the flow rate like a function. Further, the required amount may be added several times. It is necessary to form the silver chalcogenide nucleus by the end of the grain formation. The formation of silver chalcogenide nuclei after grain formation may or may not be performed, but the silver chalcogenide nuclei formed after grain formation are taken in as part of the chemical sensitization nuclei formed in the chemical sensitization process, It does not substantially contribute to the effects of the present invention. Similarly, when chemical sensitization is performed inside the grain, the chalcogenide silver nuclei formed on the same surface as the chemical sensitization are
It does not substantially contribute to the effects of the present invention.

As a means for forming tabular grains of the present invention, various methods well known in the art can be used. That is, any combination of the single jet method, the controlled double jet method, the controlled triple jet method, etc. can be used, but in order to obtain advanced monodisperse grains, it is necessary to produce silver halide grains. It is important to control the pAg in the liquid phase to be adjusted according to the growth rate of the silver halide grains.
As the pAg value, a region of 7.0 to 12 is used, and preferably a region of 7.5 to 11 can be used.

In determining the addition rate, use
No.-48521, and the technology described in JP-A-58-49938 can be referred to.

The preparation step of the tabular grains of the present invention is roughly classified into a nucleation step, an ripening step (nucleus ripening step) and a subsequent growing step. It is also possible to separately grow a previously prepared nuclear emulsion (or seed emulsion). The growth process may include several stages, such as a first growth process and a second growth process. The growth process of the tabular grains of the present invention means all growth processes from the nucleus (or seed) formation to the end of grain growth, and the start of growth refers to the start of the growth process.

The tabular grains of the present invention can contain at least one or more polyvalent metal compounds in the grain peripheral region.

Here, although the terms are defined, "doping" or "doping" indicates that a substance other than silver ions or halide ions is contained in silver halide grains. The term "dopant" refers to a compound that dopes the silver halide grains. The term "metal dopant"
Represents a polyvalent metal compound doped into silver halide grains.

As metal dopants, Mg, Al,
Ca, Sc, Ti, V, Cr, Mn, Fe, Co, C
u, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo,
Tc, Ru, Rh, Pd, Cd, Sn, Ba, Ce, E
u, W, Re, Os, Ir, Pt, Hg, Tl, Pb,
Metal compounds such as Bi and In can be preferably used.

The metal compound to be doped is preferably selected from a single salt or a metal complex. When selecting from metal complexes, 6-coordinate, 5-coordinate, 4-coordinate and 2-coordinate complexes are preferred, and octahedral 6-coordinate and planar 4-coordinate complexes are more preferred. The complex may be a mononuclear complex or a polynuclear complex. The ligands constituting the complex include CN ⁻ , C
O, NO ₂ ^-, 1,10-phenanthroline, 2,2'-
Bipyridyl, SO ₃ ⁻ , ethylenediamine, NH ₃ , pyridine, H ₂ O, NCS ⁻ , CO ⁻ , NO ₃ ⁻ , SO ₄ ⁻ , O
_{^{H -, N 3 -, S}} 2 -, F -, Cl -, Br -, I - or the like can be used. Particularly preferred metal dopants are K ₄ Fe (CN) ₆ , K ₃ Fe (CN) ₆ , Pb (NO
₃ ) ₂ , K ₂ IrCl ₆ , K ₃ IrCl ₆ , K ₂ IrBr ₆ , I
nCl ₃ .

The concentration distribution of the metal dopant in the silver halide grains is such that the grains are gradually dissolved from the surface to the inside,
It is determined by measuring the dopant content of each part. Specific examples include the method described below.

Prior to metal quantification, the silver halide emulsion is pretreated as follows. First, 50 ml of a 0.2% actinase aqueous solution is added to about 30 ml of the emulsion, and the mixture is stirred at 40 ° C. for 30 minutes to perform gelatin decomposition. This operation 5
Repeat several times. After centrifugation, 5 times with 50 ml of methanol,
Washing is repeated twice with 50 ml of 1N nitric acid and five times with ultrapure water. After centrifugation, only silver halide is separated. The surface portion of the obtained silver halide grains is dissolved with an aqueous ammonia solution or ammonia whose pH has been adjusted (the ammonia concentration and pH are changed according to the type and amount of silver halide to be dissolved). As a method for dissolving the extreme surface of silver bromide grains in silver halide, about 1 g of silver halide is dissolved in 2 g of silver halide.
About 20% of the particles can be dissolved by using 20 ml of 0% aqueous ammonia. At this time, the amount of silver halide dissolved was determined by centrifuging the aqueous ammonia solution after dissolving the silver halide and the silver halide, and determining the amount of silver present in the obtained supernatant by a high frequency induction plasma mass spectrometer. (ICP-MS), high frequency induction plasma emission spectroscopy (ICP-AES), or atomic absorption. From the difference between the amount of metal contained in the silver halide after surface dissolution and the total amount of silver halide not dissolved, the amount of metal per mole of silver halide present in about 3% of the grain surface can be determined. it can. Metal quantification methods include an aqueous solution of ammonium thiosulfate, an aqueous solution of sodium thiosulfate, or an aqueous solution of potassium cyanide, and a matrix-matched ICP-MS method.
It can be quantified by the ICP-AES method or the atomic absorption method. Of these, potassium cyanide as a solvent,
ICP-MS (FISON Eleme)
ntal Analysis), about 40 mg of silver halide is dissolved in 5 ml of 0.2N potassium cyanide, and then the internal standard element Cs is adjusted to 10 ppb.
The solution was added, and the volume was adjusted to 100 ml with ultrapure water to obtain a measurement sample. ICP- using a calibration curve matching the matrix with metal-free silver halide
The metal in the measurement sample is quantified by MS. At this time, the exact amount of silver in the measurement sample can be determined by ICP-AES or atomic absorption of the measurement sample diluted 100 times with ultrapure water. After such dissolution of the grain surface, the silver halide grains are washed with ultrapure water, and the dissolution of the grain surface is repeated in the same manner as described above, whereby metal in the silver halide grain internal direction is obtained. The quantity can be determined.

By combining the above-described ultrathin section preparation method and the above-described metal determination method, the metal doped in the peripheral region of the tabular grains of the present invention can be determined.

The preferred content of the metal dopant in the tabular grains of the present invention is from 1 × 10 ^-9 mol to 1 × 10 ^-4 mol, more preferably 1 × 10 ^-8 mol, per mol of silver halide.
Mol to 1 × 10 ^-5 mol.

In the tabular grains of the present invention, the ratio of the amount of metal dopant contained in the peripheral region to the amount of metal dopant contained in the central region of the main plane is 5 times or more, preferably 10 times or more, and more preferably 20 times or more. More than double.

The effect of the metal dopant is effectively exhibited by adding the metal dopant to the base grains in a state of being doped in the silver halide fine grain emulsion in advance. At this time, the concentration of the metal dopant per mole of the silver halide fine particles was 1
X 10 ^-1 mol to 1 x 10 ^-7 mol is preferred, and 1 x 10 ^-3 mol.
The mole is more preferably from 1 to 10 ⁵ mol.

As a method of doping silver halide fine particles with a metal dopant in advance, it is preferable to form fine particles while the metal dopant is dissolved in a halide solution.

