JPH11271905A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material capable of enhancing graininess and stabilizing resolution reproduction. SOLUTION: The flat silver halide grains contained in an emulsion layer in the silver halide photographic sensitive material comprises (1) having an average distance between twin crystal faces, (2) their principal faces are circular and hexangular, (3) average dislocation line lengths are >=30 nm and <30 nm, (4) the dislocation lines are located mainly on the principal faces and only on the fringe parts, (5) comprising the ones having an aspect ratio of >=8 and >=30 dislocation lines per each grain and those having an aspect ratio of 5-8 and dislocation lines of the same number per each grain, (6) having dislocation lines introduced and an average corresponding sphere diameter of >=0.6 μm, and 0.45 to 0.6 μm, and (7) the ones having a variation coefficient of dislocation lines length of <25% and the others having >=25%.

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 light-sensitive material.
In more detail, it has excellent granularity and
Silver halide photographic feeling with improved gradation stability in motion
Light materials. [0002] 2. Description of the Related Art In recent years, silver halide color photographic light-sensitive materials have been developed.
In the field of, for example, a new standard (Advanced
System by photo film system)
There is a growing demand for higher image quality. In addition, a compact camera and a film with lens
Of various environmental changes that occur in the market
Therefore, it is also an important requirement that stable tone reproduction be obtained.
ing. In response to such demands, silver halide emulsions
Much research has been done around improvement. Generally, to improve image quality, a halo
Reduce the particle size of the silver halide particles to reduce
Increase the number of particles and increase the number of coloring points (pixels)
The method is effective. However, reducing the particle size is not
In order to satisfy both high sensitivity and high image quality.
Had limitations. Therefore, one silver halide grain was hit.
Technology to improve the sensitivity / size ratio of
However, one of the techniques is to use tabular silver halide grains.
The technique is disclosed in JP-A-58-111935 and 58-11.
Nos. 1936 and 58-111937 and 58
Nos. 11313927 and 59-99433.
Are listed. Tabular silver halide emulsion (hereinafter simply referred to as
"Tabular grains") are hexahedral, octahedral or
Consisting of so-called normal crystal silver halide grains such as dodecahedron
Compared to emulsion, per unit volume of silver halide grains
Large surface area and more spectral sensitizing dye on the particle surface
Can improve color sensitization efficiency
High sensitivity can be expected. Japanese Patent Application Laid-Open No. 63-163451 discloses a flat
The longest distance between two or more twin planes (a)
Flat plate whose value of the ratio (b / a) to the thickness (b) is 5 or more
The technology using particles is further described in Japanese Patent Application Laid-Open No. Hei 1-2201649.
The gazette also states that the number of transition lines present in tabular grains
The specified technology is shown. Also, JP-A-1-131
No. 541 discloses that the shape of two parallel main outer surfaces is a straight line.
Technique using circular tabular grains having a part ratio of 4/5 or less
The art is shown. Twin planes and transitions of these tabular grains
Technology that focuses on line introduction, particle shape control, etc.
The effect of improving graininess without decreasing degree has been reported.
You. However, these silver halide grains
When using, the gradation stability is impaired by the processing fluctuation.
Problem. On the other hand, from the viewpoint of gradation stability, Japanese Patent Laid-Open No.
JP-A-304449, JP-A-4-93941, JP-A-4-93941
Japanese Patent No. -40446 discloses that at least different average particle sizes are used.
Two or more kinds of monodispersed silver halide emulsions can be mixed in the same photosensitive layer or
Indicates a technology to be included in all of the same color sensitivity groups.
You. However, in response to recent high-level demands,
However, the improvement effect of these technologies is not enough to
Further improvement in performance is desired. [0009] SUMMARY OF THE INVENTION Accordingly, an object of the present invention is as follows.
Achieves excellent graininess without compromising sensitivity,
First, stable gradation reproduction against environmental fluctuations occurring in the market
Providing silver halide photographic light-sensitive materials
You. [0010] The above objects of the present invention are as follows. (1) At least one layer of silver halide emulsion on a support
Silver halide photographic material having a layer
In both cases, the distance between twin planes is flat in one silver halide emulsion layer.
Tabular silver halide emulsion having an average value of 30 nm or more
(A), the average value of the distance between twin planes is less than 30 nm
Silver halide emulsion (A)
Tabular silver halide emulsion equal to or smaller than
(B) a silver halide photograph containing:
Photosensitive material. (First invention) (2) at least one silver halide emulsion on a support
Silver halide photographic material having a layer
In each case, the shape of the main plane is circular in one silver halide emulsion layer.
Tabular silver halide emulsion (C) and the shape of the main plane
The shape is hexagonal and the sphere-converted average particle size is
Tabular halogenation equal to or smaller than silver halide emulsion (C)
Characterized by containing a silver halide emulsion (D).
Silver halide photographic material. (Second invention) (3) At least one silver halide emulsion on a support
Silver halide photographic material having a layer
In both silver halide emulsion layers, the average length of dislocation lines
Tabular silver halide emulsion having an average value of 30 nm or more
(E) and the average length of dislocation lines is less than 30 nm
Silver halide emulsion (E)
Tabular silver halide emulsion equal to or smaller than
(F) and a silver halide photograph containing
Photosensitive material. (Third invention) (4) At least one layer of silver halide emulsion on a support
Silver halide photographic material having a layer
Both dislocation lines are mainly contained in one silver halide emulsion layer.
A tabular silver halide emulsion (G) on the main plane;
Has a dashed line only in the fringe part, and the sphere-converted average particle size is flat.
Equal to or smaller than the silver halide emulsion (G)
And a tabular silver halide emulsion (H).
Silver halide photographic light-sensitive material. (4th invention) (5) At least one layer of silver halide emulsion on a support
Silver halide photographic material having a layer
And the average aspect ratio in one silver halide emulsion layer
Is 8 or more and has 30 or more dislocation lines per particle
Tabular silver halide emulsion (I) and average aspect ratio
Is 5 or more and less than 8, and the number of dislocation lines per grain is 30 or more.
Having a sphere-equivalent mean particle size of tabular silver halide emulsion
Tabular silver halide milk equal to or smaller than (I)
Silver halide photography characterized by containing an agent (J)
True photosensitive material. (Fifth invention) (6) At least one layer of silver halide emulsion on a support
Silver halide photographic material having a layer
In both cases, dislocation lines are introduced into one silver halide emulsion layer.
Tabular halo with a sphere-converted average particle size of 0.6 μm or more
Silver Genide Emulsion (K) and sphere equivalent with dislocation lines
Flat plate with an average particle size of 0.45 μm or more and less than 0.6 μm
Characterized by containing a silver halide emulsion (L)
Silver halide photographic material. (Sixth invention) (7) At least one layer of silver halide emulsion on a support
Silver halide photographic material having a layer
In both silver halide emulsion layers, the length of dislocation lines
Tabular silver halide emulsion having a dynamic coefficient of less than 25% (M)
And the coefficient of variation of the dislocation line length is 25% or more,
Is the average particle size equal to that of the tabular silver halide emulsion (M)?
Or a small tabular silver halide emulsion (N).
A silver halide photographic light-sensitive material, characterized in that: (7th
invention) Is achieved by Hereinafter, the present invention will be described in detail. The tabular silver halide emulsion according to the present invention comprises:
A silver halide emulsion containing tabular silver halide grains.
You. [0013] Tabular grains are crystallographically classified as twins.
