JP2003322921A - Silver halide photographic emulsion and silver halide photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic emulsion and a silver halide photosensitive material which suppress lowering of sensitivity and deterioration of image quality due to natural radiation. <P>SOLUTION: In the silver halide emulsion, 70-100% of the grain projected area is occupied by tabular grains having (1) AR of 12-500 and (a) 30≤FD30AR≤300 or (b) D of 2.0-50 μm and 9≤FD30D≤200, (2) AR of 15-500 and (a) 50≤FD10AR≤300 or (b) D of 2.5-50 μm and 15≤FD10D≤200, or (3) AR of 12-500, D of 2.0-50 μm, ≥30 dislocation lines in the fringe part and dislocation lines in the principal plane, wherein AR; aspect ratio, FD30, FD10; the proportion (%) of grains having ≥30 or ≥10 dislocation lines in the fringe, D; average grain diameter, FD30AR, FD10AR; the product of FD30 or FD10 and Log<SB>10</SB>(AR), FD30D, FD10D; the product of FD30 or FD10 and Log<SB>10</SB>(D). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material.
The present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material in which sensitivity deterioration and image quality deterioration due to radiation are improved.

[0002]

2. Description of the Related Art In recent years, the demand for quality of silver halide photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) has become higher and higher. Higher standards of quality are required for the basic properties and storability of the material. In particular, recently, with the widespread use of compact zoom cameras and lens-equipped films generally referred to as single-use cameras, it has become possible to easily take pictures and they are used in various places. As a result, it is expected that the vehicle will be left under severe conditions, for example, in a car in summer. Therefore, the photographic material for photographing has been required to have higher performance with respect to storage stability in an unexposed state and between exposure and development. The conventional technology is insufficient for the above-mentioned strict requirements, and further improvement is required. On the other hand, with the increase in sensitivity of silver halide photographic light-sensitive materials, a small amount of radiation that is always present in the natural environment (also called natural radiation).
Due to the above, problems such as increased fog during storage of the silver halide photographic light-sensitive material, deterioration of sensitivity and deterioration of graininess have been considered. It is known that these effects of natural radiation can be suppressed to some extent by reducing the amount of silver coated on the silver halide photographic light-sensitive material, but reduction of the amount of coated silver causes a decrease in sensitivity and a deterioration in image quality. There is a limit to compatibility with prevention of performance deterioration due to natural radiation. Therefore, it has been desired to develop a silver halide photographic emulsion which has not only high sensitivity and high image quality but also improved performance deterioration due to the above radiation.

[0003]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic emulsion and a silver halide photographic light-sensitive material in which sensitivity deterioration and image quality deterioration due to natural radiation are improved.

[0004]

The above objects of the present invention have been achieved by the following constitutions. (1) A silver halide photographic emulsion in which tabular silver halide grains occupy 70% to 100% of the projected area of all grains, and the tabular silver halide grains have an average aspect ratio in the range of 12 to 500. The tabular silver halide grain number ratio (%) (FD30) and average aspect ratio (AR) having 30 or more dislocation lines in the fringe portion of the tabular silver halide grain in the silver halide photographic emulsion. And 3
A silver halide photographic emulsion characterized by satisfying a relationship of 0 ≦ (FD30) × Log ₁₀ (AR) ≦ 300.
(First Invention) (2) FD30 and AR are 50 ≦ (FD30) × Log
_The silver halide photographic emulsion according to (1) above, wherein the relationship of ₁₀ (AR) ≦ 300 is satisfied. (Second invention) (3) FD30 and AR are 70 ≦ (FD30) × Log
_The silver halide photographic emulsion according to (1) above, wherein the relationship of ₁₀ (AR) ≦ 300 is satisfied. (Third invention) (4) The tabular silver halide grains occupy 70% to 100% of the projected area of all the grains, and the tabular silver halide grains have an average aspect ratio of 15 to 500. A silver halide photographic emulsion having a tabular silver halide grain number ratio (%) (FD10) and an average of 10 or more dislocation lines in the fringe portion of the tabular silver halide grain in the silver halide photographic emulsion. Aspect ratio (AR) is 5
A silver halide photographic emulsion characterized by satisfying the relationship of 0 ≦ (FD10) × Log ₁₀ (AR) ≦ 300.
(Fourth Invention) (5) FD10 and AR are 80 ≦ (FD10) × Log
_The silver halide photographic emulsion as described in (4) above, wherein the relationship of ₁₀ (AR) ≦ 300 is satisfied. (Fifth
Invention) (6) FD10 and AR are 100 ≦ (FD10) × Lo
The silver halide photographic emulsion according to (4) above, wherein the relationship of g ₁₀ (AR) ≦ 300 is satisfied. (Sixth Invention) (7) A tabular silver halide grain having a tabular shape having an average projected area circle conversion grain size of 0.1 to 50 μm and an average thickness of 0.005 to 0.1 μm. The silver halide photographic emulsion as described in any one of (1) to (6) above, which is a silver halide grain. (Seventh invention)

(8) 70% to 100 of the projected area of all grains
% Of the tabular silver halide grains, and the tabular silver halide grains have an average aspect ratio in the range of 12 to 500. The average projected area circular equivalent grain size (μm) of the silver halide grains is in the range of 2.0 to 50, and 30 or more grains are contained in the fringe portion of the tabular silver halide grains in the silver halide photographic emulsion. Tabular silver halide grain number ratio (%) having dislocation lines (FD30)
And projected area of tabular silver halide grains
The average (D) of m) is 9 ≦ (FD30) × Log
_A silver halide photographic emulsion characterized by satisfying the relation of ₁₀ (D) ≦ 200. (Eighth Invention) (9) FD30 and D are 15 ≦ (FD30) × Log ₁₀
(D) The silver halide photographic emulsion as described in (8) above, wherein the relationship of ≦ 200 is satisfied. (9th invention) (10) FD30 and D are 20 <= (FD30) * Log.
_The silver halide photographic emulsion as described in (8) above, wherein the relationship of ₁₀ (D) ≦ 200 is satisfied. (10th
Invention) (11) A silver halide photographic emulsion in which tabular silver halide grains occupy 70% to 100% of the projected area of all grains and the tabular silver halide grains have an average aspect ratio of 15 to 500. And the projected area of the tabular silver halide grains in the silver halide photographic emulsion in terms of circles (μ
m) is in the range of 2.5 to 50, and the tabular silver halide grain number ratio has 10 or more dislocation lines in the fringe portion of the tabular silver halide grains in the silver halide photographic emulsion. (%) (FD10) and the average (D) of the projected area circle conversion grain size (μm) of the tabular silver halide grains satisfy the relation of 15 ≦ (FD10) × Log ₁₀ (D) ≦ 200. A silver halide photographic emulsion characterized by. (Eleventh Invention) (12) FD10 and D are 20 ≦ (FD10) × Log
₁₀ (D) ≦ 200, above (11)
The silver halide photographic emulsion according to 1. (Twelfth Invention) (13) FD10 and D are 30 ≦ (FD10) × Log
_The silver halide photographic emulsion as described in (11) above, wherein the relationship of ₁₀ (D) ≦ 200 is satisfied. (First
3 invention) (14) The tabular silver halide grains have an average thickness of 0.0
Any one of the above (8) to (13), which is a tabular silver halide grain having a size of 05 to 0.1 μm.
A silver halide photographic emulsion as described in the above item. (14th invention) (15) A silver halide photographic emulsion containing tabular silver halide grains, wherein the silver halide photographic emulsion has an average aspect ratio of 12 to 500. The average grain size of the projected area of the emulsion in terms of circle is 2.0 to
50 μm range, 70% to 1 of the projected area of all particles
00% is tabular silver halide grains, the tabular silver halide grains have 30 or more dislocation lines in the fringe portion, and the tabular silver halide grains have dislocation lines in the main plane portion. A silver halide photographic emulsion comprising:
(15th invention) (16) 50% to 100% of tabular silver halide grains
The silver halide photographic emulsion as described in any one of (1) to (15) above, wherein the (number) is a tabular silver halide grain having a dislocation line on the principal plane. (Sixteenth Invention) (17) At least one silver halide emulsion layer containing the silver halide photographic emulsion according to any one of (1) to (16) above is provided on a support. And a silver halide photographic light-sensitive material. (17th invention)

The details of the present invention will be described below. In the silver halide photographic emulsion of the present invention, tabular silver halide grains occupy 70% to 100% of the projected area of all grains, and tabular silver halide grains further account for 80% of the projected area of all grains. It is preferable that the tabular silver halide grains account for 90% to 1% of the projected area of all grains.
It is particularly preferable to occupy 00%. The tabular silver halide grains (hereinafter, also simply referred to as tabular grains) of the silver halide photographic emulsion of the present invention are crystallographically classified as twins. A twin is a crystal having one or more twin planes in one grain, and the morphology of twins in silver halide grains is classified by Klein and Moiser in the report “Photog.
raphishé Korrespondenz "99
Volumes 99, 100, 57.
In the present invention, tabular silver halide grains preferably have two or more twin planes parallel to each other within the grain. These twin planes are present substantially parallel to the plane (referred to as the main plane) having the largest area among the planes forming the surface of tabular grains. A particularly preferred form in the present invention is a case having two twin planes parallel to the main plane. In the present invention, the number of silver halide grains having two twin planes parallel to the main plane is preferably 70% or more, more preferably 80% or more,
It is particularly preferably 90% or more. In the tabular grains according to the present invention, the average distance between two or more twin planes parallel to the main plane is preferably 10 to 160Å, and 10 to 14Å is preferable.
0Å is more preferable, and 10 to 120Å is more preferable. In the tabular grains according to the present invention, the variation coefficient of the distance between twin planes is preferably 40% or less, more preferably 30% or less. The twin plane can be observed with a transmission electron microscope. Specifically, a silver halide emulsion is coated on a support so that the main planes of the tabular silver halide grains contained therein are oriented substantially parallel to each other to prepare a sample, which is then prepared using a diamond cutter. The presence of twin planes can be confirmed by cutting to obtain a thin slice having a thickness of about 0.1 μm and observing this thin slice with a transmission electron microscope.

In the present invention, the average of the distances between two or more twin planes parallel to the principal plane is determined by observing a section using the above-mentioned transmission electron microscope. It can be obtained by arbitrarily selecting 100 or more tabular silver halide grains in the plane, determining the distances between twin planes, and averaging them. In the present invention, the distance between twin planes is a factor that affects the supersaturated state during nucleation,
For example, gelatin concentration, temperature, iodine ion concentration, pB
It can be controlled by appropriately selecting a combination of various factors such as r, ion supply rate, stirring rotation speed, and gelatin type. In general, the higher the supersaturation state of nucleation, the smaller the distance between twin planes. Details of the supersaturation factor are described in, for example, JP-A-63-92942 or JP-A-1-213637, and this description can be referred to.

In the first invention, the eighth invention and the fifteenth invention, the tabular silver halide grains have an average aspect ratio of 1
The average aspect ratio of the tabular silver halide grains is preferably in the range of 15 to 500, more preferably 25 to 500, and more preferably 4 to 500.
It is more preferably in the range of 0 to 500. In the fourth and eleventh inventions, the tabular silver halide grains have an average aspect ratio in the range of 15 to 500, but the tabular silver halide grains have an average aspect ratio of 25.
It is preferably in the range of 500 to 500, and more preferably in the range of 40 to 500. The aspect ratio of a silver halide grain can be obtained by the following equation by determining the grain size and grain thickness of each silver halide grain. Aspect ratio = grain size / grain thickness The tabular silver halide grain according to the present invention is a tabular silver halide grain having a (111) main plane having two twin planes parallel to the main plane. preferable. In the first invention and the fourth invention, the average grain size of the tabular silver halide grains in terms of projected area circle equivalent grain size is preferably in the range of 0.1 to 50 μm, and in the range of 1.0 to 50 μm. More preferably, and most preferably in the range of 3.5 to 50 μm. In the eighth invention and the fifteenth invention,
The tabular silver halide grains have an average grain diameter of 2.0 to 50 μm in terms of a projected area circle converted grain size, but the tabular silver halide grains have a projected area in terms of a circle converted grain size of 3.5. It is preferably in the range of ˜50 μm. 11th
In the present invention, the average grain size of the tabular silver halide grains in terms of projected area circle equivalent grain size is in the range of 2.5 to 50 μm, preferably 3.5 to 50 μm.

In the present invention, the average grain size of tabular grains is the arithmetic average of grain size ri. However, the number of measured particles was indiscriminately set to 1,000 or more, and three significant digits and the least significant digit were rounded off. Here, the grain size ri is assumed to be a circular image having the same area as the area of the projected image when viewed from a direction perpendicular to the main plane of the tabular silver halide grain, and is represented by the diameter of the assumed circular image. The particle size (projected area circle converted particle size).
The average thickness of tabular silver halide grains in the silver halide photographic emulsion of the present invention is preferably 0.25 μm or less, more preferably 0.005 to 0.20 μm, and 0.005 to 0. Particularly preferably, it is 10 μm. In the present invention, the tabular silver halide grains preferably have a variation coefficient of thickness of 40% or less, 30
% Or less is more preferable. In the present invention,
The projected area and thickness of individual grains for calculating the grain size and aspect ratio of silver halide grains can be determined by the following method. A silver halide grain was coated with a latex ball having a known particle diameter as an internal standard so that the main plane of the tabular grain was oriented parallel to the substrate to prepare a sample, and carbon deposition was performed from a certain angle. After shadowing the particles, a replica sample is prepared by a normal replica method. Next, an electron micrograph of the same sample is taken, and the projected area and thickness of each particle are obtained using an image processing device or the like. In this case, the projected area of the particles is based on the projected area of the latex ball of known particle size that is the internal standard, and
The thickness of the particles can be calculated based on the length of the shadow of the latex ball having a known particle size as an internal standard. In the silver halide photographic emulsion of the present invention, arbitrary silver halide grains such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution can be used in addition to the tabular grains. For a silver halide photographic emulsion, when the grain size distribution (coefficient of variation of grain size) is defined by the following formula, the grain size distribution is 5
Silver halide emulsions of less than 0%, more preferably less than 40% are preferred. Particle size distribution (%) = (standard deviation of particle size distribution / average particle size) ×
100 The average particle size and the standard deviation of the particle size distribution are obtained from the particle size ri defined above.