The halogen composition of the silver halide fine grains may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. It is preferable that

The silver halide fine particles containing a metal dopant can be deposited on the base grains at any time after the formation of the base grains and before the start of chemical sensitization. The period before the start is particularly preferable. By adding the fine grain emulsion in a state where the salt concentration of the base emulsion is low, the silver halide fine grains are deposited together with the metal dopant in a portion where the activity of the base grains is highest. That is, the tabular grains of the present invention can be efficiently deposited on the outer peripheral region including the corners and edges. This deposition does not mean that the silver halide fine particles are aggregated and adsorbed on the base particles as they are, but the silver halide fine particles are dissolved in the reaction system in which the silver halide fine particles and the base particles coexist, and are deposited on the base particles. Regenerating as silver halide. That is, when a part of the emulsion obtained by the above method was taken out and observed with an electron microscope, no silver halide fine particles were observed, and no epitaxial protrusions were observed on the surface of the base particles. Say.

The silver halide fine particles to be added are preferably added in an amount of 1 × 10 ^-7 mol to 0.5 mol per mol of base grains, preferably 1 × 10 ^-5 mol to 1 × 10 ^-1 mol. More preferably, the amount of silver is added.

The physical ripening conditions for depositing the silver halide fine grains can be arbitrarily selected from 30 ° C. to 70 ° C./10 minutes to 60 minutes.

In the production of the tabular grains of the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like may be present, or a silver halide solvent may not be used.

In the tabular grains of the present invention, in order to selectively form dislocation lines in the central region of the main plane, the pH is increased in the ripening step after nucleation, and ripening is performed so as to increase the thickness of the tabular grains. Is important, but if the pH is too high, the aspect ratio is too low, and it is difficult to control the aspect ratio in a subsequent growth step. It also causes unexpected fog deterioration. Therefore, the pH / temperature of the aging step is preferably from 7.0 to 11.0 / 40 ° C to 80 ° C, more preferably from 8.5 to 10.0 / 50 ° C to 70 ° C.

In the tabular grains of the present invention, in order to form dislocation lines selectively in the outer peripheral region, an iodine ion source (for example, silver iodide fine particles, It is important to increase the pAg in the grain growth after adding the iodide ion releasing agent) to the base grains. However, if the pAg is too high, so-called Ostwald ripening proceeds simultaneously with the grain growth, and the monodispersity of the tabular grains increases. Deteriorates. Therefore, the pAg at the time of forming the outer peripheral region of the tabular grain in the growth step is:
8-12 are preferable, and 9.5-11 are more preferable. When an iodine ion releasing agent is used as an iodine ion source, dislocation lines can be effectively formed in the outer peripheral region by increasing the amount of iodine ion releasing agent. The amount of the iodide ion releasing agent added is 0.5 to 1 mol of silver halide.
It is preferably at least mol, and more preferably 2 to 5 mol.

The tabular grains in the present invention may be those obtained by removing unnecessary soluble salts after the growth of the silver halide grains, or may be those containing them.

It is also possible to carry out desalting at any point during silver halide growth, as in the method described in JP-A-60-138538.

When the salts are removed, Research Disclosure (Research Disclosure) is used.
ure (hereinafter, abbreviated as RD)) No. 17643 No. II. More specifically, in order to remove the soluble salt from the emulsion after the formation of the precipitate or after the physical ripening, it is possible to use a Noudel washing method performed by gelling gelatin, and inorganic salts, anionic surfactants, A precipitation method (flocculation) using an anionic polymer (eg, polystyrene sulfonic acid) or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used. A method using a modified gelatin obtained by substituting an amino group of gelatin described in JP-A-5-72658 can be preferably used. In particular, modified gelatin in which amino groups of gelatin are phenylcarbamoylated, that is, chemically modified gelatin is preferable.

When chemically modified gelatin is used for removing salts, the substitution ratio of amino groups is preferably 30% or more.
% Or more, more preferably 80% or more.

The addition amount of the chemically modified gelatin in the silver halide emulsion forming step of the present invention is from 15% by weight to less than 100% by weight of the total amount of gelatin added in the silver halide emulsion forming step. , 40% by weight or more is more preferable.

Examples of the substituents useful for obtaining a chemically modified gelatin by substituting an amino group in the present invention are shown below, but the present invention is not limited thereto.

[0118]

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In general, the step of preparing a silver halide emulsion is roughly divided into a nucleation step (consisting of a nucleation step and a ripening step) and a subsequent step of growing the nucleus. It is also possible to separately grow a previously prepared nuclear emulsion (or seed emulsion). The growth process may include several stages, such as a first growth process and a second growth process.

In the present invention, the growth process of silver halide grains means all the growth steps from the nucleus (or seed) formation to the end of grain growth, and the start of growth means the start of the growth step.

In the present invention, by appropriately using an operation of removing unnecessary substances such as salts and ions by an ultrafiltration membrane during the formation of the grains, the particles remain after being used in the formation of the silver halide phase.
A silver halide capable of removing excess or unnecessary halogen ions, preventing unintended conversion in subsequent manufacturing steps, and facilitating control of the halogen composition during formation of the other silver halide phase. An example of the apparatus will be described with reference to FIG.

The reaction vessel 1 initially contains the dispersion medium 3. The apparatus comprises a reaction vessel 1 and a silver addition line 4 for adding at least one aqueous solution of a silver salt, preferably an aqueous solution of silver nitrate, and at least one aqueous solution of a halide salt, preferably an alkali metal such as bromine, iodine or chlorine. It has a halide addition line 5 for adding an aqueous salt solution, an aqueous ammonium salt solution, or a mixture thereof. Further, it has a stirring mechanism 2 for stirring the dispersion medium and the reactant solution (a mixture of the dispersion medium and the silver halide grains) in the process of preparing the silver halide emulsion. The stirring mechanism can be in any conventional manner. Silver salt aqueous solution is silver addition line 4
From the reaction vessel at a flow rate controlled by the silver addition valve 20. The halide aqueous solution is added to the reaction vessel from the halide addition line 5 at a flow rate controlled by the halide addition valve 21. The addition of the solution through the silver addition line 4 and the halide addition line 5 may be performed at the liquid level, but is more preferably performed in the liquid near the stirring mechanism 2. The stirring mechanism 2 mixes the aqueous silver salt solution and the aqueous halide salt solution with a dispersion medium, and enables the soluble silver salt to react with the soluble halide salt to produce silver halide.

During the first stage of silver halide formation, ie, in the nucleation step, a dispersion (reactant solution) containing the base silver halide nucleus particles is formed. Subsequently, the nucleation step is completed through an aging step as required. Thereafter, when the addition of the silver salt aqueous solution and the halogen salt aqueous solution is continued, the second stage silver halide formation, that is, the process proceeds to the growth process stage,
Additional silver halide produced as a reaction product in the process deposits on the initially formed silver halide nucleus grains, increasing the size of these grains.

In the present invention, during the particle formation process by adding the aqueous silver salt solution and the aqueous halogen salt solution to the reaction vessel, a part of the reactant solution in the reaction vessel is
The liquid is sent to the ultrafiltration unit 12 through the liquid take-out line 8 and returned to the reaction vessel through the liquid return line 9. At that time, the pressure applied to the ultrafiltration unit 12 is adjusted by a pressure adjusting valve 18 provided in the middle of the liquid return line 9 to partially remove the water-soluble salt solution contained in the reaction solution. Separated by filtration unit, permeate discharge line 1
Discharge out of the system through 0.

When this method is applied in the present invention, it is preferable to arbitrarily control the permeate amount (ultrafiltration flux) of the solution of the water-soluble salt separated by the ultrafiltration membrane. For example, in that case, the permeated liquid discharge line 10
The ultrafiltration flux can be arbitrarily controlled using the flow control valve 19 provided in the middle of the process. At that time, in order to minimize the pressure fluctuation of the ultrafiltration unit 12, the valve 25 provided in the middle of the permeate return line 11 may be opened to use the permeate return line 11. Alternatively, the valve 25 may be closed and the permeate return line 11 may not be used, which can be arbitrarily selected according to the operating conditions.