Silver halide grains. A twin is a single particle
A silver halide crystal having at least one twin plane within
However, the classification of twin morphology was reported by Klein and Moiser.
Text photography respondents (Photogr
aphische Korrespondenz) Vol. 99, p100, ibid.
The details are described in Vol. 100, p.57. In the present invention, the tabular grains are flat on the main plane.
It has two twin planes. Twin planes in transmission electron microscope
More can be observed. The specific method is as follows
is there. First, the tabular grains contained are substantially
The silver halide photographic emulsion is oriented so that the main plane is oriented parallel.
Apply to make a sample. This is a diamond cutter
To obtain a thin section with a thickness of about 0.1 μm.
You. By observing this section with a transmission electron microscope,
The existence of a twin plane can be confirmed. Two tabular grains in the tabular grains according to the present invention are used.
The distance between crystal planes was calculated using the above-mentioned transmission electron microscope.
Cross section cut almost perpendicular to the main plane during observation
Arbitrarily selected 1000 or more tabular grains showing
Of the even number of twin planes parallel to
Determine the distance between crystal planes for each particle, and perform averaging.
It is obtained by doing. In the present invention, the distance between twin planes is determined by nucleation.
Factors affecting supersaturation at the time, for example, gelatin
Concentration, gelatin type, temperature, iodine ion concentration, pBr, p
Combination of various factors such as H, ion supply speed, stirring speed
Can be controlled by appropriate selection
Wear. Generally speaking, nucleation is performed in a highly supersaturated state.
For example, the distance between twin planes can be reduced. For details on the supersaturation factor, see, for example,
JP-A-63-92924 or JP-A-1-213
637 can be referred to. In the present invention, the thickness of the tabular grains is
Observation of the section using the transmission electron microscope
To obtain the thickness of each particle, and perform averaging.
It is obtained by doing. The thickness of the tabular grains is 0.05
μm-1.5 μm, more preferably 0.07
μm to 0.50 μm. In the present invention, tabular grains are formed on the entire projection surface.
50% or more of the product has an aspect ratio (particle size / particle thickness) of 5
The above is mentioned, but preferably, 60% of the total projected area
The above is an aspect ratio of 5 or more, and more preferably,
70% or more of the projected area has an aspect ratio of 5 or more. [0020] The present invention relates to a method for preparing a support, comprising:
Silver halide photographic material having a silver halide emulsion layer
In at least one silver halide emulsion layer,
Contains two types of tabular silver halide emulsions. In the present invention, the sphere-converted particle size is defined as halogen
Of a sphere with the same volume as silver halide particles
Is the diameter. The tabular grains of the present invention have an average particle diameter in terms of sphere.
Is preferably 0.2 μm or more, more preferably
Is from 0.3 μm to 3.0 μm. In the first invention of the present invention, the flat halo
The sphere-equivalent average particle size of the silver gemide emulsions (A) and (B) is
(A) ≧ (B) in the second invention,
Spherical equivalent particle diameter of silver halide emulsions (C) and (D)
The relationship of (C) ≧ (D) is satisfied.
Average particle diameter of spherical silver halide emulsions (E) and (F)
The values satisfy the relationship of (E) ≧ (F) in the fourth invention of the present invention.
Of the tabular silver halide emulsions (G) and (H)
The calculated average particle size is in the relationship of (G) ≧ (H), which is the fifth value of the present invention.
In the invention, the tabular silver halide emulsion (I) and
The sphere-converted average particle diameter value of (J) is expressed by the relationship of (I) ≧ (J),
In the seventh invention, a tabular silver halide emulsion (M) and
And (N) mean particle size in sphere are (M) ≧ (N)
is there. In the present invention, the sphere-converted particle size is, for example,
Enlarge silver halide grains from 10,000 to 70,000 times with an electron microscope.
Take a picture of the particle size and particle size on the print.
It can be obtained by actual measurement. Measurement particle number
Are indiscriminately 1000 or more. The sphere-converted average particle diameter r has a sphere-converted particle diameter ri.
Particle frequency ni and ri^ThreeProduct ni × ri^ThreeIs the largest
Is defined as the particle size ri (significant digits, minimum digits)
Numbers are rounded.) The tabular grains of the present invention may be a monodisperse halogen.
It is preferably a silver halide emulsion. Where monodisperse halogen
The silver halide emulsion has a sphere-converted average particle size r of ± 20.
% Of the silver halide within the grain size range
What is 60% or more of the weight of silver gemide particles is preferred,
More preferably 70% or more, further preferably 80% or more
It is. In the first invention, the tabular silver halide milk
The average value of the distance between twin planes of the agent (A) is 30 nm or more.
Is preferably 35 nm or more, more preferably 3 nm or more.
8 nm or more. On the other hand, a tabular silver halide agent (B)
The average value of the distance between twin planes is less than 30 nm.
Or less than 25 nm, more preferably less than 22 nm.
Is full. In the second invention, the shape of the main plane is circular.
In a certain tabular silver halide emulsion (C), the main plane
Tabular grains having a circular shape in the silver halide emulsion
50% or more of the total projected area of silver halide grains of
Occupies at least 70%, more preferably at least 90%.
You. Here, a flat plate whose main plane is circular
Particles are those whose (111) main plane has a circular shape.
Are shown. Generally, tabular grains having two parallel twin planes
The shape of the (111) main plane is hexagonal.
The round tabular grains referred to in the above have rounded hexagonal corners.
Equivalent to Main Circular Tabular Grains in the Present Invention
The plane is circular, but need not be perfectly circular. Immediately
That is, a straight portion may be partially provided. Has straight section
In this case, the side length of the hexagonal flat plate having an adjacent side ratio of 2-1 is 4/5 to
0 (hereinafter referred to as the linear portion ratio of 4/5 or less)
preferable. However, the corners of the hexagonal tabular grains are rounded.
If the length of the side, extend the straight line portion of the side,
Distance between the intersection of the straight line of the adjacent side and the extended line
It is represented by separation. Of course, there is no straight part (ie, straight line
Circular particles having a part ratio of zero) may be used. Preferably the linear part ratio
The rate is 1/2 to 0. A flat halogen having a circular main plane.
Nucleation-1st Ostwald
Ripening-Method for performing second Ostwald ripening after crystal growth
There is. This second aging is preferably performed under the following conditions.
Good. That is, temperature: 40 ° C. to 80 ° C., preferably
50 ° C. to 80 ° C., time; 10 to 100 minutes, preferably
20-60 minutes, gelatin concentration; 0.05-10 weight
%, Preferably 1.0 to 5% by weight, and the concentration of the silver halide solvent.
Degree: 0 to 0.4 mol / L, preferably 10^-Four~ 0.1
mol / L. pBr is preferably 1.8 to 3.5.
Is 2.0 to 3.0. In particular, ripening at low pAg side
In general, tabular grains have their edges dissolved and dissolved
Things settle on the major surfaces of the tabular grains. That is,
As a result of dissolution, the aspect ratio decreases while forming a circular shape.
Go a little. This indicates that the equilibrium crystal habit at the low pAg side is (10
Because it is a 0) plane, the morphology tends to shift to the equilibrium habit side.
It is. It should be noted that as the edges of the hexagonal tabular grains are rounded,
The temperature is the temperature at the time of the second ripening, the pBr value, the halogenation used.
It depends on the type and concentration of the silver solvent.
Change and observe the electron micrograph image of the resulting particles.
Thus, conditions can be set. Usually a haloge
Increasing the concentration of the silver bromide solvent promotes rounding,^-Dark
When the degree is increased, rounding is suppressed. In the second aging step, hexagonal tabular grains are used.