In the tabular silver halide grains in the present invention, 70% or more of the number of grains are preferably hexagonal tabular silver halide grains. Here, the hexagonal tabular silver halide grain is a replica sample coated with silver halide grains so that the main plane is oriented parallel to the substrate, and the ratio of the lengths of adjacent linear sides is 0.1. It refers to hexagonal tabular silver halide grains in the range of 10 to 10. A more preferable hexagonal tabular silver halide grain is a hexagonal tabular silver halide grain having a ratio of lengths of adjacent straight sides of 0.2 to 5. In the silver halide photographic emulsion of the present invention, the average silver iodide content of silver halide grains is 0.1 to
It is preferably 40 mol% and 0.3 to 30 mol%
Is more preferable, and 0.5 to 20 mol% is the most preferable. The silver iodide content of silver halide grains is determined by the EPMA method (Electron Probe Mi
It can be determined by the Cro Analyzer method). Specifically, a sample in which silver halide grains are well dispersed so that they do not come into contact with each other is prepared, and the sample is subjected to -10 with liquid nitrogen.
The silver iodide content of each silver halide grain is determined by irradiating an electron beam while cooling to 0 ° C. or less and determining the characteristic X-ray intensities of silver and iodine emitted from each silver halide grain. You can decide. The average silver iodide content is determined by determining the silver iodide content of 100 or more silver halide grains by the above method and averaging the content. Further, the tabular silver halide grain according to the present invention is preferably a silver halide grain having a plurality of silver halide phases having different silver iodide contents inside the silver halide grain. The number of a plurality of silver halide phases having different silver iodide contents inside the grain is arbitrary, but is preferably 3 or more, more preferably 4 or more, and further preferably 5 or more. preferable. Further, core-shell type silver halide grains in which the silver iodide content in the silver halide phase outside the grain is higher or lower than the silver iodide content in the silver halide phase inside the grain are also preferable.

The tabular silver halide grains according to the present invention are
It has at least a five-phase structure including a central part, an internal phase, a first high iodine localized phase, an intermediate phase, a second high iodine localized phase, and a shell phase described in JP-A-2000-305211, and The ratio of the internal phase is 5% or more and 60% or less of the total grain silver amount, the average silver iodide content is 0 mol% or more and 10 mol% or less, and the ratio of the first and second high iodine localized phases Are 0.5% or more and 5% or less of the total grain silver amount, the average silver iodide contents are higher than 40 mol% and 100 mol% or less, respectively, and the ratio of the intermediate phase is 10% or more of the total grain silver amount. 70% or less, the average silver iodide content is 0 mol% or more and 10 mol% or less, the ratio of the shell phase is 10% or more and 50% or less of the total grain silver amount, and the average silver iodide content is 0 mol% or less. % To 10 mol% inclusive, tabular silver halide grains described in JP-A-2000-321699 Core from parts, the first shell, second shell, third shell has at least 5-layer structure of the fourth shell, and 5% to 50% with respect to the ratio of the core total silver
Below, the average silver iodide content is 0 mol% or more and 3 mol% or less, and the ratio of the first shell is 5% or more and 3% with respect to the total silver amount.
0% or less, the average silver iodide content is 3 mol% or more and 10 mol% or less, and the ratio of the second shell is 10% with respect to the total silver amount.
% Or more and 30% or less, the average silver iodide content is 0% or more and 3% or less, and the ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, the average iodide content is The silver content is 40 mol% or more and 100 mol% or less, the ratio of the fourth shell is 10% or more and 40% or less, and the average silver iodide content is 3 mol% or more and 10 mol% or less. It is also preferable that the tabular silver halide grains are Further, the tabular silver halide grains according to the present invention are disclosed in JP-A-11-153841.
No. average silver iodide content I ₁ of the main planar portion of the surface layer described in Japanese, the average silver iodide content I ₂ of the side portion, I _1> I ₂
Tabular silver halide grains having the following relation, JP-A-2000-
Tabular silver halide grains having a plurality of silver halide phases described in JP-A-258863, JP-A-2001-100346 and JP-A-2001-242576 are also preferable.

The tabular silver halide grains according to the present invention are
Although it has dislocation lines in the fringe portion, dislocation lines other than the fringe portion may be present, and the form of these dislocation lines is arbitrary, and examples of such forms include the following: A linearly existing dislocation line or a curved dislocation line can be selected. Further, it may exist throughout the grain or in a specific portion of the grain, for example, a form in which a dislocation line exists on the main plane or a form in which a dislocation line exists near the apex. The tabular silver halide grains according to the present invention preferably have dislocation lines on the main plane. In addition, tabular silver halide grains having a grain size of 30
% To 100% (number) preferably have dislocation lines on the principal plane, and particularly 50% to 100% (number) preferably have dislocation lines on the principal plane. It is also preferable that dislocation lines exist in the fringe portion and the main plane portion. In the present invention, the tabular silver halide grain having a dislocation line in the fringe portion means that the dislocation line exists near the outer periphery of the tabular grain, near the ridgeline, or near the apex. To be more specific, the fringe portion means a center of the principal plane of the tabular grains, that is, a center of gravity when the principal plane is regarded as a two-dimensional figure and an edge, which are observed by observing the tabular grains perpendicularly to the principal plane. When the length of the line segment is L, it refers to an area outside the figure connecting the points having the length of 0.50 L of the line connecting from the center of gravity in the direction of each edge on the main plane.

In the first invention, silver halide photographic milk is used.
30 in the fringe portion of the tabular silver halide grains in the agent.
Number ratio of tabular silver halide grains having one or more dislocation lines
The ratio (%) (FD30) and the average aspect ratio (AR) are
30 ≦ (FD30) × Log _TenRelationship of (AR) ≦ 300
Is satisfied, but further 50 ≦ (FD30) × Log
_TenIt is preferable that the relationship of (AR) ≦ 300 is satisfied, and 7
0 ≦ (FD30) × Log _Ten(AR) ≤ 300
It is particularly preferable to satisfy. In the fourth invention, halo
The tabular silver halide grain flux in a silver genide photographic emulsion.
A tabular halogen having 10 or more dislocation lines in the fringe part
Silver halide grain number ratio (%) (FD10) and average aspect ratio
Ratio (AR) is 50 ≦ (FD10) × Log _Ten(AR)
The relationship of ≦ 300 is satisfied, but 80 ≦ (FD1
0) x Log_Ten(AR) ≦ 300 may be satisfied
Preferably, 100 ≦ (FD10) × Log_Ten(AR) ≤
It is particularly preferable to satisfy the relationship of 300. Also, the eighth
In the present invention, tabular grains in silver halide photographic emulsions
More than 30 dislocation lines in the fringe of silver halide grains
Number of tabular silver halide grains having (%) (FD3
0) and projected area of tabular silver halide grains in terms of circles
The average (D) of (μm) is 9 ≦ (FD30) × Log_Ten
(D) satisfies the relationship of ≦ 200, but further satisfies 15 ≦ (F
D30) x Log_Ten(D) Satisfies the relationship of ≦ 200
Is preferred, and 20 ≦ (FD30) × Log_Ten(D) ≦ 2
It is particularly preferable to satisfy the relationship of 00. Also, the eleventh
In the present invention, tabular grains in silver halide photographic emulsions
There are 10 or more dislocation lines in the fringe of silver halide grains.
Number of tabular silver halide grains having (%) (FD1
0) and projected area of tabular silver halide grains in terms of circles
The average (D) of (μm) is 15 ≦ (FD10) × Log
_Ten(D) satisfies the relationship of ≦ 200, but further 20 ≦
(FD10) x Log_Ten(D) satisfies the relationship of ≦ 200
Preferably, 30 ≦ (FD10) × Log_Ten(D)
It is particularly preferable to satisfy the relationship of ≦ 200.

Dislocation lines of silver halide grains are, for example,
J. F. Hamilton, Photo. Sci. En
g. , Vol. 11, 57 (1967) and T.W. Shi
Ozawa, J .; Soc. Photo. Sci. Japan
n, Vol. 35, 213 (1972) and can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, dislocation lines should be placed on a mesh for an electron microscope with the silver halide grains taken out from the emulsion, taking care not to apply pressure to the grains so that new dislocation lines are generated. Out, etc.)
The sample can be cooled so as to prevent it and observed by a transmission method. At this time, the thicker the particles, the more difficult it is for an electron beam to pass therethrough. Therefore, in order to observe more clearly, a high acceleration voltage type (200 kV for particles of 0.25 μm thickness)
It is preferable to use the above electron microscope. From the grain photograph obtained by such a method, the number and position of dislocation lines in each grain can be known. In the tabular silver halide grain according to the present invention, it is preferable that dislocation lines are present in the fringe portion and the main plane portion other than the fringe portion.

In the present invention, as a method of introducing dislocation lines into silver halide grains, for example, a method of adding an aqueous solution containing an iodine ion such as potassium iodide and a water-soluble silver salt solution by double jet, and iodide Examples thereof include a method of adding a fine grain emulsion containing silver, a method of adding only a solution containing iodide ions, and a method of using an iodide ion releasing agent as described in JP-A-6-11781. Can be used to form dislocations that are the origin of dislocation lines at desired positions. Among these methods, a method of adding an aqueous solution containing iodide ions and a water-soluble silver salt solution by a double jet, a method of adding fine silver iodide grains, and a method of using an iodide ion-releasing agent are preferable.

Examples of the iodine ion releasing agent include, for example,
Examples thereof include compounds represented by the following general formula (1) that release iodine ions by reaction with a base or a nucleophile. General formula (1) RI In general formula (1), R represents a monovalent organic group. The monovalent organic group represented by R is preferably an organic group having 30 or less carbon atoms, more preferably 20 or less, and further preferably 10 or less. Examples of the monovalent organic group represented by R include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, An alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group are preferable. The monovalent organic group represented by R preferably has a substituent, and the substituent may be further substituted with another substituent. Preferred substituents are halide, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, heterocyclic group, acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, aryl. Sulfonyl group, sulfamoyl group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, urethane group, sulfonylamino group, sulfinyl group, phosphoric acid amide group, alkylthio group, arylthio group, cyano group, sulfo group, carboxyl Group, hydroxy group, nitro group and the like. As the iodine ion releasing agent represented by the general formula (1), iodoalkanes, iodoalcohols, iodocarboxylic acids, iodoamides and their derivatives are preferable, and iodoamides, iodoalcohols and their derivatives are more preferable, and heterocyclic groups are preferable. More preferred are iodoamides substituted with. The most preferred example is (iodoacetamido) benzene sulfonate. Specific examples of the iodine ion releasing agent that can be preferably used in the present invention are shown below.

[0017]

[Chemical 1]

In the present invention, when the iodine ion-releasing agent and the nucleophilic reagent are reacted to release the iodine ion, examples of the nucleophilic reagent include hydroxide ion, sulfite ion, thiosulfate ion, sulfinate salt, and carboxylate. Acid salts, ammonia, amine cheeks, alcohols, ureas, thioureas,
Phenols, hydrazines, sulfides, hydroxamic acids and the like can be used. Among these,
Hydroxide ions, sulfite ions, thiosulfate ions, sulfinates, carboxylates, ammonia and amines are preferable, and hydroxide ions and sulfite ions are more preferable. An example of preferable reaction conditions when introducing a dislocation line into a silver halide grain with an iodine ion releasing agent is shown below. The reaction temperature is preferably 30 to 80 ° C., and 4
It is more preferably 0 to 70 ° C. The pAg immediately before the introduction of the dislocation lines is preferably 7.0 or more and 10.0 or less, and more preferably 7.5 or more and 9.5 or less.
The amount of iodide ion-releasing agent added is preferably 1 to 5 mol% with respect to the total amount of silver halide after grain growth. The pH during the iodine ion releasing reaction is 7.0.
It is preferably 11.0 or less and 8.0 or more 1
It is more preferably 0.0 or less. When a compound other than hydroxide ion is used as the nucleophile, the amount of the nucleophile is preferably 0.25 times or more and 2.0 times or less the amount of the iodine ion releasing agent, and 0.5 The ratio is more preferably not less than 1.5 times and not more than 1.5 times, more preferably not less than 0.8 times and not more than 1.2 times. An example of preferable reaction conditions in the case of introducing a dislocation line by adding a fine grain emulsion containing silver iodide to silver halide grains is shown below. The temperature at which the fine grain emulsion containing silver iodide is added is preferably 30 to 80 ° C, more preferably 40 to 70 ° C. The amount of the silver iodide-containing fine grain emulsion to be added is 1 to 1 with respect to the total amount of silver halide after completion of grain growth.
It is preferably 5 mol%.

In the silver halide photographic emulsion of the present invention,
The average surface silver iodide content of the silver halide grains is preferably 0.5 mol% to 20 mol%, and 1 mol% to 1 mol%.
It is more preferably 5 mol%. Here, the surface silver iodide content of the silver halide grains includes the surface of the silver halide grains and has a depth of 50 from the surface of the silver halide grains.
It refers to the silver iodide content in the silver halide phase up to Å.
The surface silver iodide content of the above silver halide grains is determined by the XPS method (X-ray Photoelectron Spec).
trocopy: X-ray photoelectron spectroscopy). That is, the sample was cooled to −110 ° C. or lower in an ultrahigh vacuum of 1 × 10 ⁻⁸ torr or less, and MgKα (X-ray source voltage 15 kV, X-ray source current 40 mA) was used as a probe X-ray.
And the Ag3d5 / 2, Br3d, and I3d3 / 2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor (SensitivityFactor), and the halide composition of the surface layer is determined from the intensity ratio of these.

The XPS method is disclosed in JP-A-2-24188 as a method for obtaining the silver iodide content on the surface of silver halide grains. However, when the measurement is performed at room temperature, the sample is destroyed by the X-ray irradiation, so that the accurate silver iodide content of the surface layer cannot be obtained. By cooling the sample to a temperature at which no destruction occurs, the silver iodide content in the surface layer can be accurately determined. In particular, for particles such as core / shell particles having a different composition between the surface and the interior, or particles in which a high iodine layer or a low iodine layer is localized on the surface, the measured value at room temperature is halogenated by X-ray irradiation. Due to the decomposition of silver and the diffusion of halides (especially iodine), the composition is very different from the true composition. The XPS method used here is specifically shown below.
0.05% by weight of proteolytic enzyme (pronase) in emulsion
An aqueous solution was added, and gelatin was decomposed by stirring at 45 ° C. for 30 minutes. This is centrifuged to precipitate the emulsion particles and remove the supernatant. Next, distilled water is added to disperse the emulsion particles in distilled water, and the mixture is centrifuged to remove the supernatant. next,
Emulsion particles are redispersed in water and thinly coated on a mirror-polished silicon wafer to obtain a measurement sample. The surface iodide was measured by the XPS method using the sample thus manufactured. In order to prevent the sample from being destroyed by X-ray irradiation, the sample is in an ultra-high vacuum of 1 × 10 ^-8 torr or less X
Cool to -10 to -120 ° C in the PS measurement chamber. MgKα (X-ray source voltage 15
kV, X-ray source current 40 mA), Ag3d5 /
2, Br3d, and I3d3 / 2 electrons were measured. The integrated intensity of the measured peak is determined by the sensitivity factor (Sensiti).
The brightness of the surface layer is calculated from the intensity ratio.