For detecting the ultrafiltration flux, a flow meter 14 provided in the middle of the permeated liquid discharge line 10 may be used, or the flux may be detected by a weight change using a permeated liquid container 27 and a scale 28. May be.

In the present invention, the concentration by the ultrafiltration method in the particle growing process may be performed continuously throughout the particle forming process or may be performed intermittently. However, when applying the ultrafiltration method in the particle growth process, after starting the circulation of the reactant solution to the ultrafiltration step, the circulation of the reactant solution may be continued at least until the end of the particle formation. preferable. Therefore, it is preferable that the circulation of the reactant solution to the ultrafiltration unit be continued even when the concentration is interrupted. This is to avoid uneven distribution between particles in the reaction vessel and particles in the ultrafiltration step. Further, it is preferable that the circulation flow rate through the ultrafiltration step is sufficiently high. Specifically, the residence time of the silver halide reactant solution in the ultrafiltration unit including the liquid take-out line and the liquid return line is preferably within 30 seconds, and is preferably within 1 second.
It is more preferably within 5 seconds, and particularly preferably within 10 seconds. The lower limit is at least 5 seconds.

The volume of the ultrafiltration step including the liquid take-out line 8, the liquid return line 9, the ultrafiltration unit 12, the circulation pump 13 and the like is preferably 30% or less of the volume of the reaction vessel, and 20% or less. It is more preferably at most 10%, particularly preferably at most 10%. The lower limit is 5%
That is all.

As described above, by applying the ultrafiltration step, the volume of the total silver halide reactant solution can be arbitrarily reduced during grain formation. Further, by adding water from the addition line 7, the volume of the silver halide reactant solution can be arbitrarily maintained.

In the present invention, there are no particular restrictions on the ultrafiltration module and the circulating pump which can be used in carrying out the ultrafiltration. It is preferable to avoid any material and structure. In order to obtain the tabular grains of the present invention, it is important to select the molecular weight cut-off of the ultrafiltration membrane. The molecular weight cut off is 1000 or more,
0 is preferable, and those with 4000 to 50,000 are more preferably used.

The tabular grains of the present invention can be chemically sensitized by a conventional method. That is, sulfur sensitization, selenium sensitization,
A noble metal sensitization method using gold or another noble metal compound can be used alone or in combination.

The tabular grains of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye which has no spectral sensitizing effect by itself together with the sensitizing dye or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. May be.

An antifoggant, a stabilizer and the like can be added to the tabular grains of the present invention. The emulsion layer and other hydrophilic colloid layers can be hardened,
A dispersion (latex) of a water-insoluble or soluble synthetic polymer can be included.

A coupler is used in the emulsion layer of the color photographic light-sensitive material. Further, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifogging agent, and a coupling with a competing coupler having a color correcting effect and an oxidized form of a developing agent, Compounds that release photographically useful fragments can be used, such as chemical sensitizers, spectral sensitizers, and desensitizers.

The light-sensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an anti-irradiation layer. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained.

The light-sensitive material can contain a matting agent, a lubricant, an image stabilizer, a formalin scavenger, an ultraviolet absorber, a fluorescent brightener, a surfactant, a development accelerator and a development retarder. As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

[0137]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Comparative Example-1 << Preparation of Comparative Example Emulsion EM-1 >> [Nucleation Step] The following reaction mother liquor (Gr-1) in a reaction vessel
The pH was adjusted to 1.96 with 1N sulfuric acid while stirring at a stirring rotation speed of 400 rpm using a mixing and stirring apparatus described in JP-A-62-160128. Thereafter, the liquid (S-1) and the liquid (H-1) were added at a constant flow rate for one minute by using a double jet method to form nuclei.

(Gr-1) Alkali-treated inert gelatin (average molecular weight 100,000) 40.50 g Potassium bromide 12.40 g Finish up to 16.2 liters with distilled water (S-1) 862.5 g of silver nitrate 4 with distilled water (H-1) Potassium bromide 604.5 g Finish to 4.06 liter with distilled water [Aging step] After the above nucleation step, add the (G-1) solution and take 30 minutes. The temperature was raised to 60 ° C. During this time, the silver potential of the emulsion in the reaction vessel (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 2N potassium bromide solution. Subsequently, the pH was adjusted to 9.3 by adding an aqueous ammonia solution, and after maintaining the mixture for 7 minutes, the pH was adjusted to 8.0 using an aqueous acetic acid solution. During this period, the silver potential was adjusted to 6 mV using a 2N potassium bromide solution.
Was controlled.

(G-1) Alkali-treated inert gelatin (average molecular weight 100,000) 173.9 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol solution 5.80 ml Finish up to 4.22 liters with distilled water [Growth step] After the ripening step, the solution (S-1) is successively applied by a double jet method. And (H-1) solution while accelerating the flow rate (the ratio of the addition flow rate at the end and at the start is about 12 times)
Added in 37 minutes. After the addition was completed, the solution (G-2) was added, and the pH was adjusted to 5.0 with an aqueous acetic acid solution. After adjusting the stirring rotation speed to 550 rpm, the (S-2) solution and the (H-2) solution are successively accelerated while increasing the flow rates (the ratio of the addition flow rate at the end to the addition at the start is about 1.4). Fold) for 100 minutes. During this time, the silver potential of the emulsion was controlled at 6 mV using a 2N potassium bromide solution. After the addition is completed, the pH is adjusted to 5.0 using an aqueous acetic acid solution, and then the silver potential in the reaction vessel is adjusted to −25 m using a 3N potassium bromide solution.
After adjusting to V, the flow rates of the (S-2) solution and the (H-3) solution were accelerated (the ratio of the addition flow rate at the end to the addition was about 1.
5 times) for 15 minutes.

(S-2) Silver nitrate 2.14 kg Finished to 3.60 liters with distilled water.

(H-2) Potassium bromide 859.5 g Potassium iodide 24.45 g Make up to 2.11 liters with distilled water.

(H-3) Potassium bromide 587.0 g Potassium iodide 8.19 g Make up to 1.42 liters with distilled water.

(G-2) Ossein gelatin 284.9 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 7.75 ml of a 10% by weight methanol solution of the above is made up to 1.93 liters with distilled water.

After the completion of grain growth, 500.0 g of phenylcarbamoylated gelatin (substitution rate of amino groups: 90%)
An aqueous solution containing (43.5% of the total amount of gelatin added) was added, the pH was adjusted to 4.60 with acetic acid, the emulsion was sedimented, and the supernatant was drained. Subsequently, 17.0 liters of pure water at 40 ° C. was added and the mixture was stirred, then the emulsion was sedimented and the supernatant was drained twice. Then 150.0 g of gelatin
(13.0% of the total amount of gelatin added) and dispersed.
At ℃, the pH was adjusted to 5.80 and the EAg to 70 mV.
The emulsion thus obtained is designated as EM-1. From the electron micrograph of the obtained emulsion particles, the average particle size was 1.50 μm (the average value of the projected area in terms of circle), and the aspect ratio was 7.5.
(60% of the total projected area) and tabular grains having a particle size distribution of 15.0% were confirmed.

<< Preparation of Comparative Example Emulsion EM-2 >> In the nucleus forming step, grains were formed in the same manner as in EM-1, and then the ripening step and the growing step were changed as follows to obtain Comparative Example emulsion EM-2.
Was prepared.