Effect of reducing a small amount of non-flat fine particles present after particle formation
It also has fruit. Another method for producing circular tabular grains is as follows.
After making hexagonal tabular grains, further reduce the pAg
And in the presence of an AgX solvent under low supersaturation
There is a way to grow, and by doing this,
Edge part becomes round, (100) face appears at edge part
It is. The low pAg conditions are defined as pBr 1.8 to
4.0, preferably 2.0-3.5, with low supersaturation
Is 0 to 40% of the critical growth rate of the emulsion. Ma
The concentration of the AgX solvent used is from 0 to 10^-1m
ol / L is preferred. In the second invention, the shape of the main plane is hexagonal
In the tabular silver halide emulsion (D),
Tabular grains having a hexagonal surface shape are made of silver halide milk.
Not less than 50% of the total projected area of silver halide grains in the agent.
Preferably at least 70%, more preferably at least 90%
ing. Here, the hexagonal tabular grains are defined as
Of the (111) plane is a hexagon, and its maximum adjacent side
The particles having a ratio of 1.0 to 2.0 are shown. Next to here
The tangent side ratio is the side with the minimum length that forms a hexagon
Is the ratio of the length of the side with the maximum length to the length of
You. The hexagonal tabular grains of the present invention have a maximum adjacent side ratio of 1.0
If it is ~ 2.0, its corners may be slightly rounded
No. If the corners are slightly rounded, the length of the side
Extend the straight part of the side and extend the straight part of the adjacent side
It is represented by the distance between the intersection with the line. The hexagonal tabular grains of the present invention form a hexagon.
Of each side is at least 1/2 of a substantially straight line
Is preferable, and in particular, 4/5 or more is substantially a straight line.
Is preferred. In the present invention, the adjacent side ratio is 1.
More preferably, it is 0 to 1.5. The silver halide emulsion of the present invention contains an average silver iodide content.
The percentage is preferably at least 1 mol%, more preferably
And preferably 1 to 10 mol%, particularly preferably 2 to 8 mol%.
%. The tabular grains of the present invention mainly contain silver iodobromide.
Is preferable, but the effect of the present invention is
Silver halide of other composition within the range not impairing, for example,
Silver chloride can be included. Distribution of silver iodide in silver halide grains
Condition can be detected by various physical measurement methods.
For example, lectures of the Photographic Society of Japan, 1981 Annual Conference
Luminescence at low temperatures, as described in the abstract
Measurement by using the EPMA method or X-ray diffraction method
Can be. In the present invention, individual silver halide grains
Silver iodide content and average silver iodide content of
(Electron Probe Micro Analyzer method)
Can be obtained by This method uses emulsion grains
Create well-dispersed samples so that they do not touch each other
Irradiate an electron beam to generate X
Perform elemental analysis of extremely small parts by analyzing lines
Things. By this method, the silver emitted from each particle
By determining the characteristic X-ray intensity of iodine and iodine,
The halogen composition of the child can be determined. At least 50 grains
If the silver iodide content is determined by the EPMA method for
From these averages, the average silver iodide content is determined. The tabular grains of the present invention contain silver iodide between grains.
Preferably, the prevalence is more uniform. EPMA
When the distribution of silver iodide content between grains was measured by the method,
And the relative standard deviation is 30% or less, further 20% or less.
Is preferred. Silver iodide content on the surface of tabular grains of the present invention
Is preferably 1 mol% or more, and 2 to 20 mol
More preferably, it is 1%. In the present invention, the surface of the tabular grains refers to
The outermost layer of the silver halide grains, including the outermost surface.
Means the depth from the outermost surface of the particle to 50 °. The present invention
The halogen composition on the surface of the tabular grains was determined by the XPS method (X-ray
 Photoelectron Spectroscopy method: X-ray photoelectron spectroscopy)
Is determined as follows. That is, 1 × 10^-8super torr
In a high vacuum, cool down to -110 ° C or less,
MgKα as an X-ray source voltage 15 kV, X-ray source current 4
Irradiation at 0 mA, Ag 3d5 / 2, Br 3d, I
It measures about 3d3 / 2 electrons. Measured peak
Of the integrated intensity of the image with a sensitivity factor
From these intensity ratios, the halide groups on the silver halide surface
Ask for success. Next, the dislocation lines of the silver halide grains
explain about. The dislocation lines of silver halide grains are, for example,
For example, J.F.Hamilton, Photo.Sci.Eng. 11 (1967) 5
7, T. Shiozawa, J. Soc. Phot. Sci. Japan 35 (197
2) A low-temperature transmission electron microscope described in 213 was used.
Observable by direct methods. That is, from emulsion to grain
Be careful not to apply enough pressure to cause dislocations.
The extracted silver halide grains into a mesh for an electron microscope.
To prevent damage caused by electron beams (such as printouts).
Observation by the transmission method with the sample cooled
U. At this time, the thicker the particle, the harder the electron beam penetrates.
, It is clearer to use a high-pressure electron microscope
Can be observed. Obtained by such a method
From the obtained particle photograph, the location of dislocation lines in individual particles,
The number and length can be determined. In the fourth invention, the dislocation lines are mainly
The tabular silver halide grains (G) on the surface are
The number of dislocation lines in the central region of the plane
Particles that are 80% or more of the total number of dislocation lines
U. The central region of the main plane of the tabular grains referred to here
Is the radius of a circle having an area equal to the major plane of the tabular grain
With a radius of 80% of the center of the circle
Is a region having a thickness of tabular grains. one
On the other hand, the fringe portion of the tabular grain is outside the central region.
Around tabular grains having an area equivalent to the annular region of
Region having a thickness of tabular grains.
U. Measurement of the number of dislocation lines existing in one particle
This is performed as follows. Change the tilt angle with respect to the incident electrons
A series of grain photographs were taken for each particle, and the existence of dislocation lines
Check your location. At this time, the number of dislocation lines can be counted.
For, count the number. Dislocation lines exist densely
Or when dislocation lines intersect each other,
When the number of dislocation lines per particle cannot be counted
In this case, it is counted that many dislocation lines exist. Present in the central region of the main plane of tabular grains
Many dislocation lines form a so-called dislocation network,
The number may not be clearly counted.
Dislocation lines in the outer region of tabular grains
Is a line that extends radially from the center of the particle to the side.
But often meanders. In the third to seventh inventions, the tabular grains
Indicates that the number ratio of 30% or more has a transition line,
Preferably, at least 50% of the ratio has a transition line
And that 70% or more of the number ratio has a transition line.
More preferred. In the third invention, the tabular silver halide milk
The average value of the length of the transition line of the agent (E) is 30 nm or more.
And preferably 35 nm or more. On the other hand, flat halo
The average value of the length of the transition line of the silver gemide emulsion (F) is 30 nm.
, Preferably less than 25 nm. Here, the average value of the length of the transition line is one particle.
The average value of the length of the transition line existing in
In the silver gemide emulsion (E), particles satisfying the above conditions are contained in a number ratio.
At a rate of 30% or more,
It is preferable that the particles have 50% or more in number ratio.
No. In the fourth invention, the tabular silver halide milk
Agent (G) has a transition line mainly on the main plane. here
And having a transition line mainly on the main plane means that
Of the transition lines existing on the principal plane
The number of lines is 70% or more, but 80% or more
It is preferably present on the main plane, and 90% or more of the main plane
More preferably, it exists in a planar shape. On the other hand, the tabular silver halide emulsion (H)
It has a transition line mainly in the fringe part, and its number is
10 or more. Here the transition line is mainly the fringe
Has only the total number of transition lines in one particle
On the other hand, the number of transition lines existing in the fringe part is 70% or more.