Further, the silver halide photographic emulsion of the present invention comprises
It is preferable to contain at least one kind of polyvalent metal atom, polyvalent metal ion, complex or complex ion inside or on the surface of the silver halide grain. Examples of the polyvalent metal atom, the polyvalent metal ion, the complex, or the polyvalent metal in the complex ion include Fe, Co, Ni, Ru, Rh, Pd, and R.
e, Os, Ir, Pt, Mg, Al, Ca, Sc, T
i, V, Cr, Mn, Cu, Zn, Ga, Ge, As,
Se, Sr, Y, Mo, Zr, Nb, Cd, In, S
n, Sb, Ba, La, W, Au, Hg, Tl, Pb,
Examples include polyvalent metals of the 3rd to 7th periods (most commonly the 4th to 6th periods) of the periodic table of elements such as Bi, Ce and U.
In order to contain a polyvalent metal atom, a polyvalent metal ion, a complex or a complex ion inside or on the surface of a silver halide grain of a silver halide photographic emulsion, the polyvalent metal atom, the polyvalent metal ion or the complex ion may be added. Further, salts containing these (including complex salts), compounds containing these, and the like can be used, but it is preferable to select from a single salt or a metal complex. The metal complex is preferably a 6-coordination complex, a 5-coordination complex, a 4-coordination complex, a 2-coordination complex, an octahedral 6-coordination complex, a plane 4
Coordination complexes are more preferred. As the ligand constituting the complex, CN ⁻ , CO, NO ₂ ⁻ , 1,10-phenanthroline, 2,2′-bipyridine, SO ₃ ⁻ , ethylenediamine, NH ₃ , pyridine, H ₂ O, NCS ⁻ , NCO ^-,
O ₃ , SO ₄ ²⁻ , OH ⁻ , N ₃ ⁻ , S ₂ ⁻ , F ⁻ , Cl ⁻ , B
r ⁻ , I ^−, etc. can be used.

In order to incorporate a polyvalent metal atom, a polyvalent metal ion, a complex or a complex ion into the inside or the surface of the silver halide grain of the silver halide photographic emulsion used in the present invention, for example, B.I. H. Carroll, "Iridiu
m Sensitization, A Literat
ure Review ”, PhotographicS
science and Engineering, No. 2
Volume 4, Issue 6, December 1980, December 265-2
Page 67, U.S. Pat. Nos. 1,951,933, 2,628,167, and 3,687,676.
No. 3,761,267, No. 3,
890,154, 3,901,711, 3,901,713, 4,17.
No. 3,483, No. 4,269,927, No. 4,413,055, No. 4,47.
No. 7,561, No. 4,581,327, No. 4,643,965, No. 4,80.
No. 6,462, No. 4,828,962, No. 4,835,093, No. 4,90.
No. 2,611, No. 4,981,780, No. 4,997,751 and No. 5,05.
No. 7,402, No. 5,134,060, No. 5,153,110, No. 5,16
No. 4,292, No. 5,166,044, No. 5,204,234, No. 5,16.
No. 6,045, No. 5,229,263, No. 5,252,451, No. 5,25.
No. 2,530, EPO No. 0244184, No. 0488737, No. 0488601.
No. 0368304, No. 0405
No. 938, No. 0509674, No. 0
The techniques described in Japanese Patent No. 563946, Japanese Patent Application No. 2-249588, WO 93/02390, etc. can be applied. Further, U.S. Pat. Nos. 4,847,191, 4,933,272 and 4,98.
No. 1,781, No. 5,037,732, No. 4,937,180, No. 4,94
5,035, 5,112,732, EPO, 0509674, 05137.
No. 38, WO 91/10166, No. 92/16876, and German Patent No. 298,3.
The techniques described in No. 20, U.S. Pat. No. 5,360,712, No. 5,024,931 and the like can be applied. In addition, Research Di
sclosure (hereinafter referred to as RD), No. 367
Vol., November 1994, Item 36736, provides a clear description of the criteria for selecting shallow electron trap dopants.

In the present invention, of the silver halide grains,
Part or surface of polyvalent metal atom, polyvalent metal ion, complex or
Or a complex ion is contained, 6
Preference is given to using coordination complex ions. [ML₆]ⁿ In the formula, M represents a filled frontier orbital polyvalent metal ion
But preferably Fe²⁺, Ru²⁺, Os²⁺, Co³⁺, Rh
³⁺, Ir³⁺, Pd⁴⁺Or Pt⁴⁺Is. L ₆Is independent
Represents a 6-coordination complex ligand that can be selected by
However, at least four of the ligands are anionic ligands
At least one of the ligands (preferably at least
3 and optimally at least 4) any halogenation
It is preferred that the electronegativity is higher than that of the substance ligand. n
Represents-, 2-, 3- or 4-.

Specific examples of hexacoordinated complex ions that can provide a shallow electron trap are shown below. SET-1 [Fe (CN) ₆ ] ^4- SET-2 [Ru (CN) ₆ ] ^4- SET-3 [Os (CN) ₆ ] ^4- SET-4 [Rh (CN) ₆ ] ^3- SET- 5 [Ir (CN) ₆ ] ^3- SET-6 [Fe (pyrazine) (CN) ₅ ] ^4- SET-7 [RuCl (CN) ₅ ] ^4- SET-8 [OsBr (CN) ₅ ] ^4- SET -9 [RhF (CN) _5] ^3- SET-10 [IrBr (CN) _5] ^3- SET-11 [FeCO (CN) _5] ^3- SET-12 [RuF ₂ (CN) _4] ^4-SET- 13 [OsCl ₂ (CN) ₄ ] ^4- SET-14 [RhI ₂ (CN) ₄ ] ^3- SET-15 [IrBr ₂ (CN) ₄ ] ^3- SET-16 [Ru (CN) ₅ (OCN)] ^4-SET-17 _{[Ru (CN) 5 (N 3} ) ] ^4-SET-18 [Os (CN) ₅ (SCN)] ^4-SET 19 [Rh (CN) ₅ (SeCN)] ^3- SET-20 [Ir (CN) ₅ (HOH)] ^2-SET-21 [Fe (CN) ₃ Cl _3] ^3- SET-22 [Ru (CO) ₂ (CN) _4] ^- SET-23 [Os (CN) Cl _5] ^4-SET-24 [Co (CN) _6] ^3- SET-25 [Ir (CN) ₄ (oxalate)]
^3- SET-26 [In (NCS) ₆ ] ^3- SET-27 [Ga (NCS) ₆ ] ^3-

When an Ir compound is used in the present invention, preferred examples of the compound include K ₂ IrCl ₆ and K ₃ Ir.
Cl ₆ , K ₂ IrBr _{6 and the} like. Specific examples of other polyvalent metal compounds preferably used in the present invention include InCl ₃ , K ₄ Fe (CN) ₆ , and K ₃ Fe (C
N) ₆ , K ₄ Ru (CN) ₆ , Pb (NO ₃ ) _{2 and the} like, and hydrates thereof. In the present invention, in order to contain a polyvalent metal atom, a polyvalent metal ion, a complex or a complex ion inside or on the surface of the silver halide grain, Ir,
Ru, Os, Fe, Rh, Co, In, Ga, Ge, P
It is particularly preferable to use each atom such as d or Pt, its ion, and its complex. In the present invention, in order to contain a polyvalent metal atom, a polyvalent metal ion, a complex or a complex ion inside or on the surface of the silver halide grain, doping may be carried out during the physical ripening of the silver halide grain. Doping may be performed during the process of forming silver halide grains (generally, during the addition of a water-soluble silver salt and a water-soluble alkali halide). Further, it is also possible to carry out the doping while the silver halide grain formation is temporarily stopped, and thereafter continue the grain formation. In addition, after the formation of silver halide grains, doping may be performed to introduce a polyvalent metal atom, a polyvalent metal ion, a complex or a complex ion into the surface of the silver halide grain. To introduce a polyvalent metal atom, a polyvalent metal ion, a complex or a complex ion, nucleation, physical ripening, or particle formation should be performed in the presence of the polyvalent metal atom, the polyvalent metal ion, the complex or the complex ion. Can be implemented by

Polyvalent metal atom in the silver halide grain,
Generally, the concentration of polyvalent metal ion, complex or complex ion is appropriately in the range of 1 × 10 ^{−7 to} 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ⁻² mol or less. It is in the range of ^{x10 -6} mol or more and 1 x 10 ^-3 mol or less, particularly preferably in the range of 2 x 10 ^-6 to 1 x 10 ^-4 mol. When the above-mentioned polyvalent metal is contained in the silver halide grains, they may be dispersed directly in the emulsion, or water, methanol, ethanol or the like may be added alone or in a mixed solvent. Alternatively, a method of adding an additive to a silver halide photographic emulsion can be applied in the art. Further, a polyvalent metal atom, a polyvalent metal ion, a complex or a complex ion may be added to the silver halide photographic emulsion together with the silver halide fine grains, or a polyvalent metal atom, a polyvalent metal ion, a complex or Fine silver halide grains containing complex ions can be added to the silver halide photographic emulsion. Regarding the method of adding a polyvalent metal atom, a polyvalent metal ion, a complex or a silver halide fine particle containing a complex ion to a silver halide photographic emulsion, the method described in Japanese Patent Application No. 10-014194 can be used. Can be referenced.

The silver halide photographic emulsion of the present invention can have any halide composition, but silver bromide, silver iodobromide and silver iodobromochloride are preferred, and silver iodobromide and iodoodor are preferred. Particularly preferred is silver chloride. Also, silver iodobromochloride,
When silver chlorobromide is used, the silver chloride content in the silver halide photographic emulsion is preferably 0 to 50 mol%, more preferably 0 to 30 mol%, and 0-1.
It is more preferably 0 mol%. Further, the tabular silver halide grain according to the present invention is preferably a silver halide grain having a plurality of silver halide phases having different silver iodide contents inside the silver halide grain, and a plurality of silver halide grains having different halide compositions. It is preferably a core-shell type particle composed of phases. The core-shell type particles preferably have three or more phases having different halide composition ratios, more preferably have four or more phases, and further preferably have five or more phases. The halide composition ratios of the adjacent phases are preferably different by 1 mol%, more preferably 3 mol% or more. The volume ratio of each phase of the core-shell type particles to the whole particles is 1% or more, preferably 3% or more, more preferably 5% or more.
The core-shell type particles have a low iodine inside,
It may have a high iodide, and may have alternating high and low iodide composition phases. The outermost layer of the core-shell type grains is preferably a low iodide phase having a silver iodide content of less than 3 mol%, more preferably less than 1 mol%, and particularly preferably not containing silver iodide. Is.

In the preparation of the silver halide photographic emulsion of the present invention, the formation of nuclei is controlled by the low molecular weight gelatin having an average molecular weight of 5,000 to 70,000 and / or the content of methionine of 30.
It is preferably carried out in the presence of less than μmol / g gelatin. In this case, the average molecular weight of the low molecular weight gelatin used for nucleation is more preferably 6,000 to 50,000,
More preferably, it is from 00 to 30000. The methionine content of gelatin is more preferably 20 μmol / g
Less, and more preferably 0.1 to 10 μmol /
It is g. The low molecular weight gelatin can be obtained by a method such as hydrolysis of ordinary gelatin, enzymatic decomposition using a gelatin degrading enzyme, and cross-linking cleavage using ultrasonic irradiation.
In addition, the methionine content in gelatin is 30 μmol /
In order to reduce the amount to less than g, it is effective to oxidize the alkali-treated gelatin with an oxidizing agent. Examples of the oxidizing agent that can be used in the oxidation treatment include hydrogen peroxide, ozone, peroxy acids, halogens, thiosulfonic acid compounds, quinones, and organic peracids.
Hydrogen peroxide is preferred. There are many documents on the method for measuring the methionine content in gelatin, and the measurement of the methionine content can be carried out, for example, by Journal of Photographic Science, Vol. 28, page 111, Vol.
41, p. 172, p. 42, 117, Journal of Imaging Science vol. 33, page 10, Journal of Imaging Science and Technology vol. 39, page 367, etc., referring to amino acid analysis method, HPLC method, gas chromatography. Method, silver ion titration method, or the like. In the present invention,
The low methionine-containing gelatin having a methionine content of less than 30 μmol / g is preferably used during the nucleation of silver halide grains, but the ripening step following the nucleation step,
It may be added to the growth step.

In the preparation of the silver halide photographic emulsion of the present invention, as described above, it is preferable to use low molecular weight gelatin and / or gelatin having a methionine content of less than 30 μmol / g in the nucleation step, but the nucleation step. Any protective colloid can be used in the other steps. Examples of protective colloids that can be used include gelatin and hydrophilic colloids. These gelatins are usually alkali-treated gelatin, acid-treated gelatin having a molecular weight of about 100,000, oxidized gelatin, or Bull. Soc. Sci. Photo. J
apan. No. 16. The enzyme-treated gelatin as described in P30 (1966) can be preferably used. As the hydrophilic colloid, for example, a gelatin derivative, a graft polymer of gelatin and another polymer,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
A wide variety of synthetic hydrophilic polymeric substances such as homo- or copolymers such as polyvinyl pyrazole can be used. Further, it is also preferable to use chemically modified gelatin in the step of growing silver halide grains. Examples of these chemically modified gelatins include the amino group-substituted gelatins described in JP-A-5-72658, JP-A-9-197595 and JP-A-9-251193. Further, in the present invention, US Pat.
It is preferable to use the polyalkylene oxide compounds described in the specification of No. 252,453.

In the preparation of the silver halide photographic emulsion of the present invention, for example, US Pat. Nos. 4,680,256, 4,684,607 and 4,68 can be used.
The surface index controlling agents for silver halide grains described in Nos. 0,254 and 4,680,255 can also be used. In the silver halide photographic emulsion of the present invention,
The side faces of tabular silver halide grains (111) and (10)
The ratio of the (0) plane is arbitrary, but the (100) plane is preferably 20% or more, and more preferably 30% or more of all the side surfaces. In the preparation of the silver halide photographic emulsion of the present invention, reduction sensitization can be carried out during the formation of silver halide grains. When carrying out reduction sensitization, radical scavengers and other additives for controlling the oxidation of silver nuclei can be used. In the preparation of the silver halide photographic emulsion of the present invention, it is preferable to provide a desalting step once or more during grain formation. The desalting step here means washing the silver halide emulsion with water to remove soluble salts. Regarding the desalting step, the technique described in II of RD17643 can be referred to, and a flocculation method using an inorganic salt, an anionic surfactant or an anionic polymer (for example, polystyrene sulfonic acid) can be used. It can be preferably carried out by using it. The desalting step is preferably carried out at the time when the growth of the silver halide grains is performed until the volume becomes less than 10% of the volume of the silver halide grains at the completion of the growth, and the volume becomes less than 5 vol% It is more preferable to carry out at the time when it has been carried out. When preparing the silver halide photographic emulsion of the present invention, the temperature at the nucleation of silver halide grains is preferably less than 30 ° C, more preferably less than 21 ° C. The temperature during aging and growth is preferably 30 ° C or higher and 90 ° C or lower, more preferably 40 ° C or higher and lower than 80 ° C.