[Maturation Step] After the above nucleation step, (G
-1) The solution was added, and the temperature was raised to 60 ° C. over 30 minutes.
During this time, the silver potential of the emulsion in the reaction vessel (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 2N potassium bromide solution. continue,
Aqueous ammonia was added to adjust the pH to 9.3, and after keeping the mixture for 7 minutes, the pH was adjusted to 6.1 using an acetic acid aqueous solution. During this time, the silver potential was controlled at 6 mV using a 2N potassium bromide solution.

[Growth Step] After the completion of the ripening step, the (S-1) solution and (H-1) solution are accelerated by the double jet method while increasing the flow rates (the addition flow rates at the end and at the start). (The ratio is about 12 times). (G-
2) After adding the liquid and adjusting the stirring rotation speed to 550 rpm, the (S-2) liquid and the (H-2) liquid were successively accelerated while increasing the flow rates (the addition flow rate at the end and at the start). The ratio is about 1.4
X) for 40 minutes. During this time, the silver potential of the emulsion was controlled at 6 mV using a 2N potassium bromide solution. After the completion of the addition, the emulsion temperature in the reaction vessel was raised to 4 over 15 minutes.
The temperature was lowered to 0 ° C. Then, the liquid (Z-1) and then (S
S) The solution was added, the pH was adjusted to 9.3 using an aqueous solution of potassium hydroxide, and iodine ions were released while aging for 4 minutes. Thereafter, the pH was adjusted to 5.0 using an aqueous acetic acid solution, and then the silver potential in the reaction vessel was adjusted to −39 mV using a 3N potassium bromide solution. 3) The liquid was added for 25 minutes while accelerating the flow rate (the ratio of the addition flow rate at the end to the start was about 1.5 times).

(Z-1) 192.5 g of sodium p-iodoacetamidobenzenesulfonate Finished to 2.30 liters with distilled water.

(SS) 66.8 g of sodium sulfite Make up to 0.70 liter with distilled water.

After completion of the grain growth, the pH was adjusted to 5.80 and the EAg to 70 mV at 40 ° C. in the same manner as in EM-1. The emulsion thus obtained is designated as EM-2. From the electron micrograph of the obtained emulsion particles, the average particle size was 1.50.
It was confirmed that the tabular grains had a μm (average value of the diameter of the projected area in circle), an aspect ratio of 7.5 (60% of the total projected area), and a particle size distribution of 15.0%.

<< Preparation of Comparative Example Emulsion EM-3 >> In the nucleation step and the ripening step, grains were formed in the same manner as in EM-1, and the growth step was changed as follows to obtain Comparative Example Emulsion EM-3.
Was prepared.

[Growth Step] After the ripening step, the (S-1) solution and (H-1) solution are successively accelerated by the double jet method (the addition flow rate at the end and at the start is increased). (The ratio is about 12 times). (G-
2) After adding the solution, the pH was adjusted to 5.0 using an aqueous acetic acid solution. After adjusting the stirring speed to 550 rpm,
Subsequently, while increasing the flow rates of the liquid (S-2) and the liquid (H-2) (the ratio of the addition flow rate at the end to the addition at the start is about 1.4 times).
Added in 100 minutes. During this time, the silver potential of the emulsion was controlled at 6 mV using a 2N potassium bromide solution. After the addition was completed, the solution (Z-1) and then the solution (SS) were added, the pH was adjusted to 9.3 with an aqueous potassium hydroxide solution, and iodine ions were released while aging for 4 minutes. Thereafter, the pH was adjusted to 5.0 using an aqueous acetic acid solution, and then the silver potential in the reaction vessel was adjusted to −25 m using a 3N potassium bromide solution.
After adjusting to V, the flow rates of the (S-2) solution and the (H-3) solution were accelerated (the ratio of the addition flow rate at the end to the addition was about 1.
5 times) for 15 minutes.

After completion of the particle growth, an aqueous solution containing Demol (manufactured by Kao Atlas) was added, and the pH was adjusted to 4.6 with acetic acid.
The emulsion was settled to 0 and the supernatant was drained. Subsequently, 17.0 liters of pure water at 40 ° C. was added and stirred, and then the operation of sedimenting the emulsion and draining the supernatant was repeated twice. Thereafter, gelatin was added and dispersed, and the pH was adjusted to 5.80 at 40 ° C.
g was adjusted to 70 mV. The emulsion thus obtained was subjected to EM
-3. From the electron micrograph of the obtained emulsion particles,
It was confirmed that the tabular grains had an average particle size of 1.50 μm (average value of the circle-converted diameter of the projected area), an aspect ratio of 7.5 (60% of the total projected area), and a particle size distribution of 15.0%.

<< Preparation of Emulsion EM-4 of the Present Invention >> Emulsion EM-
Emulsion EM-4 of the present invention was prepared in the same manner as in Production Method 3, except that the desalting step was changed as follows.

After the completion of grain growth, 500.0 g of phenylcarbamoylated gelatin (substitution rate of amino groups: 90%)
An aqueous solution containing (43.5% of the total amount of gelatin added) was added, the pH was adjusted to 4.60 with acetic acid, the emulsion was sedimented, and the supernatant was drained. Subsequently, 17.0 liters of pure water at 40 ° C. was added and stirred, and then the operation of sedimenting the emulsion and draining the supernatant was repeated twice. Thereafter, 150.0 g of gelatin (13.0% of the total amount of gelatin) was added and dispersed, and the pH was adjusted to 5.80 and the EAg to 70 mV at 40 ° C. The emulsion thus obtained is designated as EM-4.

From the electron micrograph of the obtained emulsion particles,
It was confirmed that the tabular grains had an average particle size of 1.52 μm (average diameter of the projected area in terms of circle), an aspect ratio of 7.7 (60% of the total projected area), and a particle size distribution of 15.4%.

<< Preparation of Emulsion EM-5 of the Present Invention >> In the nucleus forming step and the ripening step, grains were formed in the same manner as in EM-2.
-5 was prepared.

After the aging step, the liquids (S-1) and (H-1) are accelerated by double jet method while increasing the flow rate (the ratio of the flow rate at the end to the time at the start is about 12). Times)
Added in 37 minutes. After the addition was completed, the solution (R-1) was rush-added, then the solution (G-2) was added, and the stirring speed was adjusted to 550 rpm, followed by the solution (S-2) and the solution (H-). 2) The solution was added for 40 minutes while accelerating the flow rate (the ratio of the addition flow rate at the end to the start was about 1.4 times). During this time, the silver potential of the emulsion was adjusted to 6 using a 2N potassium bromide solution.
Controlled to mV. After the addition was completed, the emulsion temperature in the reaction vessel was lowered to 40 ° C. over 15 minutes. afterwards,
The solution (Z-1) and then the solution (SS) were added, the pH was adjusted to 9.3 using an aqueous potassium hydroxide solution, and iodine ions were released while aging for 4 minutes. Thereafter, the pH was adjusted to 5.0 using an aqueous acetic acid solution, and then the silver potential in the reaction vessel was adjusted to −39 mV using a 3N potassium bromide solution. 3) While increasing the flow rate of the liquid (the ratio of the addition flow rate at the end to the
In the meantime, when the remaining amount of the solution (S-2) reached 498 cc, rush addition of the solution (T-1) was carried out while the addition was continued, and the emulsion EM-2 was added except that it was added in 25 minutes. Emulsion EM-5 of the present invention was prepared by the same production method as in Example 1.

(R-1) thiourea dioxide 26.6 mg distilled water 46.6 ml (T-1) sodium ethanethiosulfonate 879.9 mg distilled water 293.3 ml After the above particle growth, the same as EM-4 The resulting emulsion is designated as EM-5.