It means that 80% or more exists in the fringe part
Preferably, 90% or more is present in the fringe portion
Is more preferred. Tabular silver halide emulsion (G) and tabular
In the silver halide emulsion (H), the presence of the above transition line
Particles that satisfy the position condition are more likely to have a transition line.
Must be at least 50%, but at least 70%
Preferably, it is 90% or more. In the fifth invention, the tabular silver halide milk
The agent (I) has an average aspect ratio of 8 or more and is composed of 1 particle.
With 30 or more transition lines per particle
It is preferable to have 40 or more lines,
More preferably, the number of lines is 50 or more. On the other hand, the tabular silver halide emulsion (J)
The average aspect ratio is 5 or more and less than 8, and hits one particle.
Have more than 30 transition lines, but the transition line per particle
Preferably, it has 40 or more transition lines per particle
More preferably 50 or more. Here, particles satisfying the above condition of the number of transition lines
Must be 50% or more of the number of particles having a transition line.
However, it is preferably 70% or more, and more preferably 9% or more.
0% or more. In the seventh invention, the tabular halogonized silver milk
Agent (M) has a coefficient of variation of the transition line length of less than 25%.
However, it is preferably 20% or less. On the other hand, the tabular silver halide emulsion (N)
The coefficient of variation of the length of the transition line is 25% or more, but 30%
It is preferable that it is above. Here, the variation coefficient of the length of the transition line is 1
Determined from the transition line present in the particles. The above coefficient of variation
Particles satisfying the condition are 70% of the number of particles having a transition line
Although the above is necessary, it is preferably 80% or more.
Is preferably 90% or more. The method for introducing dislocation lines into silver halide grains is as follows.
Include, for example, iodide ions such as potassium iodide
For adding aqueous solution and water-soluble silver salt solution by double jet
Method or a method of adding a fine grain emulsion containing silver iodide,
Method for adding only a solution containing elementary ions
Iodide ion release as described in US Pat.
A known method such as a method using an agent can be used.
It is possible to form dislocations that originate dislocation lines at desired positions.
it can. Among these methods, fine grain milk containing silver iodide is used.
The method of adding an iodine ion releasing agent and the method of using an iodine ion releasing agent
Preferred. When an iodine ion releasing agent is used,
Sodium dodoacetamidobenzenesulfonate, 2-
Preferred is iodoethanol, 2-iodoacetamide, etc.
It can be used properly. In the present invention, tabular grains are mainly composed of a latent image.
As particles formed on the surface or mainly inside the particles
The particles may be any of the particles formed on the surface. The tabular grains used in the present invention are dispersed
Manufactured in the presence of a medium, i.e., in a solution containing a dispersion medium.
You. Here, the aqueous solution containing the dispersion medium refers to gelatin or other
Substances that can constitute hydrophilic colloids
The protective colloid formed in the aqueous solution
That are protected, preferably colloidal protective gelatin
It is an aqueous solution containing tin. Where gelatin is used as a colloid
If the gelatin is lime-treated, use an acid
Any of the processed ones may be used. Gelatin manufacturing method
For more information, see The Macromolecular, by Arthur Guice
-Chemistry of gelatin (Academic
Les, published in 1964). Use as a protective colloid other than gelatin
Examples of hydrophilic colloids that can be used include gelatin
Graft polymer of gelatin derivative and other polymer
-, Albumin, proteins such as casein; hydroxyethyl
Cellulose, carboxymethylcellulose, cellulose
Cellulose derivatives such as sulphates, algin
Saccharide derivatives such as acid soda and starch derivatives; polyvinyl alcohol
Coal, polyvinyl alcohol partial acetal, poly-
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic
Luic acid, polyacrylamide, polyvinylimidazole,
Homopolymer or copolymer such as polyvinylpyrazole
There are various kinds of synthetic hydrophilic polymer substances such as In the case of gelatin, the gel is
It is preferable to use one having a strength of 200 or more. The tabular grains in the present invention form grains.
Cadmium during the process of growing and / or growing
Salt, zinc salt, lead salt, thallium salt, iron salt, rhodium salt,
Selected from iridium salts and indium salts (including complex salts)
At least one metal ion is added to the inside of the particle.
And / or to include these metal elements on the particle surface
be able to. Means for forming tabular grains are described in the art.
Various well-known methods can be used.
That is, the single jet method and the controlled
Bull jet method, controlled triple jet method
Can be used in any combination.
Production of silver halide grains
The pAg in the liquid phase to the growth rate of silver halide grains
It is important to control them together. pAg value
Is used in the range of 7.0 to 12, preferably 7.0.
Five to eleven regions can be used. In determining the addition rate, refer to
No. 48521, JP-A-58-49938.
You can refer to the techniques listed above. The step of preparing tabular grains includes a nucleation step,
Growth process (nucleus ripening process) and subsequent growth process
It is. In addition, the nuclear emulsion (or seed emulsion) prepared in advance
It can be grown separately. The growing step includes a first step.
Several stages, such as the growth process, the second growth process, etc.
May be included. The growth process of the tabular grains of the present invention and
Is the total time from nucleation (or seed) formation to the end of grain growth.
Start of growth process means start of growth process
Time point. During the production of tabular grains, ammonia,
Known silver halide solvents such as ether and thiourea
And without the use of silver halide solvents
You may. Selectively in the central region of the main plane of tabular grains
In order to form dislocation lines, a ripening step after nucleation is performed.
Aging to increase the pH and increase the thickness of tabular grains
It is important that the pH is too high,
The spect ratio is too low and the aspect ratio is
It becomes difficult to control to increase the ratio. Also unexpected
It also causes fog deterioration. Therefore, the pH of the aging step is
7.0 to 11.0, the temperature is preferably 40 ° C to 80 ° C,
pH 8.5 to 10.0, temperature 50 to 70 ° C
Is more preferred. Dislocation lines are selectively formed in the peripheral region of tabular grains.
In order to form, in the growth process,
Iodine ion source (eg, silver iodide fine
Particles after adding iodine ion releasing agent) to the base particles
It is important to increase pAg in offspring growth,
If the Ag is set too high, the so-called male
As Twirl ripening progresses, the monodispersity of the tabular grains deteriorates.
Would. Therefore, the outer periphery of the tabular grains in the growth process
The pAg for forming the region is preferably 8 to 12,
9.5 to 11 are more preferred. In addition, iodine ion source
When using an iodine ion releasing agent,
Effectively forms dislocation lines in the outer peripheral region by increasing
Can be achieved. The amount of iodine ion releasing agent added
Is preferably 0.5 mol or more per mol of silver halide.
And 2 to 5 mol is more preferable. The tabular grains of the present invention are silver halide grains.
After the end of the growth of
Or it may still be contained
Is also good. Further, Japanese Patent Application Laid-Open No. 60-138538 discloses
Desalting is performed at any point during silver halide growth as described.
It is also possible. In addition, salt removal is a research
・ Disclosure (R)
(Abbreviated as D) based on the method described in 17643 No. II.