The silver halide photographic emulsion of the present invention may be reduction sensitized. The reduction sensitization is carried out by adding a reducing agent to a protective colloid aqueous solution in which silver halide grains are grown, or by using a protective colloid aqueous solution in which the silver halide grains are grown under a low pAg condition of pAg 7.0 or less. under,
Alternatively, it can be performed by growing or ripening silver halide grains under a high pH condition of pH 7.0 or more. You may perform these methods in combination. Examples of the reducing agent used for reduction sensitization include thiourea dioxide, ascorbic acid and its derivatives, stannous salt, borane compounds, hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, and sulfites. Although it can be used, thiourea dioxide, ascorbic acid and derivatives thereof, and stannous salt are preferably used. When a reducing agent is used, its addition amount is preferably 10 ^-2 to 10 ^-8 mol, and more preferably 10 ^-3 to 10 ^-7 mol, per 1 mol of silver halide. When reduction sensitization is performed by growing or ripening silver halide grains under a low pAg condition of pAg 7.0 or less, a silver salt is added to the protective colloid aqueous solution to obtain an appropriate pAg. , Growth of silver halide grains, or
Aging should be done. The silver salt used is preferably a water-soluble silver salt, and particularly preferably an aqueous solution of silver nitrate. The pAg during aging is suitably 7.0 or less, preferably 2.0 to 5.0.
Is. (Here, the pAg value is the common logarithm of the reciprocal of the Ag ⁺ concentration.)

When the reduction sensitization is carried out by growing or ripening silver halide grains under a high pH condition of pH 7.0 or higher, the protective colloid solution is appropriately added with an alkaline compound. After adjusting to a proper pH, it is preferable to grow or ripen silver halide grains. As the alkaline compound, for example, sodium hydroxide, potassium hydroxide, ammonia and the like can be used, but compounds other than the ammonium compound are preferable. The reducing agent, the silver salt for reduction ripening, and the alkaline compound may be added by rush or over a certain period of time. In this case, constant rate addition may be used,
Function addition may be performed. Also, the required amount may be added in several divided portions. Further, the reducing agent, the silver salt for the reduction ripening, and the alkaline compound are allowed to exist in the reaction vessel prior to the addition of the soluble silver salt and / or the soluble halide for the formation of silver halide grains into the reaction vessel. Alternatively, it may be mixed in a solution of a soluble halide and added to the reaction vessel. Furthermore, the addition may be performed separately from the soluble silver salt and the soluble halide.

An oxidizing agent can be used to inactivate the reducing agent used for reduction sensitization of the silver halide photographic emulsion. The oxidizing agent may also serve a purpose other than deactivating the reducing agent. Examples of the oxidizing agent used for deactivating the reducing agent used for reduction sensitization of these silver halide photographic emulsions and for other purposes include the following oxidizing agents. Hydrogen peroxide (water) and an adduct _{thereof: H 2 O 2, H 2} O 2 -3H
₂ O, 2NaCO ₃ -3H ₂ O ₂ , Na ₄ P ₂ O ₇ -2H
₂ O ₂ , 2 Na ₂ SO ₄ —H ₂ O ₂ -2H ₂ O, etc., peroxy acid salt: K ₂ S ₂ O ₃ , K ₂ C ₂ O ₃ , K ₄ P ₂ O ₃ , K ₂ [Ti
(O ₂ ) C ₂ O ₄ ] -3H ₂ O, peracetic acid, ozone, I ₂ ,
Thiosulphonic acid, NaBO _2, etc. The amount of oxidant added is
The reducing agent used depends on the type of reducing agent, reduction sensitization conditions, oxidizer addition timing, oxidizer addition conditions, etc.
It is preferably 10 ⁻³ to 10 ⁵ mol per mol. The oxidizing agent may be added at any time during the silver halide emulsion preparation process. It can also be added prior to the addition of the reducing agent.
The oxidizing agent can be added using a general method for adding an additive to a silver halide emulsion. For example, it can be dissolved in advance in a suitable organic solvent represented by alcohols or added as an aqueous solution.

After adding the oxidizing agent, it is also possible to add a new reducing substance in order to deactivate the excess oxidizing agent. As these reducing substances, any substance can be used as long as it can reduce the added oxidizing agent, and examples thereof include sulfinic acids, di- and trihydroxybenzenes, chromanes, hydrazines and hydrazides, p-phenylene. Diamines, aldehydes, aminophenols, enediols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives can be used. The amount of the reducing substance, the amount per mole ^10-3 to ³ molar excess of oxidizing agent.

The silver halide grains of the silver halide photographic emulsion of the present invention may have silver halide protrusions on the surface. A silver halide photographic emulsion having silver halide protrusions on the surface of a silver halide grain means a silver halide grain having 30% or more of the total projected area of the silver halide grains having silver halide protrusions on the surface. The term means a silver emulsion. The silver halide grains having silver halide protrusions are 50% or more of the total projected area of the silver halide grains, and further 7
It is preferably 0% or more. It is preferable that the silver halide protrusions on the surface of the silver halide grains are epitaxially arranged at selected portions of silver halide grains (hereinafter, also referred to as “host grains”) serving as a substrate. . Epitaxial placement of silver halide protrusions at selected sites on the host grain reduces the competition for conduction band electrons emitted by photon absorption during imagewise exposure to the sensitized site, and improves sensitivity. In U.S. Pat. No. 4,435,501, silver salts are present at selected sites on the surface of tabular host grains (hereinafter also referred to as "host tabular grains"). It is disclosed that the sensitivity is improved by epitaxially depositing. Regarding the increase in sensitivity, the US patent alleges that the increase in sensitivity limits the epitaxial deposition of silver salt to a small portion of the surface area of host tabular grains. That is, epitaxial placement of tabular grains on a limited portion of the major plane is more efficient than epitaxial placement over all or most of the major plane. In addition, an epitaxial configuration that is substantially limited to the edges of the host grain and has a limited coverage on the major plane is preferred, and an epitaxial configuration that is further limited to the corners of the host grain or its vicinity or other discrete sites is further preferred. Efficient and preferred. The spacing of the principal plane corners of the host particles themselves reduces optoelectronic competition enough to achieve near maximum sensitivity. U.S. Pat. No. 4,435,501 teaches that slowing the epitaxial deposition rate can reduce the number of epitaxially located sites on the host grain.

The same applies to the silver halide photographic emulsion of the present invention, and the silver halide protrusions epitaxially arranged on the surface area of the host grain are preferably limited to a small part of the surface area of the host grain, and the corner or the corner thereof. It is particularly preferable to be limited to the vicinity. Specifically, the surface area of the host particles is preferably less than 50%, more preferably less than 30%. Also,
The silver amount of the silver halide protrusions epitaxially arranged is preferably 0.3 to 25%, and more preferably 0.5 to 15%, with respect to the silver amount of the host grains. One of the most preferred embodiments of the silver halide photographic emulsion of the present invention is an embodiment in which the silver halide protrusions to be epitaxially formed are formed at the corners of the host grain or at limited positions in the vicinity thereof. This aspect can be achieved by applying a known method, for example,
The spectral sensitizing dyes and aminoazaindenes described in US Pat. No. 4,435,501 are used as site-directing agents (si).
The method of adsorbing as a te director) can be preferably used. In order to avoid structural collapse of the host grains, it is preferable that the silver halide protrusions arranged epitaxially have a total solubility higher than that of the silver halide forming the host grains. The epitaxially arranged silver halide protrusions are preferably silver chloride. Since silver chloride forms a face-centered cubic lattice structure like silver bromide, epitaxial deposition can be easily performed. In order to maintain the structural integrity of the host grains, the epitaxial deposition is preferably conducted under conditions that limit the solubility of the halide forming the host grains. When the halide of the epitaxially arranged silver halide protrusions is from the host grain, it is a silver chloride protrusion containing a small amount of bromide and possibly iodide.

In preparing the silver halide photographic emulsion of the present invention, various methods well known in the art can be used for forming silver halide grains. That is, the single jet method, the double jet method, the triple jet method
The jet method, the method for supplying fine silver halide grains, or the like, or any combination of these methods can be used. In addition, the pH in the liquid phase where silver halide is produced, p
A method of controlling Ag according to the growth rate of silver halide can also be used together. The formation of silver halide grains is preferably carried out under conditions close to the critical growth rate.

A seed emulsion may be used in the preparation of the silver halide photographic emulsion of the present invention. When a seed emulsion is used, the silver halide grains in the seed emulsion may have a regular crystal structure such as a cube, octahedron or tetradecahedron, or a spherical or plate-like irregularity. It may have a specific crystal form. In these particles, (100) plane and (11) plane
1) Any surface ratio can be used. Further, these crystal forms may be a composite, and grains of various crystal forms may be mixed, but the silver halide grains in the seed emulsion are twinned halogenated having a twin plane. Silver grains are preferred, and twinned silver halide grains having two opposing parallel twin planes are particularly preferred. Whether a seed emulsion is used or not, a method and conditions known in the art can be used as the method and conditions for silver halide nucleus formation and ripening. In preparing the silver halide photographic emulsion of the present invention, a silver halide solvent known in the art can be used. It is recommended to avoid using silver halide solvent. For the preparation of the silver halide photographic emulsion of the present invention, any of an acidic method, a neutral method and an ammonia method can be used, but the acidic method or the neutral method is preferable. The silver halide photographic emulsion of the present invention, even if halide ions and silver ions are mixed at the same time,
It can also be prepared by mixing one with the other. Further, in consideration of the critical growth rate of silver halide crystals, pAg and pH in the mixing vessel may be controlled to add halide ions and silver ions sequentially or simultaneously. The halogen composition of the silver halide grains may be changed by using a conversion method at any step of silver halide formation.

The silver halide fine particles used in the nucleation and / or the silver halide grain formation performed by supplying the silver halide fine grains when the silver halide photographic emulsion of the present invention is prepared are the halogens relating to the present invention. It may be prepared in advance prior to the preparation of silver halide grains, or may be prepared in parallel with the preparation of silver halide grains. When the latter is prepared in parallel, JP-A-1-183417, 2-4
The silver halide fine particles can be prepared by using a mixer separately provided outside the reaction vessel in which the silver halide particles are formed as shown in Japanese Patent No. 4335, etc., but prepared separately from the mixer. Provide a container and prepare the silver halide fine particles once prepared in the mixer in the preparation container so that they are suitable for the growth environment in the reaction container where the silver halide particles are prepared, and then supply them to the reaction container. Is preferred. Regarding the continuous process nucleation facility, see Japanese Patent Laid-Open No. 2000-2000.
Reference can be made to the description in, for example, JP-A-112049. In the preparation of silver halide fine grains, when it is not intended to prepare reduction sensitized fine grains, acidity or neutrality (p
It is preferable to prepare fine silver halide grains in an environment of H ≦ 7). When the reduction sensitized fine particles are intended to be prepared, silver halide fine particles may be prepared by appropriately combining the reduction sensitization methods described above. The fine silver halide grains can be prepared by mixing a water-soluble silver salt containing silver ions and an aqueous solution containing halide ions while appropriately controlling the supersaturation factor. Regarding the control of the supersaturation factor, JP-A-63-92942 and 63.
Reference can be made to the description in, for example, JP-A-3111244. The pAg at the time of preparing the silver halide fine particles is preferably 3.0 or more, and more preferably 5.0, when it is intended to suppress the generation of reduced silver nuclei in the silver halide fine particles themselves. Or more, more preferably 8.0 or more. The temperature for preparing the fine silver halide grains is preferably 50 ° C. or lower, more preferably 40 ° C.
Or less, and most preferably 35 ° C. or less. Also,
As the protective colloid used for preparing the silver halide fine grains, the above-mentioned protective colloid used for preparing the silver halide grains can be used.

By preparing the silver halide fine grains at a low temperature, coarsening of the grain size due to Ostwald ripening after the formation of the silver halide fine grains can be suppressed, but gelatin tends to coagulate at a low temperature.
Low molecular weight gelatin as described in JP-A-2, etc., a synthetic molecular compound having a protective colloid action on silver halide grains,
Alternatively, it is preferable to use a natural polymer compound other than gelatin. The concentration of the protective colloid is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more. The grain size of the silver halide fine grains is preferably 0.1 μm or less, more preferably 0.05 μm or less. For silver halide fine grains,
If necessary, the reduction sensitization described above may be performed, and a metal ion or the like may be optionally contained. In the preparation of the silver halide photographic emulsion of the present invention, it is preferable to perform the concentration operation of the silver halide emulsion by the ultrafiltration method in at least a part of the growing step. When a tabular emulsion having a high aspect ratio is prepared, a diluting environment is preferable. Therefore, it is preferable to concentrate the silver halide emulsion by an ultrafiltration method in order to improve productivity. For the concentration operation of the silver halide emulsion by the ultrafiltration method, JP-A-10-3399 is known.
The production facility for silver halide emulsions disclosed in Japanese Patent No. 23 can be preferably used. When the concentration operation of the silver halide emulsion by the ultrafiltration method is carried out in the preparation of the silver halide photographic emulsion of the present invention, the ultrafiltration concentration mechanism is connected to the reaction vessel with a pipe or the like, and the reaction is performed by a circulation mechanism such as a pump. It is possible to circulate the product solution between the reaction vessel and the concentrating mechanism at an arbitrary flow rate, or to stop it at any time.Furthermore, the volume of the aqueous solution containing salt extracted from the reaction solution by the concentrating mechanism can be adjusted. It is possible to use equipment having a device for detecting and having a mechanism capable of arbitrarily controlling the amount. Further, it is possible to add other functions to the equipment, if necessary.

Concentration by ultrafiltration is carried out by the following (1),
It can be preferably applied in the form of (2) or a combination of (1) and (2). (1) The volume of the reaction solution is reduced by using the above-mentioned concentration mechanism in the step of forming silver halide grains. (2) Using the concentration mechanism described above in the step of forming silver halide grains, reacting an aqueous solution containing a soluble substance in an amount equal to or less than the amount added to the raw material solution for silver halide formation The reaction solution in the reaction vessel is kept substantially constant or the increase in volume is suppressed. In addition, since the dislocation line grain ratio can be improved by providing the step of introducing dislocation lines after reducing the volume of the reactant solution by the method of (1), the above (1 It is a preferred embodiment to reduce the volume of the reactant solution by the method (1). The ultrafiltration may be carried out by interrupting the silver halide grain growth at any point in the silver halide grain formation process, or may be carried out for any period while continuing the silver halide grain growth. Ultrafiltration can also be carried out multiple times during the silver halide grain formation process.