From the electron micrograph of the obtained emulsion particles,
It was confirmed that the tabular grains had an average particle size of 1.52 μm (average value of the circle-converted diameter of the projected area), an aspect ratio of 7.5 (60% of the total projected area), and a particle size distribution of 15.0%.

<< Preparation of Emulsion EM-6 of the Present Invention >> In the nucleus forming step and the ripening step, grains were formed in the same manner as in EM-5, and then the growing step was changed as follows to obtain the emulsion EM-6 of the present invention.
Was prepared.

After the aging step, the liquids (S-1) and (H-1) are accelerated by the double jet method while increasing the flow rates (the ratio of the flow rates at the end and the start is about 12). Times)
Added in 37 minutes. After completion of the addition, the solution (R-2) was rush-added, then the solution (G-2) was added, and the stirring speed was adjusted to 550 rpm, followed by the solution (S-2) and the solution (H-). 2) While accelerating the flow rate of the liquid (the ratio of the addition flow rate at the end to the addition at the start is about twice), the addition is continued when the remaining amount of the liquid reaches 3.33 liters in the middle (S-2). As it was, the (R-3) solution was rush-added and added over 40 minutes. During this time, the silver potential of the emulsion was controlled at 6 mV using a 2N potassium bromide solution. After the addition is completed, (R-
4) The solution was rushed and the emulsion temperature in the reaction vessel was reduced to 15
The temperature was lowered to 40 ° C. over a period of minutes. Then, (Z-1)
The solution and then the (SS) solution were added, the pH was adjusted to 9.3 with an aqueous solution of potassium hydroxide, and iodine ions were released while aging for 4 minutes. Thereafter, p is added using an aqueous acetic acid solution.
H was adjusted to 5.0, and then the silver potential in the reaction vessel was adjusted to -39 mV using a 3N potassium bromide solution.
While accelerating the flow rates of the liquid (S-2) and the liquid (H-3) (the ratio of the addition flow rate at the end to the addition at the start is about 1.5 times), the solution (S-2)
-2) When the remaining amount of the solution reaches 498 cc, while the addition is continued, the lash addition of the solution (T-1) is performed, and
Emulsion EM-6 of the present invention was prepared in the same manner as in the preparation of emulsion EM-5, except that the mixture was added in minutes.

(R-2) thiourea dioxide 6.65 mg distilled water 11.7 ml (R-3) thiourea dioxide 8.87 mg distilled water 15.5 ml (R-4) thiourea dioxide 11.1 mg distilled water 19. 4 ml After the completion of the grain growth, the emulsion obtained in the same manner as EM-4 is referred to as EM-6.

From the electron micrograph of the obtained emulsion particles,
It was confirmed that the tabular grains had an average particle size of 1.53 μm (average value of the diameter of the projected area in circle), an aspect ratio of 7.5 (60% of the total projected area), and a particle size distribution of 15.0%.

<< Comparative Example Preparation of Emulsion EM-7 >> Emulsion EM-
In the production method 4, the silver potential in the reaction vessel was controlled to −34 mV throughout the entire growth step to grow the grains, and otherwise the variation coefficient of the grain size was deteriorated by the same production method as the emulsion EM-4. The prepared emulsion EM-7 was prepared. From the electron micrograph of the obtained emulsion particles, the average particle size was 1.67 μm.
(Average value of projected area in circle equivalent diameter), aspect ratio 1
It was confirmed that the tabular grains had a particle size distribution of 0.1 (60% of the total projected area) and a particle size distribution of 33.0%.

<< Preparation of Emulsion EM-8 of the Present Invention >> Emulsion EM-
In the step of adding and dispersing gelatin after the desalting treatment in the production method of 4, the following (F-2) is added and 50
An emulsion EM-8 was prepared in the same manner as the emulsion EM-4, except that the mixture was aged at 20 ° C. for 20 minutes.

(F-2) Fine grain emulsion of silver bromide doped with K ₂ IrCl ₆ 4.70 g * The preparation method of the fine grain emulsion (F-2) is as follows: 0.0
5000 ml of a 6.0% by weight gelatin solution containing 6 mol of potassium bromide, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate, 7.06 mol of potassium bromide and 4.
2000 m aqueous solution containing 4 × 10 ^-3 mol of K ₂ IrCl ₆
was added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are formed, the pH is adjusted to 6.0 using an aqueous solution of sodium carbonate.
Was adjusted. The finished weight was 12.53 kg.

From an electron micrograph of the obtained emulsion particles,
It was confirmed that the tabular grains had an average particle size of 1.54 μm (average value of the circle-converted diameter of the projected area), an aspect ratio of 7.4 (60% of the total projected area), and a particle size distribution of 15.6%.

<< Preparation of Emulsion EM-9 of the Present Invention >> Emulsion EM-
(S-1) and (S-
During the addition of 2), an ultrafiltration apparatus described in JP-A-10-33923 was used, and the liquid volume in the kettle was constantly kept constant.
An emulsion prepared in the same manner as EM-4 except for the preparation was designated as EM-9.

From the electron micrograph of the obtained emulsion particles,
It was confirmed that the tabular grains had an average particle size of 1.54 μm (average value of the circle-converted diameter of the projected area), an aspect ratio of 7.5 (60% of the total projected area), and a particle size distribution of 14.5%.

<< Preparation of Emulsion EM-10 of the Present Invention >> Emulsion EM
After adjusting the silver potential in the reaction vessel to -25 mV using a 3N potassium bromide solution in the preparation of -4, (S-
2) Solution and (H-3) solution were added while accelerating the flow rate (the ratio of the addition flow rate at the end to the start was about 1.5 times), and the addition was stopped at 94% of the total silver amount. Then, after adjusting the silver potential in the reaction vessel to -40 mV using a 3N potassium bromide solution, the same procedure as in EM-4 was carried out except that the residual liquid (S-2) and the liquid (H-4) were added again. The resulting emulsion is designated as EM-10.

(H-4) Potassium bromide (3.5 N) From the electron micrograph of the obtained emulsion particles, it was found that the average particle size was 1.
53 μm (average value of projected area in terms of circle), aspect ratio 7.4 (60% of total projected area), particle size distribution 15.1
% Tabular grains.

<< Preparation of Emulsion EM-11 of the Present Invention >> Emulsion EM
(S-1) and (S-
During the addition of (2), particles were formed using an ultrafiltration apparatus described in JP-A-10-33923, while keeping the liquid volume in the kettle constant, and the reaction vessel was charged with a 3N potassium bromide solution. Was adjusted to -25 mV, and the solution (S-2) and the solution (H-3) were added while accelerating the flow rate (the ratio of the flow rate at the end to the time at the start was about 1.5 times). ), 9 of total silver
The addition was stopped at the time of 4%, and after adjusting the silver potential in the reaction vessel to -40 mV using a 3N potassium bromide solution,
Again, the (S-2) residual liquid and the (H-4) liquid were added. Furthermore,
In the step of adding and dispersing the gelatin after the desalting treatment, (F-2) was added and the mixture was aged at 50 ° C. for 20 minutes. Otherwise, in the same manner as the emulsion EM-4, the emulsion EM-
11 was produced.

From the electron micrograph of the obtained emulsion particles,
It was confirmed that the tabular grains had an average particle size of 1.54 μm (average diameter of the projected area in terms of circle), an aspect ratio of 7.5 (60% of the total projected area), and a particle size distribution of 14.8%.

<< Preparation of Emulsion EM-12 of the Present Invention >> Emulsion EM
In this way, the emulsion EM-12 of the present invention was prepared in the same manner as in Production Method 4, except that the steps after grain growth were changed as follows.