Can be. In addition, after precipitation, or
In order to remove soluble salts from the ripened emulsion,
You can use the Nudel washing method, which is performed by gelling
Also, inorganic salts, anionic surfactants, anions
Polymer (eg, polystyrene sulfonic acid) or
Is a gelatin derivative (eg, acylated gelatin, carba
Precipitation method using flocculated gelatin
May be used. As a specific example,
The method described in JP-A-5-72658 is mentioned.
Can be preferably used. The tabular grains of the present invention can be chemically enhanced by an ordinary method.
I can feel it. That is, sulfur sensitization, selenium sensitization, gold
Single noble metal sensitization method using other noble metal compounds
Or in combination. The tabular grains according to the present invention can be used in the photographic industry.
In dyes known as sensitizing dyes in
Optically sensitized in the wavelength range. Sensitizing dye used alone
However, two or more types may be used in combination. Increase
Some dyes do not have spectral sensitizing effect by themselves with dyes
Or a compound that does not substantially absorb visible light.
Include supersensitizer in emulsion to enhance dye sensitization
You may. The tabular grains according to the present invention have anti-fogging properties.
Stoppers, stabilizers and the like can be added. With a binder
Therefore, it is advantageous to use gelatin. Emulsion layer
Other hydrophilic colloid layers can be hardened,
Dispersion of plasticizers, water-insoluble or soluble synthetic polymers
(Latex). In the emulsion layer of the color photographic light-sensitive material, a coupler was used.
Is used. Competitive caps that also have the effect of color correction
Color and coupling with oxidized developer
Image accelerator, developer, silver halide solvent, toning agent, hardening
Agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers
Releases photographically useful fragments such as and desensitizers
Can be used. The photosensitive material includes a filter layer,
Auxiliary layers such as an anti-irradiation layer and irradiation prevention layer are provided.
be able to. In these layers and / or in the emulsion layers
Effluent from photosensitive material during development processing or bleaching
May be contained. The photosensitive material includes a matting agent, a lubricant, an image stabilizer
Agent, formalin scavenger, UV absorber, fluorescence enhancement
Whitening agents, surfactants, development accelerators and development retarders can be added.
You. As a support, polyethylene or the like
Paper, polyethylene terephthalate film,
Use a film of writer paper, cellulose triacetate, etc.
Can be. [0090] EXAMPLES The present invention will be described below in more detail with reference to examples.
However, the present invention is not limited by these examples.
Not. Embodiment 1 (Preparation of silver halide emulsion) JP-A-7-191425
In the same manner as described in the publication, the distance between twin planes shown in Table 1 was determined.
Iodobromide having average value, average particle size in terms of sphere, and average AgI amount
A silver emulsion was prepared. [0092] [Table 1]Each emulsion was observed by electron microscopy,
The ratio of tabular grains to particles is 80% (number) or more.
Was. (Preparation of Support) 2,6-Naphthalenedica
100 parts of dimethyl ribonate, 60 parts of ethylene glycol
Calcium acetate hydrate 0.1 as transesterification catalyst
Was added and a transesterification reaction was performed according to a conventional method.
To the obtained product, 0.05 parts of antimony trioxide, phosphoric acid
0.03 parts of trimethyl ester were added. Then Xu
Raise the temperature and reduce the pressure to 290 ° C and 0.05mmHg.
The polymerization is carried out in the
2,6-Naphthalate was obtained. This was vacuum dried at 150 ° C. for 8 hours.
After that, it is melt-extruded in layers from a T-die at 300 ° C.
Adhere to the cooling drum while applying static electricity,
To obtain an unstretched sheet. Roll this unstretched sheet
Using a longitudinal stretching machine, stretch the film 3.3 times in the machine direction at 135 ° C.
Was. The obtained uniaxially stretched film is placed in a tenter type horizontal film.
Using a stretching machine, the total stretching time in the first stretching zone at 145 ° C
Stretching so that the ratio becomes 50%, and further, the second stretching zone
The film is stretched at 155 ° C. so that the total transverse stretching ratio becomes 3.3 times.
Was. Next, heat treatment is performed at 100 ° C. for 2 seconds.
Heat fixing at 200 ° C for 5 seconds in the fixing zone, and the second heat fixing zone
Heat set at 240 ° C. for 15 seconds. Next, 5
While slowly cooling to room temperature over 30 seconds
85 μm polyethylene naphthalate film
Was. This is wound around a stainless steel core, and
Heat treatment (annealing treatment) at 10 ° C for 48 hours
Produced. (Coating of undercoat layer)
W / m^Two/ Min corona discharge treatment on one side
The following undercoating coating solution B-1 was dried to a thickness of 0.4 μm.
And apply 12W / m^Two/ Min corona discharge
After the treatment, the following undercoating coating solution B-2 was dried to a thickness of 0.06.
It was applied to a thickness of μm. 12 W / m^Two/ Min corona discharge treatment
On the other side, the following coating solution B-3 was dried and hardened.
0.2 μm, and 12 W / m^Two
/ Min corona discharge treatment and the following undercoating coating solution B-
4 was applied to a dry film thickness of 0.2 μm. Each layer was dried at 90 ° C. for 10 seconds after coating.
Dry and apply 4 layers, then heat treat at 110 ° C for 2 minutes
After that, a cooling treatment was performed at 50 ° C. for 30 seconds. [0100] <Undercoat coating solution B-1> Butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl Acrylate copolymer (30/20/25/25% by weight) latex liquid (solid Min 30%) 125g 0.4 g of compound (UL-1) Hexamethylene-1,6-bis (ethylene urea) 0.05 g   Finish to 1 liter with water [0101] <Undercoat coating solution B-2> Sodium hydroxide of styrene / maleic anhydride copolymer Aqueous solution (solid content 6%) 50g 0.6 g of compound (UL-1) Compound (UL-2) 0.09 g 0.2 g of silica particles (average particle size: 3 μm)   Finish to 1 liter with water [0102] <Undercoat coating solution B-3> Butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl Acrylate copolymer (30/20/25/25% by weight) latex liquid (solid 30%) 50g Compound (UL-1) 0.3 g Hexamethylene-1,6-bis (ethylene urea) 1.1 g   Finish to 1 liter with water UL-1: o, p- (C₉H₁₉)_TwoC₆H_ThreeO (CH_TwoCH_Two
O)₁₂SO_ThreeNa UL-2: CH_ThreeSO_TwoO (CH_Two)_ThreeOSO_TwoCH_Three [0103] <Undercoat coating solution B-4> An aqueous dispersion (solid content) of tin oxide-antimony oxide composite fine particles (average particle size 0.2 μm) 40 g) 109 g Aqueous dispersion A 67g   Finish to 1 liter with water Aqueous dispersion A; terephthalic acid dime as a dicarboxylic acid component
60 mol% of tyl, 30 mol% of dimethyl isophthalate, 5
-10 mol of dimethyl sulfoisophthalate sodium salt
%, Ethylene glycol 50 mol as glycol component
% And diethylene glycol 50 mol% by the usual method.
And the copolymer was stirred in hot water at 95 ° C. for 3 hours.
A 15% by weight aqueous dispersion A was obtained. (Coating of Transparent Magnetic Recording Layer) <Preparation and coating of magnetic coating liquid 1> The following composition (A) was prepared.
After dispersion for 40 hours using a sand mill, the average pore size was 10 μm.
The mixture was filtered through a filter to obtain a magnetic paint. Composition (A) Co deposited γ-Fe_TwoO_Three(Long axis 0.15 μm, short axis 0.03 μm, specific surface area 40 m^Two / G, Hc = 900 Oersted) 5 parts 100 parts of diacetyl cellulose (degree of acetylation = 55%, Mw = 180,000) α-alumina (average particle size 0.3 μm) 10 parts Acetone 780 parts 340 parts of cyclohexanone [0105] Air is applied to the magnetic paint using a disper.