By utilizing ultrafiltration, unnecessary water-soluble salts can be removed and desalted in the process of forming silver halide grains. Further, a reducing agent, an oxidizing agent, a halogen ion-releasing compound, a silver halide solvent, a polyvalent metal atom, a polyvalent metal ion, a polyvalent metal complex or a polyvalent metal complex ion, which is added when the silver halide grains are formed, is not added. It is possible to remove and deactivate reactants, undoped residues, and the like. Furthermore, control of the distance between silver halide grains, control of any silver halide grain growth conditions such as control of silver halide grain growth pH, pBr, and control of the volume of the reaction solution at the time of silver halide grain formation, Concentration and the like can be carried out. Ultrafiltration can be performed using, for example, membrane separation. For ultrafiltration using membrane separation, Chemical Engineering Handbook, 5th revised edition (edited by Chemical Engineering Society, Maruzen) 924-
954, RD, Vol. 102, Vol. 10208 and Vol. 131, 13122, or Japanese Examined Patent Publication Nos. 59-43727, 62-27008, and JP-A-62-1131.
37, 57-209823, 59-4.
No. 3727, No. 62-113137, No. 61
No. 219948, No. 62-23035, No. 63-40137, No. 63-40039,
It is described in JP-A-3-140946, JP-A-2-172816, JP-A-2-172817, JP-A4-222942 and the like, and the ultrafiltration can be carried out by referring to the described method. it can. When ultrafiltration is used in the preparation of the silver halide photographic emulsion of the present invention, JP-A-11-339923 or JP-A-11-23 is used.
It is preferable to use the apparatus or method described in Japanese Patent No. 1448.

Further, in the preparation of the silver halide photographic emulsion of the present invention, it is preferable to carry out desalting after the formation of silver halide grains to remove unnecessary soluble salts.
Desalting can be performed, for example, by the method of RD17643 item II. For desalting, a Nudel water washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants, anionic polymers (eg polystyrene sulfonic acid) or gelatin derivatives (eg acylation) may be used. A precipitation method using gelatin, carbamoylated gelatin) can be used. Further, desalting by ultrafiltration utilizing the above-mentioned membrane separation can also be preferably used. Conditions other than the above when preparing the silver halide photographic emulsion of the present invention are described in JP-A-61-6643,
61-14630, 61-112142, 62-157024, 62-18556.
No. 63-92942 and No. 63-1516.
18 gazette, the same 63-163451 gazette, the same 63-2.
20238, 63-311244, RD
It is described in the paragraphs I and III of 38957, the XV paragraph of RD40145, etc., and appropriate conditions can be selected with reference to the description. The silver halide photographic emulsion of the present invention can be subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RD389.
57, IV and V, RD40145, XV, etc.

Further, known photographic additives can be used in the silver halide photographic emulsion of the present invention. For these photographic additives, see RD 38957 II-X.
Item, I to XIII of RD40145.
The silver halide photographic emulsion of the present invention can be used as a silver halide emulsion for various photosensitive materials such as monochrome photosensitive materials such as monochrome films and color photosensitive materials such as color films. Typical examples of the color light-sensitive material include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. When the silver halide photographic light-sensitive material of the present invention is a color light-sensitive material, red, green and blue light-sensitive silver halide emulsion layers can be provided and a coupler can be contained in each layer. The color-forming dye formed from the coupler contained in each of these layers preferably has a spectral absorption maximum of at least 20 nm apart, and as the coupler, a cyan coupler, a magenta coupler and a yellow coupler are usually used. The combination of each emulsion layer and the coupler is usually
Although a combination of a yellow coupler and a blue-sensitive layer, a magenta coupler and a green-sensitive layer, and a cyan coupler and a red-sensitive layer is used, the combination is not limited to these and other combinations may be used. Specific examples of the coupler are described in Section II of RD40145. A DIR compound can be used in the silver halide photographic light-sensitive material of the present invention. Specific examples of DIR compounds that can be used include D-1 to D-34 described in JP-A-4-114153, and these compounds can be preferably used. In addition to the above, specific examples of the DIR compound include, for example, US Pat.
4,678, 3,227,554, 3,647,291 and 3,95.
No. 8,993, No. 4,419,886, No. 3,933,500, and JP-A-57-5.
No. 6837, No. 51-13239, U.S. Pat. No. 2,072,363, No. 2,070,26.
Examples thereof include those described in No. 6 specification, section XIV of RD40145, and the like. These additives are R
It can be added to the silver halide photographic emulsion of the present invention by the dispersion method described in Item VIII of D40145.

The silver halide photographic light-sensitive material of the present invention comprises
Known supports described in, for example, the XV section of RD38957 can be used. The silver halide photographic light-sensitive material of the present invention can be provided with auxiliary layers such as the filter layer and the intermediate layer described in the above-mentioned item XI of RD38957. The silver halide photographic light-sensitive material of the present invention can have various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above-mentioned item XI of RD38957. For the development processing of these color light-sensitive materials, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (The Theory of The Ph)
otographic Process Forth E
pp.291-334 and Journal of the American Chemical Society (Jo
urna1 of the American Che
medical Society) Vol. 73, No. 3,100
Developers known per se described on page (1951) can be used, and the above-mentioned RD38957 XVII to XX can be used.
Section and the general method described in RD40145, section XXIII.

[0046]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1 (Preparation of emulsion Em-1) [Nucleation / nuclear ripening step] The following gelatin aqueous solution-1 in the reaction vessel was kept at 40 ° C and the mixing and stirring apparatus described in JP-A-62-160128 was used. Stirring vigorously,
Using the double jet method, the following silver nitrate aqueous solution-1 and halide aqueous solution-1 were added at a constant flow rate for 1 minute to perform nucleation. <Gelatin solution -1> alkali-treated inert gelatin (average molecular weight 100,000) 9.02 g Potassium bromide 2.75 g H ₂ O 3.6 L <an aqueous solution of silver nitrate -1> silver nitrate 14.0 g H ₂ O 62.8 ml <halide aqueous -1> potassium bromide 9.82 g H ₂ O rate of 62.4 ml added after the end immediately following aqueous gelatin solution -2 addition, 3
After requiring 0 minutes to raise the temperature to 60 ° C., the pH was adjusted to 5.0, and the state was aged for 20 minutes. <Gelatin solution -2> alkali-treated inert gelatin (average molecular weight 100,000) 38.7 g 10 wt% surfactant (EO-1) methanol solution _{1.3ml H 2 O 908.6ml * EO-} 1: 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)

[Particle Growth Step-1] After completion of the nuclear ripening step,
Then, using the double jet method, the following silver nitrate aqueous solution −
2 and aqueous halide solution-2 were added while accelerating the flow rate. After the addition was completed, the following gelatin aqueous solution-3 was added, and subsequently the following silver nitrate aqueous solution-3 and halide aqueous solution-3 were added while accelerating the flow rate. During this period, the silver potential in the reaction vessel (measured with a silver ion selective electrode using a saturated silver-silver sulfide electrode as a reference electrode) was controlled to 12 mV using a 1 mol / L potassium bromide solution. <Nitrate aqueous -2> nitrate 178.0g H ₂ O 795.0ml <halide solution -2> Potassium bromide 124.7g H ₂ O 792.7ml <gelatin solution -3> alkali-treated inert gelatin (average molecular weight 100,000 ) 175.9 g surfactant (EO-1) of 10 wt% methanol solution 0.67ml H ₂ O 4260.1ml <nitrate aqueous -3> nitrate 1907.6g H ₂ O 2769.5ml <halide solution -3> odor Potassium iodide 1322.7 g Potassium iodide 18.6 g H ₂ O 2721.6 ml

[Particle Growth Step-2] After completion of the particle growth step-1, the following aqueous solution-A1 and then the following aqueous solution-B1.
Is added, and 1 mol / L potassium hydroxide aqueous solution is used to p
After adjusting H to 9.3 and aging for 4 minutes, iodine ions were released. Then, using 1 mol / L nitric acid aqueous solution, p
H was adjusted to 5.0, and then the silver potential in the reaction vessel was set to -19 mV using a 3.5 mol / L potassium bromide aqueous solution.
Then, the following silver nitrate aqueous solution-4 and halide aqueous solution-4 were added while accelerating the flow rate. When 757 ml of silver nitrate aqueous solution-4 was added, the following M-11
Solution a was added, and then the rest of the aqueous silver nitrate solution-4 was added. <Aqueous -A1> p-iodoacetamide sodium benzenesulfonate 83.5g H ₂ O 660.1ml <aq -B1> sodium sulfite 29.0g H ₂ O 312.9ml <nitrate aqueous -4> nitrate 900.3g H ₂ O 1307.0ml <halide solution -4> potassium potassium bromide 627.4g iodide _{4.4g H 2 O 1284.8ml <M-} 11a was> K ₄ aqueous solution containing 195.6mg the [Ru (CN) _6] 110ml In addition, through the grain growth steps-1 and 2, the addition rates of the aqueous solution of silver nitrate and the aqueous solution of halide are set so that new silver halide grains are not generated, and the grain size due to Ostwald ripening between the growing silver halide grains. Optimal control was performed so that deterioration of distribution did not occur.

After completion of the above-mentioned grain growth step, JP-A-5-7
According to the method described in Japanese Patent No. 2658, a chemically modified gelatin in which an amino group is phenylcarbamoyl (modification rate 95
%) 224 g of an aqueous solution was added for desalting and washing, and gelatin was added to disperse well, and the pH was adjusted to 40 ° C.
Was adjusted to 5.8 and pAg was adjusted to 8.9 to obtain a tabular silver halide emulsion Em-1. Tabular silver halide emulsion Em-
As a result of analyzing the silver halide grains contained in 1, the tabular silver halide grains occupy 90% of the projected area of all the grains,
The average aspect ratio is 6.5, the average projected area circle converted grain size is 2.0 μm, the projected area circle converted grain size distribution is 20%, the average grain thickness is 0.31 μm, and the average twin plane distance is 22
It was 0Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 85% of the number of grains. Further, in the tabular silver halide grains contained in the tabular silver halide emulsion Em-1, 92% of the grains have dislocation lines,
72% have dislocation lines in the main plane, 70% have dislocation lines in the fringe portion and the main plane, 88% have 10 or more dislocation lines in the fringe portion, and 70% have 30 dislocation lines in the fringe portion. It had more than one dislocation line. The silver halide grains contained in the tabular silver halide emulsion Em-1 had an average silver iodide content of 2.1 mol% and a surface silver iodide content of 5.3 mol% on average. The coefficient of variation of the distance between twin planes is 34%
The coefficient of variation of grain thickness is 32%, the (100) plane ratio of all side surfaces of the tabular silver halide grain is 35%, and 83% or more of the number of grains is hexagonal tabular silver halide grain. Was occupied by.

(Preparation of Emulsion Em-2) << Preparation of Tabular Seed Emulsion T-A1 >> [Nucleation Step] Oxidized gelatin A (methionine content 0.3 μmol / g gelatin) 70.7 in a reaction vessel.
g and potassium bromide 12.3 g, an aqueous solution of 10.47 L was kept at 20 ° C., and was stirred at a high speed with a mixing and stirring apparatus described in JP-A-62-160128 while stirring at a rate of 0.
The pH was adjusted to 1.90 with 5 mol / L sulfuric acid. After that, the following S-01 solution and the following X-01 solution were added at a constant flow rate for 1 minute to form nuclei by using the double jet method, and then the following G-01 solution was added. S-01 liquid: 88.7 1.25 mol / L silver nitrate aqueous solution
5 ml X-01 solution: 1.25 mol / L potassium bromide aqueous solution 8
8.75 ml G-01 solution: 1260 ml of aqueous solution surfactant A: HO (CH ₂ CH ₂ O) containing 52.0 g of oxidized gelatin A and 3.78 ml of a 10 mass% methanol solution of the following surfactant A. _m [CH (CH ₃ )
CH ₂ O] ₂₀ (CH ₂ CH ₂ O) _n H (m + n = 10) [Aging step] It takes 73 minutes after completion of the nucleation step to obtain 7
The temperature was raised to 5 ° C. Immediately after the start of temperature increase, pA was measured using a 1.75 mol / L potassium bromide aqueous solution for 45 minutes.
The g was adjusted to 8.6. Forty-five minutes after the start of temperature increase, which is in the middle of heating to 75 ° C., 96.8 ml of an aqueous solution containing 9.68 g of ammonium nitrate was added, and then 285 ml of a 10% potassium hydroxide aqueous solution was added and held for 6 minutes and 30 seconds. Then, the pH was adjusted to 7.6 with a 56% acetic acid aqueous solution.

[Growth step] After completion of the ripening step, pAg was adjusted to 8.6 using a 1.75 mol / L potassium bromide aqueous solution, and pH was maintained at 6.1 using a 56% acetic acid aqueous solution. Meanwhile, the following liquid S-02 and liquid X-02 were added using a double jet method in 8 minutes while accelerating the flow rate. S-02 solution: 1.25 mol / L silver nitrate aqueous solution 1130
ml X-02 solution: 1.25 mol / L potassium bromide 1130
After the addition of ml S-02 solution and X-02 solution was completed, desalting (destroyed by Kao Atlas) aqueous solution and magnesium sulfate aqueous solution were subjected to coagulation precipitation desalting and washing treatment, and alkali-treated inactive gelatin B (methionine content). 50.0 μmol /
g) was added and well dispersed to prepare a tabular seed emulsion T-A1. In the tabular seed emulsion T-A1, 50% of the projected area of all grains are tabular grains having an aspect ratio of 11 or more,
The average aspect ratio is 10, the average grain size of projected area circles is 0.62 μm, the grain size distribution of projected area circles is 27%, the average grain thickness is 0.06 μm, and the average distance between twin planes is 12.
The number of silver halide grains having 0Å and two twin planes parallel to the principal plane accounted for 95%.