After completion of the grain growth, 200.0 g of phenylcarbamoylated gelatin (substitution rate of amino group: 90%)
An aqueous solution containing (17.4% of the total amount of gelatin) was added, the pH was adjusted to 4.60 with acetic acid, the emulsion was sedimented, and the supernatant was drained. Subsequently, 17.0 liters of pure water at 40 ° C. was added and stirred, and then the operation of sedimenting the emulsion and draining the supernatant was repeated twice. Thereafter, 150.0 g of gelatin (39.1% of the total amount of gelatin added) was added and dispersed, and the pH was adjusted to 5.80 and the EAg to 70 mV at 40 ° C. The emulsion thus obtained is designated as EM-12.

From the electron micrograph of the obtained emulsion particles,
It was confirmed that the tabular grains had an average particle size of 1.52 μm (average diameter of the projected area in terms of circle), an aspect ratio of 7.7 (60% of the total projected area), and a particle size distribution of 15.4%.

<< Comparative Example Preparation of Emulsion EM-13 >> Emulsion EM
-4, after the completion of grain growth in the production method of -4, phenylcarbamoylated gelatin (substitution rate of amino group: 90%)
g (13.0 of the total amount of gelatin added in Emulsion EM-4)
%) And the pH is adjusted to 4.60 with acetic acid.
As a result, poor desalting occurred and no emulsion was obtained.

<< Preparation of Emulsion EM-14 of the Present Invention >> Emulsion EM
In the production method of -4, G-1 and G-2, and gelatin added after completion of desalting, were all phenylcarbamoylated gelatin (substitution rate of amino groups: 90%, total amount of gelatin: 9%).
The emulsion was the same as EM-4 except that the emulsion was changed to 6.5%).
M-14.

From the electron micrograph of the obtained emulsion particles,
It was confirmed that the tabular grains had an average particle size of 1.58 μm (average value of the circle-converted diameter of the projected area), an aspect ratio of 8.0 (60% of the total projected area), and a particle size distribution of 16.0%.

<< Comparative Example Preparation of Emulsion EM-15 >> Emulsion EM
EM-15 is an emulsion prepared in the same manner as EM-4 except that all the gelatin added in the production method of -4 is replaced with phenylcarbamoylated gelatin (substitution rate of amino group is 90%).

From the electron micrograph of the obtained emulsion particles,
It was confirmed that the tabular grains had an average particle size of 1.65 μm (average value of the circle-converted diameter of the projected area), an aspect ratio of 9.5 (60% of the total projected area), and a particle size distribution of 25.5%.

Table 1 summarizes the analysis results of the compositions, structures, and the like of the emulsions EM-1 to EM-15.

[0185]

[Table 1]

<< Chemical Sensitization / Spectral Sensitization Treatment of Each Emulsion >> While keeping each of the emulsions EM-1 to EM-15 at 52 ° C.,
The following sensitizing dyes SSD-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 so as to obtain optimum sensitivity-fogging for each emulsion, 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1,3,3a,
Stabilized by adding 7-tetrazaindene. The amount of sensitizing dye, sensitizer, and stabilizer added to each emulsion and the ripening time are as follows:
The sensitivity-fog relation at the time of 1/200 second exposure was set to be optimal.

<< Preparation / Evaluation of Coated Sample >> Each of the sensitized emulsions EM-1 to EM-15 was treated with the following coupler M
A dispersion in which CP-1 is dissolved in ethyl acetate and tricresyl phosphate and emulsified and dispersed in an aqueous solution containing gelatin;
A general photographic additive such as a spreading agent and a hardening agent was added to prepare a coating solution, which was coated on an undercoated cellulose triacetate film support by a conventional method, dried, and dried. 101-No. 114 were produced.

[0188]

[Table 2]

[0189]

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<< Evaluation of Photographic Performance >> Each obtained sample was subjected to wedge exposure for sensitometry using green light (G), and the relative sensitivity, granularity, pressure characteristics and reciprocity law failure were determined for the green optical density. The characteristics were evaluated.

The relative sensitivity is such that color development processing is started within 1 minute after exposure (1/200 second), and Dmin (minimum density)
It was obtained as a relative value of the reciprocal of the exposure amount giving a density of +0.15, and was shown as a value with the sensitivity of the sample 101 being 100 (1
The larger the value is, the higher the sensitivity is.

The granularity was determined by using the relative sensitivity evaluation sample
The density was expressed as a relative value of the standard deviation (RMS value) of the fluctuation of the density value generated when scanning the density of in + 0.5 with a microdensitometer having an aperture scanning area of 250 μm ² . The smaller the RMS value is, the better the graininess is and the more effective it is. Sample 1
The RMS value of 01 is shown as a value of 100 (a value smaller than 100 indicates an improvement).

The pressure characteristic is 23 ° C./55% (relative humidity)
After scanning at a constant speed with a load of 5 g applied to a needle having a tip having a radius of curvature of 0.025 mm using a scratch strength tester (manufactured by Shinto Kagaku) under the conditions described above, exposure (1/200 ″) was performed. , A development process, and at a density of Dmin and Dmin + 0.4, a density change ΔD
1 (cmin) and ΔD2 (Dmin + 0.4) were obtained, and ΔD1 and ΔD2 of the sample 101 were calculated as 100
(The smaller the value is, the more the value is 100, the more the value is improved.)

The reciprocity failure property was determined for each sample by exposure to green light (G) for 8 seconds (low illuminance exposure) or 1 /
Exposure for 10000 seconds (high illuminance exposure)
After performing the color development processing within minutes, the relative value of the reciprocal of the exposure amount giving a density of Dmin (minimum density) +0.15 was obtained, and the value was set to a value with the sensitivity of the sample 101 being 100 (relative to 100). , A larger value indicates higher sensitivity).

Processing Step Processing Time Processing Conditions Color development 3 minutes 15 seconds 38.0 ± 0.1 ° C. Bleaching 6 minutes 30 seconds 38.0 ± 3.0 ° C 3. Water washing 3 minutes and 15 seconds 24 to 41 ° C 4. 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Water washing 3 minutes 15 seconds 24-41 ° C 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ° C 7. Drying 50 ° C or less The composition of the processing solution used in each processing step is as follows.

<Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water was added to make 1 liter, and the pH was adjusted to 10.1. adjust.

<Bleaching solution> Iron ammonium ethylenediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and the pH was adjusted using aqueous ammonia. = 6.0.

<Fixing Solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to 1 liter, and the pH was adjusted to 6.0 with acetic acid.

<Stabilizing Solution> Formalin (37% aqueous solution) 1.5 cc KONIDAX (manufactured by Konica Corporation) 7.5 cc Add water to make 1 liter.

[0200]

[Table 3]

As shown in Table 3, the sample of the present invention is excellent in relative sensitivity and granularity, and at the same time, has improved pressure characteristics. In addition, fog improvement was obtained by including chemically modified gelatin. Further, it can be seen that the addition of the fine particles containing iridium has improved the reciprocity failure property without significantly impairing the relative sensitivity.

Example 2 (Preparation of photosensitive material sample) At 55 ° C., sensitizing dye SD-9 was added to emulsions EM-1 to EM-15 at 6.5 × 10 ^-4 mol per mol of silver and SD- 2.5 × 10 ^-4 mol per mol of silver was added and the mixture was aged for 15 minutes, and then a chemical sensitizer (sodium thiosulfate, chloroauric acid and potassium thiocyanate) was added and ripened. The addition amount of the chemical sensitizer and the ripening time after the addition of the chemical sensitizer were adjusted so that optimum sensitivity-fogging was obtained for each emulsion. After ripening, 1-phenyl-5-mercaptotetrazole was added in an amount of 10 m per mol of silver.
g and 4-hydroxy-6-methyl-1,3,3a,
It was stabilized by adding 500 mg of 7-tetraazaindene per mole of silver.