The following composition (B) mixed so as not to be involved is continuously
Was added and mixed to prepare a magnetic coating liquid 1. Composition (B) 20 parts of hardener (manufactured by Nippon Polyurethane Co., Ltd .: CL, solid content 75%) Cyclohexanone 45 parts The obtained magnetic coating liquid 1 was washed with the polyethylene
The undercoating coating solutions B-3 and B-4 of the nannaphthalate support are
On the coated side, apply a dry film thickness of 0.8 μm.
Dried. (Preparation of silver halide photographic material sample)
On the side of the medium opposite to the magnetic recording layer, the undercoating coating solution B-1
And B-2 provided with an undercoat layer coated under the same conditions.
Next, a photographic constituent layer having the composition shown below was sequentially formed from the support side.
Thus, samples 101 to 105 were obtained. Each emulsion is gold
-Coating after optimal sulfur sensitization. The addition amount of the photographic constituent layer shown below was 1 m^TwoThis
Expressed in terms of grams. However, silver halide and colloid
Silver is converted to the amount of silver, and sensitizing dye is the mole per mole of silver.
Indicated by number. [0108]                                                             Amount added First layer (anti-halation layer)   Black colloidal silver 0.16   UV absorber UV-1 0.3   Colored magenta coupler CM-1 0.044   High boiling solvent OIL-1 0.044   Gelatin 1.33 Second layer (middle layer)   Anti-staining agent AS-1 0.16   High boiling point solvent OIL-1 0.20   Gelatin 1.40 [0109] Third layer (low-sensitivity red-sensitive layer)   Silver iodobromide emulsion A 0.12   Silver iodobromide emulsion B 0.50   Sensitizing dye SD-1 3.0 × 10^-Five   Sensitizing dye SD-4 1.5 × 10^-Four   Sensitizing dye SD-3 3.0 × 10^-Four   Sensitizing dye SD-6 3.0 × 10^-6   Cyan coupler C-1 0.51   Colored cyan coupler CC-1 0.047   High boiling point solvent OIL-2 0.45   Stain inhibitor AS-2 0.005   Gelatin 1.40 4th layer (medium-speed red-sensitive layer)   Silver iodobromide emulsion C 0.64   Sensitizing dye SD-1 3.0 × 10^-Five   Sensitizing dye SD-2 1.5 × 10^-Four   Sensitizing dye SD-3 3.0 × 10^-Four   Cyan coupler C-2 0.22   Colored cyan coupler CC-1 0.028   DIR compound DI-1 0.002   High boiling point solvent OIL-2 0.21   Stain inhibitor AS-3 0.006   Gelatin 0.87 [0110] Fifth layer (high-sensitivity red-sensitive layer)   Silver iodobromide emulsion C 0.13   Silver iodobromide emulsion D 1.14   Sensitizing dye SD-1 3.0 × 10^-Five   Sensitizing dye SD-2 1.5 × 10^-Four   Sensitizing dye SD-3 3.0 × 10^-Four   Cyan coupler C-2 0.085   Cyan coupler C-3 0.084   Colored cyan coupler CC-1 0.029   DIR compound DI-1 0.027   High boiling point solvent OIL-2 0.23   Anti-staining agent AS-3 0.013   Gelatin 1.23 6th layer (middle layer)   High boiling point solvent OIL-1 0.29   Stain inhibitor AS-1 0.23   Gelatin 1.00 [0111] 7th layer (low sensitivity green color sensitive layer)   Silver iodobromide emulsion A 0.245   Silver iodobromide emulsion B 0.105   Sensitizing dye SD-6 5.0 × 10^-Four   Sensitizing dye SD-5 5.0 × 10^-Four   Magenta coupler M-1 0.21   Colored magenta coupler CM-2 0.039   High boiling point solvent OIL-1 0.25   Stain inhibitor AS-2 0.003   Stain inhibitor AS-4 0.063   Gelatin 0.98 Eighth layer (medium-sensitive green color-sensitive layer)   Silver iodobromide emulsion E 0.87   Sensitizing dye SD-7 3.0 × 10^-Four   Sensitizing dye SD-8 6.0 × 10^-Five   Sensitizing dye SD-9 4.0 × 10^-Five   Magenta coupler M-1 0.17   Colored magenta coupler CM-2 0.048   Colored magenta coupler CM-3 0.059   DIR compound DI-2 0.012   High boiling point solvent OIL-1 0.29   Stain inhibitor AS-4 0.05   Stain inhibitor AS-2 0.005   Gelatin 1.43 [0112] 9th layer (high sensitivity green color sensitive layer)   Silver iodobromide mixed emulsion (described in Table 2) 1.19   Sensitizing dye SD-7 4.0 × 10^-Four   Sensitizing dye SD-8 8.0 × 10^-Five   Sensitizing dye SD-9 5.0 × 10^-Five   Magenta coupler M-1 0.09   Colored magenta coupler CM-3 0.020   DIR compound DI-3 0.005   High boiling point solvent OIL-1 0.11   Stain inhibitor AS-4 0.026   Stain inhibitor AS-5 0.014   Stain inhibitor AS-6 0.006   Gelatin 0.78 [0113] 10th layer (yellow filter layer)   Yellow colloidal silver 0.05   High boiling point solvent OIL-1 0.18   Anti-staining agent AS-7 0.16   Gelatin 1.00 11th layer (low-sensitivity blue-sensitive layer)   Silver iodobromide emulsion F 0.29   Silver iodobromide emulsion G 0.19   Sensitizing dye SD-10 8.0 × 10^-Four   Sensitizing dye SD-11 3.1 × 10^-Four   Yellow coupler Y-1 0.91   DIR compound DI-4 0.022   High boiling point solvent OIL-1 0.37   Anti-staining agent AS-2 0.002   Gelatin 1.29 [0114] 12th layer (highly sensitive blue-sensitive layer)   Silver iodobromide emulsion G 0.13   Silver iodobromide emulsion H 1.00   Sensitizing dye SD-10 4.4 × 10^-Four   Sensitizing dye SD-11 1.5 × 10^-Four   Yellow coupler Y-1 0.48   DIR compound DI-4 0.019   High boiling point solvent OIL-1 0.21   Stain inhibitor AS-2 0.004   Gelatin 1.55 13th layer (first protective layer)   Silver iodobromide emulsion I 0.30   UV absorber UV-1 0.055   UV absorber UV-2 0.110   High boiling point solvent OIL-2 0.63   Gelatin 1.32 [0115] Fourteenth layer (second protective layer)   Polymer PM-1 0.15   Polymer PM-2 0.04   Slip agent WAX-1 0.02   Dye D-1 0.001   Gelatin 0.55 In addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersion aid SU-4, viscosity adjustment
Agent V-1, stabilizers ST-1, ST-2, antifoggant A
F-1 (polyvinylpyrrolidone, weight average molecular weight: 1)
000), AF-2 (polyvinylpyrrolidone, weight
Average molecular weight: 1,100,000), inhibitor AF-3,
AF-4, AF-5, hardeners H-1, H-2, H-3,
H-4 and preservative Ase-1 were added. The structures of the compounds used in each of the above samples are shown below.