<< Preparation of tabular silver halide emulsion Em-2 >> Using tabular seed emulsion T-A1, grain growth was carried out in the following procedure to obtain tabular silver halide emulsion Em-2.
Was prepared. As the stirring device, the mixing stirring device described in JP-A-62-160128 was used. In addition, when removing soluble components from a reaction solution by ultrafiltration, JP-A-10-
The device described in JP-A-339923 was used. 0.41
A tabular seed emulsion T-A1 equivalent to 1 mol, the surfactant A
10 mass% methanol solution (0.12 ml), pure water, and 285.4 g of the gelatin B to make the reaction mother liquor having a volume of 29.9 L, pAg9. While maintaining at 4, the following S-11 solution and the following X-11 solution were added using a double jet method over 86 minutes while accelerating the flow rate. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. S-11 solution: 1.75 mol / L silver nitrate aqueous solution 7538
ml X-11 solution: 1.741 mol / L potassium bromide and 0.
Aqueous solution 7538 containing 009 mol / L potassium iodide
ml Subsequently, the following S-12 solution was added over 16 minutes while decelerating to adjust pAg to 9.1. S-12 solution: 1.75 mol / L silver nitrate aqueous solution 727 m
l Continuously add the following solution I-11 and the following solution Z-11,
The pH was adjusted to 9.3 with a 0% aqueous potassium hydroxide solution and held for 6 minutes, and then the pH was adjusted to 5.0 with a 56% aqueous acetic acid solution.
PAg was adjusted to 9.75 mol / L with an aqueous potassium bromide solution.
Adjusted to 4. Liquid I-11: 558 ml of an aqueous solution containing 69.2 g of sodium p-iodoacetamidebenzenesulfonate Z-11 liquid: 248 ml of an aqueous solution containing 24.0 g of sodium sulfite.

Subsequently, the following S-13 solution and the following X-1
Liquid 3 was added in 16 minutes while accelerating the addition flow rate. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. 56% during addition
The pH was adjusted to 5.0 with an aqueous acetic acid solution and the pAg was controlled to 9.4 with an aqueous 1.75 mol / L potassium bromide solution. S-13 solution: 1.75 mol / L silver nitrate aqueous solution 1090
ml X-13 solution: 1.663 mol / L potassium bromide and 0.
Aqueous solution 1090 containing 088 mol / L potassium iodide
ml Subsequently, the following S-14 solution was added over 15 minutes while decelerating to adjust pAg to 8.4, and then the following M-11b solution was added. S-14 solution: 1.75 mol / L silver nitrate aqueous solution 727 m
l M-11b solution: 234.7 mg of K ₄ [Ru (CN) ₆ ]
132 ml of an aqueous solution containing the solution, and subsequently, the following S-15 solution and the following X-15 solution were added over 24 minutes while accelerating the flow rate. During the addition, the pH was adjusted to 5.0 with a 56% aqueous acetic acid solution and the pAg was controlled to 8.4 with a 1.75 mol / L potassium bromide aqueous solution. Then 1.
The pAg was adjusted to 9. with a 75 mol / L potassium bromide aqueous solution.
Adjusted to 4. Then, the following S-16 solution and the following X-1
Solution 6 was added over 17 minutes while accelerating the flow rate. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. During the addition, the pH was adjusted to 5.0 with a 56% aqueous acetic acid solution, and the pAg was controlled to 9.4 with an aqueous 1.75 mol / L potassium bromide solution. S-15 solution: 1.75 mol / L silver nitrate aqueous solution 605 m
l X-15 solution: 1.663 mol / L potassium bromide and 0.
Aqueous solution containing 088 mol / L potassium iodide 605 m
1 S-16 solution: 1.75 mol / L silver nitrate aqueous solution 1211
ml X-16 solution: 1.75 mol / L potassium bromide aqueous solution 1
211 ml

After completion of the above addition, JP-A-5-72658
According to the method described in Japanese Patent Laid-Open No. 360-360, a chemically modified gelatin having a phenylcarbamoyl amino group (modification rate 95%) 360
An aqueous solution containing g is added, and desalination and washing treatment are performed,
Gelatin was added and well dispersed, and the pH was adjusted to 5.
8, pAg was adjusted to 8.9 to obtain a tabular silver halide emulsion Em-2. As a result of analyzing the silver halide grains contained in the tabular silver halide emulsion Em-2, tabular silver halide grains occupy 95% or more of the projected area of all grains, the average aspect ratio is 15.0, and the projected area is The average circle-equivalent grain size is 2.6 μm, the projected area circle-equivalent grain size distribution is 37%, the average grain thickness is 0.19 μm, and the average distance between twin planes is 12.
It was 0Å, and tabular silver halide grains having two twin planes parallel to the main plane accounted for 95% of the number of grains. Further, in the tabular silver halide grains contained in the tabular silver halide emulsion Em-2, 35% of the grains have dislocation lines,
12% have dislocation lines in the main plane, 8% have dislocation lines in the fringe portion and the main plane, 28% have 10 or more dislocation lines in the fringe portion, and 17% have 30 dislocation lines in the fringe portion. It had more than one dislocation line. Also, tabular silver halide emulsion E
The average silver iodide content of the silver halide grains contained in m-2 was 1.9 mol%, and the average surface silver iodide content was 5.1 mol%. Further, the variation coefficient of the distance between twin planes is 31%, the variation coefficient of the grain thickness is 32%, the (100) plane ratio of all side surfaces of the tabular silver halide grain is 30%, and Hexagonal tabular silver halide grains accounted for 90% or more.

(Preparation of Emulsion Em-3) The above emulsion Em-2.
In the preparation of Emulsion E, except that the following liquids I-11a and Z-11a were used in place of the liquids I-11 and Z-11.
Emulsion Em-3 was prepared in the same manner as m-2. Solution I-11a: 806 ml of an aqueous solution containing 100.0 g of sodium p-iodoacetamidobenzenesulfonate Z-11a solution: an aqueous solution of 358 ml containing 34.7 g of sodium sulfite Silver halide grains contained in tabular silver halide emulsion Em-3 As a result of analysis, tabular silver halide grains account for 95% or more of the projected area of all grains, the average aspect ratio is 15.0, the average projected area circle converted grain size is 2.6 μm, and the projected area circle converted grain is The diameter distribution is 37% and the average particle thickness is 0.
The average number of twin planes was 19 μm, the average distance between twin planes was 120Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains. In the tabular silver halide grains contained in the tabular silver halide emulsion Em-3, 62% had dislocation lines, 20% had dislocation lines on the main plane, and 15% had fringe portions. And dislocation lines on the main plane, 47% had 10 or more dislocation lines in the fringe portion, and 32% had 30 or more dislocation lines in the fringe portion. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-3 was 2.3 mol%, and the average surface iodide content was 5.8 mol%.
Further, the variation coefficient of the distance between twin planes is 31%, the variation coefficient of the grain thickness is 32%, the (100) plane ratio of all side surfaces of the tabular silver halide grain is 30%, and Hexagonal tabular silver halide grains accounted for 90% or more.

(Preparation of emulsion Em-4) The above emulsion Em-2.
In the preparation of, the addition of S-11 solution and X-11 solution was followed by ultrafiltration over 10 minutes to obtain 5.0 L of the soluble component of the reaction solution.
Emulsion E, except that the following I-11b solution and Z-11b solution were used in place of the I-11 solution and the Z-11 solution.
Emulsion Em-4 was prepared in the same manner as m-2. Solution I-11b: 1054 ml of an aqueous solution containing 130.8 g of sodium p-iodoacetamidobenzenesulfonate Z-11b solution: an aqueous solution of 4468 ml of 45.4 g of sodium sulfite Silver halide grains contained in tabular silver halide emulsion Em-4 As a result of analysis, tabular silver halide grains occupy 95% or more of the projected area of all grains, the average aspect ratio is 15.0, the average projected area circle converted grain size is 2.6 μm, and the projected area circle converted grain is The diameter distribution is 37% and the average particle thickness is 0.
The average number of twin planes was 19 μm, the average distance between twin planes was 120Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains. In the tabular silver halide grains contained in the tabular silver halide emulsion Em-4, 78% had dislocation lines, 43% had dislocation lines in the main plane, and 40% had fringe portions. And 68% had 10 or more dislocation lines in the fringe portion, and 43% had 30 or more dislocation lines in the fringe portion. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-4 was 2.7 mol%, and the average surface iodide content was 6.3 mol%.
The variation coefficient of the distance between twin planes is 30%, the variation coefficient of the grain thickness is 32%, the (100) plane ratio of all side surfaces of the tabular silver halide grain is 30%, and the number of grains is 90
% Or more was occupied by hexagonal tabular silver halide grains.

(Preparation of Emulsion Em-5) The above emulsion Em-2.
In the preparation of, the addition of S-11 solution and X-11 solution was followed by ultrafiltration over 10 minutes to obtain 5.0 L of the soluble component of the reaction solution.
And adjusting the pAg after adding S-12 solution to 8.6, and using the following I-11c solution and Z-11c solution instead of I-11 solution and Z-11 solution. Is emulsion Em
-Emulsion Em-5 was prepared in the same manner as in Preparation of -2. Solution I-11c: 1116 ml of an aqueous solution containing 138.5 g of sodium p-iodoacetamidobenzenesulfonate Z-11c solution: an aqueous solution of 495 ml containing 48.0 g of sodium sulfite Silver halide grains contained in tabular silver halide emulsion Em-5 As a result of analysis, tabular silver halide grains account for 95% or more of the projected area of all grains, the average aspect ratio is 15.0, the average projected area circle converted grain size is 2.6 μm, and the projected area circle converted grain is The diameter distribution is 37% and the average particle thickness is 0.
The average number of twin planes was 19 μm, the average distance between twin planes was 120Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains. In the tabular silver halide grains contained in the tabular silver halide emulsion Em-5, 78% had dislocation lines, 55% had dislocation lines in the main plane, and 50% had fringe portions. And 69% had 10 or more dislocation lines in the fringe portion, and 46% had 30 or more dislocation lines in the fringe portion. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-5 was 2.8 mol% and the average surface iodide content was 6.5 mol%.
Further, the variation coefficient of the distance between twin planes is 30%, the variation coefficient of the grain thickness is 32%, the (100) plane ratio of all side surfaces of the tabular silver halide grain is 30%, Hexagonal tabular silver halide grains accounted for 90% or more.

(Preparation of emulsion Em-6) The above emulsion Em-2.
In the preparation of the above, the soluble component of the reaction solution of 12.0 was added by ultrafiltration for 30 minutes after the addition of the S-11 solution and the X-11 solution.
L was removed, and pAg after adding S-12 solution was adjusted to 8.6.
Emulsion Em-6 was prepared in the same manner as Emulsion Em-2 except that the following I-11d solution and Z-11d solution were used in place of I-11 solution and Z-11 solution. did. I-11d solution: 1550 ml of an aqueous solution containing 192.3 g of sodium p-iodoacetamidobenzenesulfonate Z-11d solution: an aqueous solution of 688 ml of 66.7 g of sodium sulfite Silver halide grains contained in tabular silver halide emulsion Em-6 As a result of analysis, tabular silver halide grains account for 95% or more of the projected area of all grains, the average aspect ratio is 15.0, the average projected area circle converted grain size is 2.6 μm, and the projected area circle converted grain is The diameter distribution is 37% and the average particle thickness is 0.
The average number of twin planes was 19 μm, the average distance between twin planes was 120Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains. In the tabular silver halide grains contained in the tabular silver halide emulsion Em-6, 96% have dislocation lines, 89% have dislocation lines in the main plane, and 88% have fringe portions. And 93% had 10 or more dislocation lines in the fringe portion, and 72% had 30 or more dislocation lines in the fringe portion. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-6 was 3.5 mol%, and the average surface iodide content was 8.8 mol%.
Further, the variation coefficient of the distance between twin planes is 30%, the variation coefficient of the grain thickness is 30%, the (100) plane ratio of all side surfaces of the tabular silver halide grain is 30%, Hexagonal tabular silver halide grains accounted for 90% or more.

(Preparation of Emulsion Em-7) << Preparation of Tabular Seed Emulsion T-A2 >> In the preparation of tabular seed emulsion T-A1, nucleation was performed as described in JP-A-2.
Using the continuous process nucleation facility described in Japanese Patent Application Publication No.
Solution a and solution X-01a below were used in the same manner as in tabular seed emulsion T-A1 except that nucleation was performed at 20 ° C. over a period of 4 minutes at a constant flow rate. Was carried out to prepare a tabular seed emulsion T-A2. S-01a solution: 18.85 g of silver nitrate and 0.5 mol / L
An aqueous solution containing 29.0 ml of sulfuric acid of 2494 ml X-01a solution: an aqueous solution containing 30.2 g of potassium bromide and 26.8 g of oxidized gelatin A (methionine content 0.3 μmol / g gelatin) 2494 ml The above tabular seed emulsion T- A2 is 50 of the projected area of all particles
% Are tabular grains having an aspect ratio of 25 or more, the average aspect ratio is 119, and the average of projected area circle conversion grain sizes is 0.7.
The average grain size distribution was 6 μm, the projected area circle-equivalent grain size distribution was 29%, the average grain thickness was 0.04 μm, and the average distance between twin planes was 100Å. The silver halide grains having two twin planes parallel to the main plane accounted for 95% of the number of grains.