The sensitized EM-1 as described below was used as the 13th layer high-sensitivity blue color-sensitive layer, and a multilayer color photographic light-sensitive material sample (hereinafter referred to as a coated sample or simply a sample) was used. 201 was produced.

[0204] The amount represents the number of grams per 1m ^2. However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-2 0.123 CC-1 0.044 OIL-1 0.167 Gelatin 1.33 Second Layer (Intermediate) Layer) AS-1 0.160 OIL-1 0.20 Gelatin 0.69 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.20 Silver iodobromide b 0.29 Sensitizing dye SD -1 2.37 × 10 ^-5 sensitizing dye SD-2 1.2 × 10 ^-4 sensitizing dye SD-3 2.4 × 10 ^-4 sensitizing dye SD-4 2.4 × 10 ^-6 C- 1 0.32 CC-1 0.038 OIL-2 0.28 AS-2 0.002 Gelatin 0.73 Fourth layer (medium-speed red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 Sensitizing dye SD-1 4.5 × 10 ^-5 Sensitizing dye SD-2 2.3 × 10 ^-4 Sensitizing dye SD-3 4.5 × 10 ^-4 C -2 0.52 CC-1 0.06 DI-1 0.047 OIL-2 0.46 AS-2 0.004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 silver iodobromide d 1.18 sensitizing dye SD-1 3.0 × 10 ^-5 sensitizing dye SD-2 1.5 × 10 ^-4 sensitizing dye SD-3 3.0 × 10 ^-4 C-2 0.047 C-3 0.09 CC-1 0.036 DI-1 0.024 OIL-2 0.27 AS-2 0.006 Gelatin 1.28 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 Gelatin 1.00 7th layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0.19 Silver iodobromide b 0.062 Sensitizing dye SD-4 3.6 × 10 ^-4 sensitizing dye ^{SD-5 3.6 × 10 -4 M} -1 0.18 CM-1 0.033 OIL-1 0.22 AS-2 0.002 AS 3 0.05 gelatin 0.61 8th layer (intermediate layer) OIL-1 0.26 AS-1 0.054 gelatin 0.80 9th layer (medium-speed green-sensitive layer) Silver iodobromide e 0. 54 silver iodobromide f 0.54 sensitizing dye SD-6 3.7 × 10 ^-4 sensitizing dye SD-7 7.4 × 10 ^-5 sensitizing dye SD-8 5.0 × 10 ^-5 M- 1 0.17 M-2 0.33 CM-1 0.024 CM-2 0.029 DI-2 0.024 DI-3 0.005 OIL-1 0.73 AS-2 0.003 AS-30 0.035 Gelatin 1.80 10th layer (high-sensitivity green color-sensitive layer) Silver iodobromide f 1.19 Sensitizing dye SD-6 4.0 × 10 ^-4 Sensitizing dye SD-7 8.0 × 10 ^-5 sensitizing dye ^{SD-8 5.0 × 10 -5 M} -1 0.065 CM-1 0.022 CM-2 0.026 DI-2 0.003 DI-3 0 003 OIL-1 0.19 OIL-2 0.43 AS-2 0.014 AS-3 0.017 Gelatin 1.23 11th layer (yellow filter layer) Yellow colloidal silver 0.05 OIL-1 0.18 AS -1 0.16 Gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide g 0.22 Silver iodobromide a 0.08 Silver iodobromide h 0.09 Sensitizing dye SD- 9 6.5 × 10 ^-4 sensitizing dye SD-10 2.5 × 10 ^-4 YA 0.77 DI-4 0.017 OIL-1 0.31 AS-2 0.002 Gelatin 1.29 13 layers (high-sensitivity blue-sensitive layer) Emulsion EM-1 1.02 YA 0.23 OIL-1 0.10 AS-2 0.004 Gelatin 1.20 14th layer (first protective layer) iodine Silver bromide i 0.30 UV-1 0.055 UV-2 0.110 OIL-2 .30 gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 gelatin 0.55 Characteristics of the above silver iodobromide Is shown below (the average particle size is one side length of a cube having the same volume).

[0206]

[Table 4]

The above-mentioned sensitizing dyes are added to the above silver iodobromides a to i, and after ripening, triphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate are added, and the mixture is treated in a conventional manner. Chemical sensitization was performed to optimize the fog and sensitivity.

Incidentally, in addition to the above composition, a coating aid Su-
1, Su-2, Su-3, dispersion aid Su-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1, AF-2, inhibitors AF-3, AF-4, AF-
5. Hardeners H-1, H-2 and preservative Ase-1 were added.

The structures of the compounds used in the above samples are shown below.

[0210]

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[0211]

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[0212]

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[0213]

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[0214]

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[0215]

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[0216]

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[0219]

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[0218]

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Emulsions EM-2 to EM-15 (however, EM-1
Also, as shown in Table 5, by using each of these emulsions instead of the emulsion EM-1 of the sample 201 as shown in Table 5, the multilayer color photographic light-sensitive material samples 202 to 214 were similarly obtained.
Was prepared. The combination of each sample and emulsion is shown.

[0220]

[Table 5]

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

The following were used as the color developing solution, bleaching solution, fixing solution, stabilizing solution and replenishers thereof.

Color developing solution and color developing replenisher Developer replenisher Water 800 cc 800 cc 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 up to 1 liter. The color developing solution was adjusted to pH 10.06 using potassium hydroxide or 20% sulfuric acid; Adjust to .18.

Bleach and Bleach Replenisher Bleach Replenisher Water 700 cc 700 cc Iron (III) 1,3-diaminopropanetetraacetate 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 To 1 liter, and adjust the pH of the bleaching solution to 4.4 and the pH of the replenisher to 4.0 using ammonia water or glacial acetic acid.

Fixing Solution and Fixing Replenisher Fixing Solution Replenisher Water 800 cc 800 cc Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g The fixing solution was adjusted to pH 6.2 using aqueous ammonia or glacial acetic acid. The replenisher is pH6. After adjusting to 5, add water to make 1 liter.

Stabilizing Solution and Stabilizing Replenisher Water 900 cc 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 cc Add water to make 1 liter, and adjust the pH to 8.5 using ammonia water or 50% sulfuric acid.

Each characteristic was evaluated as follows.

A density measurement was performed using blue light. The density of the unexposed portion was defined as the fog density.

Table 6 shows the results of the characteristic evaluations.

[0230]

[Table 6]

[0231] The photographic sensitivity is obtained by calculating the optical density as fog density + 0.
The reciprocal of the exposure required to give a density of 2 was determined, and EM
The value of -1 is set to 100, and is shown as a relative value.
(The higher the value, the higher the sensitivity is to 100.)

The latent image storability was evaluated by treating each sample under three conditions. Condition A: Exposure, storage in a freezer (-20 ° C.) until immediately before development, Condition B: Exposure, development after storage at 25 ° C., 60% relative humidity for 30 days, Condition C
After exposure, storage was performed at a temperature of 55 ° C. and a relative humidity of 80% for 3 days, followed by development. For each sample, the optical density is the fog density +
Find the reciprocal of the exposure required to give a density of 0.2,
Assuming that the value of the condition A is 100, the values of the conditions B and C are respectively converted into the range of variation of the relative value. It is shown as the image fluctuation width.