Show. SU-1: C₈F₁₇SO_TwoN (C_ThreeH₇) CH_TwoCOOK SU-2: C₈F₁₇SO_TwoNH (CH_Two)_ThreeN⁺(CH_Three)_Three
Br^- SU-3: di (2-ethylhexyl) nato sulfosuccinate
Lium SU-4: tri-i-propylnaphthalenesulfonic acid sodium
thorium ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene ST-2: Adenine AF-3: 1-phenyl-5-mercaptotetrazole AF-4: 1- (4-carboxyphenyl) -5-mer
Captotetrazole AF-5: 1- (3-acetamidophenyl) -5-me
Lcaptotetrazole H-1: [(CH_Two= CHSO_TwoCH_Two)_ThreeCCH_TwoSO_TwoC
H_TwoCH_Two]_TwoNCH_TwoCH_TwoSO_ThreeK H-2: 2,4-dichloro-6-hydroxy-s-tri
Azin sodium H-3: CH_Two= CHSO_TwoCH_TwoCH (OH) CH_TwoSO
_TwoCH = CH_Two H-4: CH_Two= CHSO_TwoCH_TwoCONHCH_TwoCH_TwoN
HCOCH_TwoSO_TwoCH = CH_Two OIL-1: tricresyl phosphate OIL-2: di (2-ethylhexyl) phthalate AS-1: 2,5-bis (1,1-dimethyl-4-hexyl)
Siloxycarbonylbutyl) hydroquinone AS-2: Dodecyl gallate AS-3: docosyl gallate AS-4: 2-octyloxy-5-t-octyl-
N, N-dibutylaniline AS-5: 2,5-di-t-octylhydroquinone AS-6: 2,5-di-t-octyl-1,4-quinone [0118] Embedded image[0119] Embedded image[0120] Embedded image[0121] Embedded image[0122] Embedded image[0123] Embedded image[0124] Embedded image[0125] Embedded image[0126] Embedded image[0127] [Table 2] Table 3 shows the silver iodobromide emulsions A to I used in the above samples.
You. [0128] [Table 3]For the obtained sample, the sensitivity,
Graininess (RMS), gradation stability in processing fluctuation (J
The evaluation of i) was performed using green light. Table showing the results obtained
It is shown in FIG. << Evaluation of Sensitivity >>
And exposed to a wedge, and developed according to the following processing steps.
Was done. (Processing process) Treatment process Treatment time Treatment temperature Replenishment amount^* Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 780ml Bleaching 45 seconds 38 ± 2.0 ℃ 150ml 1 minute 30 seconds 38 ± 2.0 ℃ 830ml Stability 60 seconds 38 ± 5.0 ℃ 830ml Drying 1 minute 55 ± 5.0 ℃ * Replenishment amount is 1m of photosensitive material^TwoThe amount per hit. Color developing solution, bleaching solution, fixing solution, stabilizing solution and
The following was used as the replenisher. Color developer and color developer replenisher                                               Developer replenisher 800 ml of water 800 ml Potassium carbonate 30g 35g Sodium bicarbonate 2.5g 3.0g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3g 0.4g Potassium iodide 1.2mg ― Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6g- 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) anili Sulphate 4.5g 6.3g Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2g 2.0g   Add water to make up to 1 liter and use potassium hydroxide or 20% sulfuric acid to develop Is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.18. [0132] Bleaching solution and bleach replenisher                                               Bleach replenisher 700 ml of water 700 ml Iron (III) ammonium 1,3-diaminopropanetetraacetate                                               125g 175g Ethylenediaminetetraacetic acid 2g 2g Sodium nitrate 40g 50g Ammonium bromide 150g 200g Glacial acetic acid 40g 56g   Add water to make up 1 liter, and use ammonia water or glacial acetic acid to adjust the bleaching solution to pH At 4.4, the replenisher is adjusted to pH 4.0. [0133] Fixer and fixer replenisher                                               Fixer replenisher 800 ml of water 800 ml Ammonium thiocyanate 120g 150g Ammonium thiosulfate 150g 180g Sodium sulfite 15g 20g Ethylenediaminetetraacetic acid 2g 2g   The fixer is adjusted to pH 6.2 using ammonia water or glacial acetic acid, and the replenisher is adjusted to pH 6.2. After adjusting to 5, add water to make 1 liter. [0134] Stabilizer and replenisher 900 ml of water 10 mol ethylene oxide adduct of p-octylphenol                                               2.0g 0.5 g of dimethylol urea Hexamethylenetetramine 0.2g 1,2-benzisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1g Ammonia water 0.5ml   After adding water to make up 1 liter, adjust the pH using ammonia water or 50% sulfuric acid. Adjust to 8.5. The green density of the processed sample was
The reciprocal of the exposure required to obtain a small density + 0.2
The sensitivity was determined. Table 4 shows that the sensitivity of sample 105 was 10
The relative value is set to 0. << Evaluation of Granularity (RMS) >> Sample Obtained
To normal wedge exposure,
Therefore, development processing was performed. The green density of the processed sample was
Eastman Kodak Co., Ltd. locates the position of small concentration + 0.2
Microphone equipped with a Ratten filter (W-99)
Rodensitometer (slit width 10 μm, slit length
180 μm), and the density measurement sampling number 100
The standard deviation of the fluctuation of the density value of 0 or more is determined, and the granularity (RM
S) was evaluated. Table 4 shows the granularity (RM
S) is shown as a relative value where 100 is set. RMS value (relative
The smaller the value, the better the graininess. << Gradation Stability (Ji) in Processing Fluctuation
Evaluation> Normal wedge exposure was applied to the obtained sample.
In addition, development processing was performed according to the processing steps described above.
In the above-mentioned processing steps, the time for the color development processing is 2 minutes 5 minutes.
The processing step was shortened to 0 seconds. From the obtained processed samples, the horizontal axis
Is the exposure amount (log E) and the vertical axis is the magenta density value.
A sex curve was prepared, and a Ji value was determined from the curve. Determination of Ji value
The method is as follows. Regarding the characteristic curve, the minimum density + 0.5
Degree d₀Exposure logE which gives₀ΔlogE = −
LogE in 1.2_FourΔlogE = −
Exposure point logE taken every 3.0 units_i(I = 0,
The density obtained in 1, 2, 3, 4) is d_i(I =
0, 1, 2, 3, 4) g_i= (D_i-D_i-1) /-(LogE_i-LogE_i-1) h = (d_Four-D₀) /-(LogE_Four-LogE₀) Is calculated, and j is calculated from the value._i= G_i/ H, respectively.
J with the largest deviation from 00_iWith Ji of each color
did. [0141] [Table 4] As is clear from Table 4, the halogenation of the present invention
Silver halide photographic light-sensitive material has
It turns out that it is excellent. In addition, the graininess is particularly good.
You can see that there is. Embodiment 2 (Preparation of silver halide emulsion) JP-A-1-131541
And the same as described in JP-A-5-173272.
By the method, the main plane shape, the sphere-converted average particle size, and the average
A silver halide emulsion having an AgI amount was prepared. Each emulsion was observed with an electron microscope.
However, the ratio of tabular grains to all grains is 80% (pieces).
Number) or more. [0145] [Table 5] (Preparation of silver halide photographic material sample)
Replaced with silver iodobromide mixed emulsion of ninth layer (highly sensitive green color sensitive layer)
EM-5 to EM-8 are mixed in the combinations shown in Table 6.
Halogen was prepared in the same manner as in Example 1 except that
Silver halide photographic light-sensitive material samples 201 to 205 were prepared. [0147] [Table 6] The obtained samples were completely different from those in Example 1.