<< Preparation of tabular silver halide emulsion Em-7 >> Using the above-mentioned tabular seed emulsion T-A2, grain growth was carried out in the following procedure to obtain tabular silver halide emulsion Em.
-7 was prepared. For grain growth, see Japanese Patent Laid-Open No. 62-160.
The mixing and stirring apparatus described in Japanese Patent No. 128 was used. Further, when removing soluble components from the reaction solution by ultrafiltration,
The device described in JP-A-10-339923 was used. A tabular seed emulsion T-A2 corresponding to 0.411 mol, 0.12 m of a 10 mass% methanol solution of the surfactant A.
1, pure water, and 428.1 g of the gelatin B were added to obtain a volume of 5
While maintaining the reaction mother liquor adjusted to 9.8 L at a pAg of 9.6 with an aqueous potassium bromide solution having a temperature of 60 ° C. and a concentration of 1.75 mol / L,
Using the double jet method, the following S-11a liquid and the following X-
The liquid 11a was added over 66 minutes while accelerating the flow rate. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. S-11a solution: 1.75 mol / L silver nitrate aqueous solution 753
8 ml X-11a solution: 75 aqueous solution containing 1.741 mol / L potassium bromide and 0.009 mol / L potassium iodide
38 ml

Next, 42.0 L of the soluble component in the reaction solution was removed by ultrafiltration over 30 minutes. Then, the following S-12
Solution a was added over 16 minutes while decelerating, and pAg was increased to 8.6.
Adjusted to. S-12a solution: 1.75 mol / L silver nitrate aqueous solution 727
The following I-11b solution and the following Z-11b solution were added, the pH was adjusted to 9.3 with a 10% aqueous potassium hydroxide solution, and the mixture was kept for 6 minutes, and then the pH was adjusted to a 5.% aqueous solution with 56% acetic acid. PA with 0, 1.75 mol / L potassium bromide aqueous solution
The g was adjusted to 9.4. Solution I-11b: 1550 ml of an aqueous solution containing 192.3 g of sodium p-iodoacetamidebenzenesulfonate Z-11b solution: 688 ml of an aqueous solution containing 66.7 g of sodium sulfite. Subsequently, the following solution S-13a and the following solution X-13a were added. Addition was carried out for 14 minutes while accelerating the flow rate. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. During the addition, the pH was controlled to 5.0 and 1 with a 56% acetic acid aqueous solution, and the pAg was controlled to 9.4 with a 75 mol / L potassium bromide aqueous solution. S-13a solution: 1.75 mol / L silver nitrate aqueous solution 109
0 ml X-13a solution: an aqueous solution 10 containing 1.663 mol / L potassium bromide and 0.088 mol / L potassium iodide.
90 ml

Subsequently, the following S-14a solution was added over 12 minutes while decelerating to adjust the pAg to 8.4. S-14a solution: 1.75 mol / L silver nitrate aqueous solution 727
ml Then, after adding the following M-11c solution, the following S
Liquid -15a and liquid X-15a below were accelerated in flow rate and added over 20 minutes. During the addition, the pH was adjusted to 5. with a 56% acetic acid aqueous solution.
The pAg was controlled to 8.4 with 0, 1.75 mol / L potassium bromide aqueous solution. Then, pAg was adjusted to 9.4 with a 1.75 mol / L potassium bromide aqueous solution. Subsequently, the following S-16a solution and the following X-16a solution were added over 13 minutes while accelerating the flow rate (the ratio of the addition flow rate at the end to the flow rate at the start of addition was 1: 1.6). At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. During the addition, the pH was adjusted to 5.0 with a 56% aqueous acetic acid solution, and the pAg was controlled to 9.4 with an aqueous 1.75 mol / L potassium bromide solution. M-11c solution: 234.7 mg of K ₄ [Ru (CN) ₆ ]
Aqueous solution containing 132 ml S-15a solution: 1.75 mol / L silver nitrate aqueous solution 605
ml X-15a solution: aqueous solution 60 containing 1.663 mol / L potassium bromide and 0.088 mol / L potassium iodide
5 ml S-16a solution: 1.75 mol / L silver nitrate aqueous solution 121
1 ml of X-16a solution: 1211 ml of 1.75 mol / L potassium bromide aqueous solution

After the completion of the addition, JP-A-5-72658
The amino group was converted to phenylcarbamoyl
Chemically modified gelatin (modification rate 95%) 360g
Add an aqueous solution containing water, desalinize and wash with water.
Chin was added to disperse well, and the pH was adjusted to 5.8 and p at 40 ° C.
Ag was adjusted to 8.9 and tabular silver halide emulsion Em-
Got 7. Included in tabular silver halide emulsion Em-7
As a result of analyzing the silver halide grains, the projected area of all grains
Tabular silver halide grains account for 97% or more, and
50% of the projected area is tabular grains with an aspect ratio of 70 or more
Yes, the average aspect ratio is 61,
Average 4.3μm, projected area circle equivalent particle size distribution 39%,
The average grain thickness is 0.07 μm, and the average distance between twin planes is
100 Å, with two twin planes parallel to the main plane
The tabular silver halide grains account for 94% of the total number of grains.
It was Also included in tabular silver halide emulsion Em-7.
95% of tabular silver halide grains have dislocation lines.
, 86% have dislocation lines in the main plane, and 84% have flylines
There are dislocation lines in the ridge and the main plane, and 89% is in the fringe
It has 10 or more dislocation lines, and 65% is 30 in the fringe area.
It had more than one dislocation line. Also, flat halogenated
Average iodide of silver halide grains contained in silver emulsion Em-7
The silver content is 3.5 mol%, and the average surface silver iodide content is
It was 7.0 mol%. Also, the variation coefficient of the distance between twin planes
Is 20%, the coefficient of variation of particle thickness is 10%,
The (100) plane ratio of all sides of the tabular silver halide grain is
30%, 90% or more of the number of particles is hexagonal tabular halo
It was occupied by silver gentide grains. In Table 1 below, Emulsion E
Average aspect ratio (AR) of m-1 to Em-7, projection plane
Average (D) of product circle equivalent grain size, average thickness, dislocation line on main plane
Number ratio of tabular grains having 30 or more in the fringe portion
Number ratio of tabular silver halide grains with upper dislocation lines
(FD30), having 10 or more dislocation lines in the fringe part
The tabular silver halide grain number ratio (FD10)
Let me show you. Also, (FD30) × (log _TenAR),
(FD10) x (log_TenAR), (FD30) x (l
og_TenD), (FD10) x (log_TenThe calculated value of D)
It is also shown.

[0064]

[Table 1]

(Color Sensitization and Chemical Sensitization of Emulsion) Emulsion E above
After heating each of m-1 to Em-7 to 57 ° C,
At a silver potential of 50 mV and a pH of 6.5, the sensitizing dyes (SD-5, SD-6 and SD-8) described in the ninth layer of Table 3 were added in an amount of silver iodobromide emulsion per surface area of silver halide grains. It is used in the same manner as in e., and trifurylphosphine selenide, chloroauric acid, potassium thiocyanate, and sodium thiosulfate pentahydrate are added for aging to optimize the sensitivity. -Methyl-4hydroxy-1,3
3a, 7-Tetrazaindene, Japanese Patent Application No. 2000-2818
Color sensitization and chemical sensitization were performed by adding the compound (1-6) described in No. 88 specification and silver iodide fine particles, and cooling and solidifying by cooling. (Preparation of color light-sensitive material) Thickness of 120μ with undercoat layer
m triacetylcellulose film support, Table 2
Each layer having the composition shown in Tables 1 to 4 was sequentially formed from the support side to prepare a multilayer color light-sensitive material sample 1001. In the table, the addition amount of each material is shown in grams per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of the amount of silver, and sensitizing dyes (indicated by SD-1 to 13) are shown in the number of moles per mole of silver. The above sample 1001
Include OIL-3, coating aids SU-1, SU-2, SU
-3, dispersion aid SU-4, viscosity modifier V-1, stabilizer S
T-1, two kinds of polyvinylpyrrolidone (AF-1, AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 100,000, calcium chloride, an inhibitor AF
-3, AF-4, AF-5, AF-6, AF-7, a hardener H-1 and a preservative Ase-1 were appropriately added.

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4] Table 5 shows the characteristics of the silver iodobromide emulsion used in the preparation of Sample 1001 described above. In the silver iodobromide emulsions shown in Table 5, the emulsions other than the silver iodobromide emulsion i were used in the respective layers of Tables 2 to 4 with respect to the surface area of the silver halide grains among the emulsions using the sensitizing dyes. After adding and aging so that the addition amount is the same, trifrylphosphine selenide, sodium thiosulfate, chloroauric acid, potassium thiocyanate are added, and fog and sensitivity are optimized according to the usual method. It was used after being chemically sensitized.

[0069]

[Table 5]

The compounds used in the preparation of the sample 1001 are shown below.

[0071]

[Chemical 2]

[0072]

[Chemical 3]

[0073]

[Chemical 4]

[0074]

[Chemical 5]

[0075]

[Chemical 6]

[0076]

[Chemical 7]

[0077]

[Chemical 8]

[0078]

[Chemical 9]

[0079]

[Chemical 10]

[0080]

[Chemical 11]

Further, in place of the emulsion Em-1 of the ninth layer, emulsions Em-2 to Em-7 were used, and samples 1002 to 1002 were used.
1007 was produced. Sample 1 produced as described above
001 to 1007 are prepared in two parts, one part is left as it is, and the remaining one part is irradiated with radiation so that the irradiation dose becomes 200 mR using 137 Cs as a radiation source, and then 1 part is irradiated with white light. / 200 seconds, 1.6 CM
Step wedge exposure is carried out in S, and then, Japanese Patent Laid-Open No.
Color development processing was carried out according to the development processing steps described in paragraph Nos. 0220 to 0227 of JP-A-123652.
The magenta density of each obtained developed sample was measured by a densitometer manufactured by X-rite, and the density (D) -exposure amount (L
A characteristic curve composed of ogE) was prepared and the sensitivities were obtained. The sensitivity was expressed by the reciprocal of the exposure amount that gives an optical density of the minimum density of magenta + 0.10. The stability of sensitivity to radiation was evaluated by obtaining the sensitivity stability of each sample by the following formula. Stability of sensitivity = [(sensitivity of radiation-irradiated sample) / (sensitivity of non-irradiated sample)] × 100 Further, the RMS value (magenta density of fog density + 0.30) of each sample is defined as an RMS value of 250 μm ²
Of the density value generated when the sample was scanned by the microdensitometer (1), and the stability of granularity with respect to radiation (granular stability) was determined for each sample by the following formula and evaluated. Granular stability = [(RMS value of irradiated sample) / (RMS value of unirradiated sample)] × 100 The obtained results are shown in Table 6.

[0082]

[Table 6] As is apparent from Table 6, samples 1003 to 1007 using the silver halide photographic emulsion of the present invention are comparative sample 10
In comparison with Nos. 01 and 1002, it showed superior performance in stability of sensitivity to radiation and stability of granularity.

Example 2 (Preparation of Emulsion Em-11) Using the tabular seed emulsion T-A1 used in Example 1, grain growth was carried out in the following procedure to prepare Emulsion Em-11. For stirring, the mixing and stirring device described in JP-A-62-160128 was used. Further, when removing soluble components from the reaction solution by ultrafiltration, the apparatus described in JP-A-10-339923 was used. Tabular seed emulsion T- equivalent to 0.264 mol
The reaction mother liquor consisting of A1, 1.2 ml of a 10 mass% methanol solution of the surfactant A, pure water, and 290.4 g of the gelatin B in a volume of 30.4 L was heated to 60 ° C. and 1.
While maintaining pAg of 9.4 with a 75 mol / L potassium bromide aqueous solution, the following liquid S-21 and liquid X-21 were added over 119 minutes while accelerating the flow rate using the double jet method. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. S-21 solution: 1.75 mol / L silver nitrate aqueous solution 7613
ml X-21 solution: 1.75 mol / L potassium bromide aqueous solution 7
613 ml Subsequently, the following S-22 solution was added over 18 minutes while decelerating, and the pAg was adjusted to 8.9. S-22 solution: 1.75 mol / L silver nitrate aqueous solution 725 m
l Continuously add the following solution I-21 and the following solution Z-21,
The pH was adjusted to 9.3 with a 0% aqueous potassium hydroxide solution and held for 6 minutes, and then the pH was adjusted to 5.0 with a 56% aqueous acetic acid solution.
PAg was adjusted to 9.75 mol / L with an aqueous potassium bromide solution.
Adjusted to 4. Solution I-21: aqueous solution 558 ml containing 69.3 g of sodium p-iodoacetamidobenzenesulfonate Z-21 solution: aqueous solution 248 ml containing 24.0 g of sodium sulfite.

Subsequently, the following S-23 solution and the following X-2 were used.
Liquid 3 was added in 16 minutes while accelerating the addition flow rate. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. 56% during addition
The pH was adjusted to 5.0 with an aqueous acetic acid solution and the pAg was controlled to 9.4 with an aqueous 1.75 mol / L potassium bromide solution. S-23 solution: 1.75 mol / L silver nitrate aqueous solution 1090
ml X-23 solution: 1.75 mol / L potassium bromide aqueous solution 1
090 ml Subsequently, the following S-24 solution was added over 16 minutes while decelerating to adjust the pAg to 8.4. S-24 solution: 1.75 mol / L silver nitrate aqueous solution 726 m
l Further subsequently, after adding the following M-21 solution, the following S-
Solution 25 and solution X-25 below were added over 24 minutes while accelerating the flow rate. During the addition, the pH was adjusted to 5. with a 56% acetic acid aqueous solution.
The pAg was controlled to 8.4 with 0, 1.75 mol / L potassium bromide aqueous solution. Then, pAg was adjusted to 9.4 with a 1.75 mol / L potassium bromide aqueous solution. Subsequently, the following S-26 solution and the following X-26 solution were added over 15 minutes while accelerating the flow rate. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. During the addition, the pH was adjusted to 5.0 with a 56% aqueous acetic acid solution.
The pAg was controlled at 9.4 with an aqueous 75 mol / L potassium bromide solution. M-21 solution: an aqueous solution containing 203.9 mg of K ₄ [Ru (CN) ₆ ] 115 ml S-25 solution: 1.75 mol / L silver nitrate aqueous solution 604 m
l X-25 solution: 1.75 potassium iodide aqueous solution 604 ml S-26 solution: 1.75 mol / L silver nitrate aqueous solution 1212
ml X-26 solution: 1.75 mol / L potassium bromide aqueous solution 1
212 ml

After completion of the addition, an aqueous solution containing 360 g of chemically modified gelatin (modification rate 95%) in which an amino group was phenylcarbamoylated was added according to the method described in JP-A-5-72658, and desalting and washing treatment were carried out. Then, gelatin is added to disperse well, and the pH is adjusted to 5.8 and p at 40 ° C.
Ag was adjusted to 8.9 and tabular silver halide emulsion Em-
I got 11. As a result of analyzing the silver halide grains contained in the tabular silver halide emulsion Em-11, tabular silver halide grains occupy 96% or more of the projected area of all grains, the average aspect ratio is 18, and the projected area is converted into a circle. The average particle size is 3.
3 μm, projected area circle conversion grain size distribution is 36%, average grain thickness is 0.20 μm, average twin plane distance is 120 Å, and tabular halogen having two twin planes parallel to the main plane. The silver halide grains accounted for 95% of the total number of grains. Further, in the tabular silver halide grains contained in the tabular silver halide emulsion Em-11, 32% of the grains have dislocation lines, and 12
% Have dislocation lines in the main plane, 10% have fringe portions and dislocation lines in the main plane, 25% have 10 or more dislocation lines in the fringe portion, and 15% have 30 dislocation lines in the fringe portion. It had the above dislocation lines. Also, tabular silver halide emulsion Em-
The average silver iodide content of the silver halide grains contained in No. 11 is 0.9 mol%, and the average surface silver iodide content is 3.5 mol%.
Met. Further, the variation coefficient of the distance between twin planes is 25%, the variation coefficient of the grain thickness is 22%, the (100) plane ratio of all the side surfaces of the tabular silver halide grain is 35%, and Hexagonal tabular silver halide grains accounted for 93% or more.