Further, each sample was stored in a freezer (−20 ° C.) before exposure, and after storage at a temperature of 55 ° C. and a relative humidity of 60% for 20 days, the increase in fog density of the exposed and developed sample was measured over time. It was shown as fogging variation and was used as an index of storage stability over time.

The pressure characteristic is 23 ° C./55% (relative humidity)
Under the conditions described above, using a scratch strength tester (manufactured by Shinto Kagaku), applying a load of 5 g to a needle having a radius of curvature of 0.025 mm at the tip, scanning at a constant speed, performing exposure and development processing, Dm
At the density of in and Dmin + 0.4, the density change ΔD1 (Dmin) of the part to which the load is applied,
And ΔD2 (Dmin + 0.4) were obtained, and the values of ΔD1 and ΔD2 of the sample 201 were each set to 100 (the smaller the value, the better the value of 100).

As is clear from the results shown in Table 6, the samples 204 to 206 and 208 of the present invention each containing the emulsion of the present invention.
To 213 have high sensitivity and improved latent image / pressure characteristics. Among these, the sample 211 using the emulsion EM-11 satisfying the best combination of the present invention is particularly excellent.

[0236]

According to the present invention, high sensitivity and low fogging, excellent granularity, reciprocity failure suitability, pressure fog / desensitization and latent image preservability, temperature / humidity dependence of latent image fluctuation, aging And a silver halide color photographic light-sensitive material having an improved silver halide emulsion.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of an apparatus for producing a silver halide emulsion of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reaction container 2 Stirring mechanism 3 Dispersion medium 4 Silver addition line 5 Halide addition line 6 Dispersion medium addition line 7 Addition line 8 Liquid take-out line 9 Liquid return line 10 Permeate discharge line 11 Permeate return line 12 Ultrafiltration unit 13 Circulation Pump 14 Flow meter 15, 16, 17 Pressure gauge 18 Pressure adjusting valve 19 Flow adjusting valve 20 Silver addition valve 21 Halide addition valve 22 Liquid extraction valve 23, 24, 25 Valve 26 Ultrafiltration permeate 27 Permeate receiver 28 scales

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[Procedure amendment]

[Submission date] July 18, 2000 (2007.1.
8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction contents]

The central region of the main plane of the tabular grain as referred to herein means the area inscribed on the main plane of the tabular grain at the contour of the main plane.
80% of the radius of the inscribed circle when drawing a circle with a diameter of
It has a radius, and is a region having a thickness of a tabular grain in the circular portion. The center of the main plane is the inscribed circle
Means the center of Further, the outer peripheral region of a tabular grain, have a surface area corresponding to the outer annular region of the central region, and means a region having a thickness of a tabular grain.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/047 G03C 1/047 1/08 1/08 1/09 1/09

Claims (6)

[Claims] 1. A silver halide emulsion containing silver halide grains and a dispersion medium, wherein all silver halide grains contained in the silver halide emulsion have a variation coefficient of particle size of 20% or less, and 50% or more of the projected area of the silver halide grains are tabular silver halide grains having an aspect ratio of 5 or more, including a step of forming the grains in a reduction sensitizing atmosphere during the formation of the tabular silver halide grains, Further, 30% or more (number ratio) of the tabular silver halide grains have dislocation lines in the central region and the peripheral region of the main plane, and there are 10 or more dislocation lines in the peripheral region per grain. A silver halide emulsion wherein chemically modified gelatin is added in an amount of 15% by weight or more and less than 100% by weight of the total amount of gelatin added during the silver halide emulsion forming step. 2. A silver halide emulsion containing silver halide grains and a dispersion medium, wherein all silver halide grains contained in the silver halide emulsion have a variation coefficient of particle size of 20% or less, and 50% or more of the projected area of the silver halide grains are tabular silver halide grains having an aspect ratio of 5 or more, including a step of forming the grains in a reduction sensitizing atmosphere during the formation of the tabular silver halide grains, In addition, 30% or more (number ratio) of the tabular silver halide grains have dislocation lines in the central region and the peripheral region of the main plane, and there are 10 or more dislocation lines in the peripheral region per grain. The outer periphery of the tabular silver halide grains contains at least one polyvalent metal compound, and the chemically modified gelatin of the gelatin added during the silver halide emulsion forming step is 15% by weight of the total amount of gelatin added. % Or more 1 A silver halide emulsion characterized by being added in an amount of less than 00% by weight. 3. A silver halide emulsion containing silver halide grains and a dispersion medium, wherein all silver halide grains contained in the silver halide emulsion have a variation coefficient of particle size of 20% or less, and At least 50% of the projected area of the silver halide grains is tabular silver halide grains having an aspect ratio of 5 or more. During the formation of the tabular silver halide grains, grains are formed under a reduction-sensitized atmosphere, and ultrafiltration is performed. A step of forming grains while appropriately extracting an aqueous solution containing a salt from the reaction solution by the method, and 30% or more (number ratio) of the tabular silver halide grains are dislocated to the central region and the peripheral region of the main plane. And at least 10 dislocation lines per grain in the outer peripheral region are present, and the chemically modified gelatin is at least 15% by weight of the total amount of gelatin added during the silver halide emulsion forming step. A silver halide emulsion characterized by being added in an amount of less than 100% by weight. 4. A silver halide emulsion containing silver halide grains and a dispersion medium, wherein the variation coefficient of the particle size of all silver halide grains contained in the silver halide emulsion is 20% or less, 50% or more of the projected area of the silver halide grains are tabular silver halide grains having an aspect ratio of 5 or more, including a step of forming the grains in a reduction sensitizing atmosphere during the formation of the tabular silver halide grains, In addition, 30% or more (number ratio) of the tabular silver halide grains have dislocation lines in the central region and the peripheral region of the main plane, and there are 10 or more dislocation lines in the peripheral region per grain. When the average silver iodide content of the outermost layer of the silver halide grains is A mol% in the main plane portion and B mol% in the side surface portion, A> B, and during the silver halide emulsion forming step, Among the gelatin added, chemically modified gelatin 15% by weight or more of the total amount added
A silver halide emulsion characterized by being added in an amount of less than 00% by weight. 5. A silver halide emulsion containing silver halide grains and a dispersion medium, wherein all silver halide grains contained in the silver halide emulsion have a variation coefficient of particle size of 20% or less, and At least 50% of the projected area of the silver halide grains is tabular silver halide grains having an aspect ratio of 5 or more. During the formation of the tabular silver halide grains, grains are formed under a reduction sensitizing atmosphere, and further, an ultrafiltration method is used. And forming a grain while appropriately extracting an aqueous solution containing a salt from the reaction product solution, and 30% or more (number ratio) of the tabular silver halide grains are dislocation lines in the central region and the peripheral region of the main plane. Wherein at least 10 dislocation lines per grain are present in the outer peripheral region, and at least one or more polyvalent metal compounds are contained in the outer peripheral portion of the tabular silver halide grains. Silver particles When the average silver iodide content of the outermost layer is A mol% in the main plane portion and B mol% in the side surface portion, A> B
Wherein the chemically modified gelatin of the gelatin added during the silver halide emulsion forming step is 1% of the total amount of gelatin added.
A silver halide emulsion which is added in an amount of 5% by weight or more and less than 100% by weight. 6. A silver halide color photographic light-sensitive material having a silver halide emulsion layer on a support, wherein a silver halide emulsion contained in at least one of the emulsion layers is provided.
6. A silver halide color photographic light-sensitive material, which is the silver halide emulsion according to any one of items 1 to 5.