(Preparation of Emulsion Em-12) The above emulsion Em-
Emulsion Em-12 was prepared in the same manner as Emulsion Em-11, except that the following I-21a liquid and Z-21a liquid were used in place of I-21 liquid and Z-21 liquid. Solution I-21a: aqueous solution 806 ml containing 100.0 g of sodium p-iodoacetamidobenzenesulfonate Z-21a solution: aqueous solution 358 ml containing 34.7 g of sodium sulfite Silver halide grains contained in tabular silver halide emulsion Em-12 As a result, the tabular silver halide grains occupy 96% or more of the projected area of all the grains, the average aspect ratio is 18, the average of the projected area circle converted grain sizes is 3.3 μm, and the projected area circle converted grain size distribution. Is 33%, average particle thickness is 0.2
0 μm, the average distance between twin planes was 120Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains. In the tabular silver halide grains contained in the tabular silver halide emulsion Em-12, 52% had dislocation lines, 18% had dislocation lines on the main plane, and 17% had fringe portions. And 37% had 10 or more dislocation lines in the fringe portion, and 27% had 30 or more dislocation lines in the fringe portion. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-12 was 1.3 mol%, and the average surface silver iodide content was 4.5 mol%.
Further, the variation coefficient of the distance between twin planes is 25%, the variation coefficient of the grain thickness is 22%, the (100) plane ratio of all the side surfaces of the tabular silver halide grain is 35%, and Hexagonal tabular silver halide grains accounted for 93% or more.

(Preparation of Emulsion Em-13) The above emulsion Em-
11. In the preparation of 11, the soluble component of the reaction solution was added by ultrafiltration after addition of the S-21 solution and the X-21 solution over 10 minutes.
Emulsion Em-13 was prepared in the same manner as Emulsion Em-11 except that 0 L was removed and the following I-21b solution and Z-21b solution were used instead of I-21 solution and Z-21 solution. did. Solution I-21b: 1054 ml of an aqueous solution containing 130.8 g of sodium p-iodoacetamidebenzenesulfonate Z-21b solution: an aqueous solution of 468 ml of 45.4 g of sodium sulfite Silver halide grains contained in tabular silver halide emulsion Em-13 As a result, the tabular silver halide grains occupy 96% or more of the projected area of all the grains, the average aspect ratio is 18, the average of the projected area circle converted grain sizes is 3.3 μm, and the projected area circle converted grain size distribution. 34%, average particle thickness 0.2
0 μm, the average distance between twin planes was 120Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains. 70% of the tabular silver halide grains contained in the tabular silver halide emulsion Em-13 had dislocation lines, 31% had dislocation lines in the main plane, and 28% had fringe portions. And dislocation lines on the main plane, 62% had 10 or more dislocation lines in the fringe portion, and 40% had 30 or more dislocation lines in the fringe portion. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-13 was 1.5 mol% and the average surface iodide content was 4.9 mol%.
Further, the variation coefficient of the distance between twin planes is 24%, the variation coefficient of the grain thickness is 22%, the (100) plane ratio of all the side surfaces of the tabular silver halide grains is 30%, Hexagonal tabular silver halide grains accounted for 92% or more of the number of grains.

(Preparation of Emulsion Em-14) The above emulsion Em-
11. In the preparation of 11, the soluble component of the reaction solution was added by ultrafiltration after addition of the S-21 solution and the X-21 solution over 10 minutes.
The pAg after removing 0 L and adding the S-22 solution was 8.
Emulsion Em-14 was prepared in the same manner as Emulsion Em-11, except that the solution No. 6 was adjusted to 6 and the following solutions I-21c and Z-21c were used in place of solutions I-21 and Z-21. did. I-21c solution: 1116 ml of an aqueous solution containing 138.5 g of sodium p-iodoacetamidebenzenesulfonate Z-21c solution: An aqueous solution of 4495 g containing 48.0 g of sodium sulfite 495 ml Silver halide grains contained in tabular silver halide emulsion Em-14 As a result, the tabular silver halide grains occupy 96% or more of the projected area of all the grains, the average aspect ratio is 18, the average of the projected area circle converted grain sizes is 3.3 μm, and the projected area circle converted grain size distribution. Is 31%, average particle thickness is 0.2
0 μm, the average distance between twin planes was 120Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains. The tabular silver halide grains contained in the tabular silver halide emulsion Em-14 had a dislocation line of 82%, a dislocation line on the main plane of 60%, and a fringe portion of 59%. And dislocation lines on the main plane, 67% had 10 or more dislocation lines in the fringe portion, and 54% had 30 or more dislocation lines in the fringe portion. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-14 was 1.8 mol%, and the average surface silver iodide content was 5.1 mol%.
Further, the coefficient of variation of the distance between twin planes is 21%, the coefficient of variation of the grain thickness is 19%, the (100) plane ratio of all side surfaces of the tabular silver halide grain is 32%, Hexagonal tabular silver halide grains accounted for 93% or more.

(Preparation of Emulsion Em-15) The above emulsion Em-
In the preparation of 11, the soluble component 1 of the reaction solution was added to the reaction solution over 30 minutes by ultrafiltration after addition of the S-21 solution and the X-21 solution.
2.0 L was removed, and the pAg after the S-22 solution was added was adjusted to 8.6, and the following I-21d solution and Z-21d solution were replaced with the I-21 solution and the Z-21 solution. Emulsion Em-15 was prepared in the same manner as Emulsion Em-11 except that it was used. Solution I-21d: 1363 ml of an aqueous solution containing 169.3 g of sodium p-iodoacetamidebenzenesulfonate Z-21d solution: An aqueous solution of 605 ml containing 58.7 g of sodium sulfite Silver halide grains contained in tabular silver halide emulsion Em-15 As a result, the tabular silver halide grains occupy 96% or more of the projected area of all the grains, the average aspect ratio is 18, the average of the projected area circle converted grain sizes is 3.3 μm, and the projected area circle converted grain size distribution. Is 33%, average particle thickness is 0.2
0 μm, the average distance between twin planes was 120Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains. In the tabular silver halide grains contained in the tabular silver halide emulsion Em-15, 92% had dislocation lines, 75% had dislocation lines in the main plane, and 73% had fringe portions. And dislocation lines on the main plane, 88% had 10 or more dislocation lines in the fringe portion, and 71% had 30 or more dislocation lines in the fringe portion. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-15 was 2.2 mol%, and the average surface iodide content was 6.1 mol%.
Further, the variation coefficient of the distance between twin planes is 23%, the variation coefficient of the grain thickness is 22%, the (100) plane ratio of all the side surfaces of the tabular silver halide grain is 35%, and Hexagonal tabular silver halide grains accounted for 93% or more.

(Preparation of Emulsion Em-16) The above emulsion Em-
In Preparation of 11, the tabular seed emulsion T-A2 used in Example 1 was used in place of the tabular seed emulsion T-A1, and
After addition of S-21 solution and X-21 solution, 30 by ultrafiltration
12.0 L of the soluble component of the reaction solution was removed over a period of time, the pAg after addition of the S-22 solution was adjusted to 8.3, and the following I- solution was used instead of the I-21 solution and the Z-21 solution. 21e
Emulsion Em-16 was prepared in the same manner as Emulsion Em-11, except that the solution and Z-21e solution were used. I-21e solution: 1550 ml of an aqueous solution containing 192.3 g of sodium p-iodoacetamidebenzenesulfonate Z-21e solution: An aqueous solution of 688 ml of 66.7 g of sodium sulfite Silver halide grains contained in tabular silver halide emulsion Em-16 As a result, tabular silver halide grains occupy 97% or more of the projected area of all grains, 50% of the projected area of all grains are tabular grains with an aspect ratio of 50 or more, and the average aspect ratio is 52. The average area circle converted grain size was 4.3 μm, the projected area circle converted grain size distribution was 35%, the average grain thickness was 0.086 μm, and the average twin plane distance was 10 μm.
It was 0Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 96% of the total number of grains. In the tabular silver halide grains contained in the tabular silver halide emulsion Em-16, 96% of the grains have dislocation lines, 93% have dislocation lines on the main plane, and 92% have fringe portions. And dislocation lines on the main plane, 90% of which is 1 in the fringe area.
It had 0 or more dislocation lines, and 87% had 30 or more dislocation lines in the fringe portion. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-16 was 2.5 mol%, and the average surface iodide content was 6.
It was 8 mol%. The variation coefficient of the distance between twin planes is 2
0%, the variation coefficient of grain thickness is 11%, and the (100) face ratio of all side faces of the tabular silver halide grains is 32%.
%, And 90% or more of the number of grains was occupied by hexagonal tabular silver halide grains. In Table 7 below, the emulsion Em-
11 to Em-16 average aspect ratio (AR), average projected area circle conversion grain size (D), average thickness, number ratio of tabular grains having dislocation lines in the main plane, and 30 or more in the fringe portion. The number ratio of tabular silver halide grains having dislocation lines (FD30) and the number ratio of tabular silver halide grains having 10 or more dislocation lines in the fringe portion (FD10) are also shown. Also, (FD30) × (log ₁₀ AR),
(FD10) × (log ₁₀ AR), (FD30) × (l
The calculated values of (log ₁₀ D) and (FD10) × (log ₁₀ D) are also shown.

[0091]

[Table 7] Using the above emulsions Em-11 to Em-16, multilayer color light-sensitive material samples 1101 to 1106 were prepared in the same manner as the multilayer color light-sensitive material sample 1001 of Example 1. With respect to the obtained samples 1101 to 1106, the sensitivity stability and the grain stability were evaluated in the same manner as in Example 1. The results obtained are shown in Table 8.

[0092]

[Table 8] As is apparent from Table 8, Samples 1102 to 1106 using the silver halide photographic emulsion of the present invention are Comparative Sample 11
In comparison with No. 01, it showed superior performance in terms of stability of radiation sensitivity and granular stability.

[0093]

INDUSTRIAL APPLICABILITY The silver halide photographic emulsion of the present invention not only has high sensitivity and high image quality, but also provides a silver halide photographic emulsion with improved sensitivity deterioration and image quality deterioration due to natural radiation. it can.

Claims (17)

[Claims] 1. A silver halide in which tabular silver halide grains occupy 70% to 100% of the projected area of all grains, and the tabular silver halide grains have an average aspect ratio in the range of 12 to 500. In a photographic emulsion, the tabular silver halide grain number ratio (%) (FD30) and average aspect ratio (FD30) having 30 or more dislocation lines in the fringe portion of the tabular silver halide grain in the silver halide photographic emulsion AR)
And 30 satisfy the relationship of 30 ≦ (FD30) × Log ₁₀ (AR) ≦ 300. 2. FD30 and AR are 50 ≦ (FD30)
2. The silver halide photographic emulsion according to claim 1, wherein the relationship of * Log ₁₀ (AR) ≤300 is satisfied. 3. FD30 and AR are 70 ≦ (FD30)
2. The silver halide photographic emulsion according to claim 1, wherein the relationship of * Log ₁₀ (AR) ≤300 is satisfied. 4. A tabular silver halide grain occupies 70% to 100% of the projected area of all grains, and the tabular silver halide grain has an average aspect ratio of 15 to 500. In a photographic emulsion, the tabular silver halide grain number ratio (%) (FD10) and the average aspect ratio (FD10) having 10 or more dislocation lines in the fringe portion of the tabular silver halide grain in the silver halide photographic emulsion AR)
And 50 satisfy the relationship of 50 ≦ (FD10) × Log ₁₀ (AR) ≦ 300. 5. FD10 and AR are 80 ≦ (FD10)
The silver halide photographic emulsion according to claim 4, wherein the relationship of × Log ₁₀ (AR) ≦ 300 is satisfied. 6. FD10 and AR are 100 ≦ (FD1
The silver halide photographic emulsion according to claim 4, wherein the relationship of 0) × Log ₁₀ (AR) ≦ 300 is satisfied. 7. A tabular silver halide grain in which tabular silver halide grains have an average projected area circle equivalent grain size of 0.1 to 50 μm and an average thickness of 0.005 to 0.1 μm. 7. The silver halide photographic emulsion according to any one of claims 1 to 6, which is a grain. 8. A silver halide in which tabular silver halide grains occupy 70% to 100% of the projected area of all grains and the tabular silver halide grains have an average aspect ratio in the range of 12 to 500. A silver halide photographic emulsion, wherein the tabular silver halide grains in said silver halide photographic emulsion have an average projected area circle conversion grain size (μm) in the range of 2.0 to 50, and Of tabular silver halide grains having 30 or more dislocation lines in the fringe portion of tabular silver halide grains (FD30) and projected area of tabular silver halide grains in terms of circle diameter (μm) Average (D) of 9 ≦ (FD30) × Log ₁₀ (D) ≦ 20
A silver halide photographic emulsion characterized by satisfying the relationship of 0. 9. FD30 and D are 15 ≦ (FD30) ×
9. The silver halide photographic emulsion according to claim 8, wherein the relationship of Log ₁₀ (D) ≦ 200 is satisfied. 10. FD30 and D are 20 ≦ (FD30)
9. The silver halide photographic emulsion according to claim 8, wherein the relationship of × Log ₁₀ (D) ≦ 200 is satisfied. 11. 70% to 100% of the projected area of all grains
A tabular silver halide grain, wherein the tabular silver halide grain has an average aspect ratio of 15 to 500, wherein the tabular silver halide grain is a tabular silver halide emulsion The average of the projected area circle conversion particle size (μm) of the particles is in the range of 2.5 to 50, and
The tabular silver halide grain number ratio (FD) having 10 or more dislocation lines in the fringe portion of the tabular silver halide grain in the silver halide photographic emulsion (FD10) and the projected area circle of the tabular silver halide grain. The average (D) of the converted particle diameters (μm) is 15 ≦ (FD10) × Log ₁₀ (D) ≦ 20.
A silver halide photographic emulsion characterized by satisfying the relationship of 0. 12. FD10 and D are 20 ≦ (FD10)
The silver halide photographic emulsion according to claim 11, wherein xLog ₁₀ (D) ≦ 200. 13. FD10 and D are 30 ≦ (FD10)
The silver halide photographic emulsion according to claim 11, which satisfies the relationship of × Log ₁₀ (D) ≦ 200. 14. The tabular silver halide grain is a tabular silver halide grain having an average thickness of 0.005 to 0.1 μm. The described silver halide photographic emulsion. 15. A silver halide photographic emulsion containing tabular silver halide grains, wherein the average aspect ratio of the silver halide photographic emulsion is in the range of 12 to 500, and the projection of the silver halide photographic emulsion. The average particle size of the area-circle converted particle size is in the range of 2.0 to 50 μm, and the projected area of all particles is 7
0% to 100% are tabular silver halide grains, the tabular silver halide grains having 30 or more dislocation lines in the fringe portion, and the main plane portion of the tabular silver halide grains. A silver halide photographic emulsion characterized by having dislocation lines at the ends. 16. 50% to 1 of tabular silver halide grains
The silver halide photographic emulsion according to any one of claims 1 to 15, wherein 00% (number) is a tabular silver halide grain having a dislocation line in the main plane. 17. A silver halide photograph having at least one silver halide emulsion layer containing the silver halide photographic emulsion according to any one of claims 1 to 16 on a support. Photosensitive material.