Similarly, sensitivity, graininess, gradation stability in processing fluctuation
The sex was evaluated. Table 7 shows the obtained results. In addition,
The sensitivity and the RMS value were 100 for the value of sample 205, respectively.
The relative values are shown. [0149] [Table 7] As is clear from Table 7, the halogenation of the present invention
Silver halide photographic light-sensitive material has
It turns out that it is excellent. In addition, the graininess is particularly good.
You can see that there is. Embodiment 3 (Preparation of silver halide emulsion) Japanese Patent Application No. 9-281955
In the same manner as described in the specification, the length of the dislocation line shown in Table 8
Halo having an average value of
A silver gemide emulsion was prepared. Each emulsion was observed with an electron microscope.
However, the ratio of tabular grains to all grains is 80% (pieces).
Number) or more. [0153] [Table 8](Preparation of silver halide photographic material sample)
Replaced with silver iodobromide mixed emulsion of ninth layer (highly sensitive green color sensitive layer)
EM-9 to EM-12 are mixed in the combinations shown in Table 9.
The halogenation was performed in the same manner as in Example 1 except that the combined emulsion was used.
Silver halide photographic light-sensitive material samples 301 to 305 were prepared. [0155] [Table 9] Each of the obtained samples was completely the same as in Example 1.
Similarly, sensitivity, graininess, gradation stability in processing fluctuation
The sex was evaluated. Table 10 shows the obtained results. What
Note that the sensitivity and RMS value were 10
The relative value is set to 0. [0157] [Table 10] As is clear from Table 10, the halogenation of the present invention
Silver halide photographic materials have excellent gradation stability in processing fluctuations.
You can see that it is. In addition, the graininess is particularly good.
You can see that. Embodiment 4 (Preparation of silver halide emulsion) Japanese Patent Application No. 9-280459
In the same manner as described in the specification, the sphere conversion average shown in Table 11
Having a particle size and an average AgI content, and as shown in Table 11
Silver halide milk having dislocation lines in the fringe part on the main plane
An agent was prepared. Each emulsion was observed with an electron microscope.
However, the ratio of tabular grains to all grains is 80% (pieces).
Number) or more. [0161] [Table 11](Preparation of silver halide photographic light-sensitive material sample)
Replaced with silver iodobromide mixed emulsion of ninth layer (highly sensitive green color sensitive layer)
EM-13 to EM-16 in the combinations shown in Table 12
In the same manner as in Example 1 except that an emulsion in which
Prepare silver log photographic light-sensitive material samples 401 to 405
Was. [0163] [Table 12] Each of the obtained samples was completely the same as in Example 1.
Similarly, sensitivity, graininess, gradation stability in processing fluctuation
The sex was evaluated. Table 7 shows the obtained results. In addition,
The sensitivity and the RMS value were 100 and 405, respectively.
The relative values are shown. [0165] [Table 13] As is clear from Table 13, the halo of the present invention
Silver photographic light-sensitive material has gradation stability in processing fluctuation
Is excellent. Especially good granularity
It can be seen that it is. Embodiment 5 (Preparation of silver halide emulsion) Japanese Patent Application No. 9-280459
In the same manner as described in the specification, the average
Ratio, average number of dislocation lines, average sphere-equivalent particle size, average AgI
An amount of silver halide emulsion was prepared. Each emulsion was observed with an electron microscope.
However, the ratio of tabular grains to all grains is 80% (pieces).
Number) or more. [0169] [Table 14](Preparation of silver halide photographic material sample)
Replaced with silver iodobromide mixed emulsion of ninth layer (highly sensitive green color sensitive layer)
EM-17 to EM-23 in the combinations shown in Table 15
In the same manner as in Example 1 except that an emulsion in which
Prepare silver logenographic photographic material samples 501 to 508
Was. [0171] [Table 15] The obtained samples were completely different from those in Example 1.
Similarly, sensitivity, graininess, gradation stability in processing fluctuation
The sex was evaluated. Table 16 shows the obtained results. What
Note that the sensitivity and RMS value were 10
The relative value is set to 0. [0173] [Table 16] As is clear from Table 16, the halo of the present invention
Silver photographic light-sensitive material has gradation stability in processing fluctuation
Is excellent. Especially good granularity
It can be seen that it is. Embodiment 6 (Preparation of silver halide emulsion) Japanese Patent Application No. 9-280459
In the same manner as described in the specification, the average
Have an average particle diameter, an average AgI amount,
As shown in Table 17, a silver halide emulsion having dislocation lines
Prepared. Each emulsion was observed with an electron microscope.
However, the ratio of tabular grains to all grains is 80% (pieces).
Number) or more. [0177] [Table 17] (Preparation of silver halide photographic material sample)
Replaced with silver iodobromide mixed emulsion of ninth layer (highly sensitive green color sensitive layer)
EM-24 to EM-29 in the combinations shown in Table 18.
In the same manner as in Example 1 except that an emulsion in which
Preparation of silver halide photographic material samples 601 to 606
Was. [0179] [Table 18] Each of the obtained samples was completely the same as in Example 1.
Similarly, sensitivity, graininess, gradation stability in processing fluctuation
The sex was evaluated. Table 19 shows the obtained results. What
In addition, the sensitivity and the RMS value were 10
The relative value is set to 0. [0181] [Table 19] As is clear from Table 19, the halo of the present invention
Silver photographic light-sensitive material has gradation stability in processing fluctuation
Is excellent. Especially good granularity
It can be seen that it is. Embodiment 7 (Preparation of silver halide emulsion) Japanese Patent Application No. 9-281955
In the same manner as described in the specification, the length of the dislocation line shown in Table 20 is shown.
Has the coefficient of variation of the average particle size, average spherical particle size, and average AgI amount.
A silver halide emulsion was prepared. Each emulsion was observed with an electron microscope.
However, the ratio of tabular grains to all grains is 80% (pieces).
Number) or more. [0185] [Table 20](Preparation of silver halide photographic light-sensitive material sample)
Replaced with silver iodobromide mixed emulsion of ninth layer (highly sensitive green color sensitive layer)
EM-30 to EM-33 in the combinations shown in Table 21
In the same manner as in Example 1 except that an emulsion in which
Silver photographic photosensitive material samples 701 to 705 were prepared.
Was. [0187] [Table 21] For each of the obtained samples, exactly as in Example 1,
Evaluation of sensitivity, graininess, and gradation stability due to process fluctuation
Was. Table 22 shows the obtained results. Note that sensitivity and R
The MS value is a relative value with the value of sample 705 as 100.
Indicated by [0188] [Table 22] As is clear from Table 22, the silver halide photographs of the present invention
The photosensitive material has excellent gradation stability in process fluctuations
You can see that. In particular, the graininess is also good.
Recognize. [0189] According to the present invention, excellent sensitivity can be obtained without loss of sensitivity.
High granularity, and against environmental changes that occur in the market
Silver halide color photographic exposure that provides stable gradation reproduction
Material can be provided.

Claims (1)

Claims 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A tabular silver halide emulsion (A) having an average twin plane distance of 30 nm or more in at least one silver halide emulsion layer; and an average twin plane distance of less than 30 nm; Tabular silver halide emulsion (A)
And a tabular silver halide emulsion (B) equal to or smaller than the above. 2. A silver halide photographic material having at least one silver halide emulsion layer on a support,
In at least one silver halide emulsion layer, a tabular silver halide emulsion (C) having a circular main plane and a hexagonal main plane having an average sphere-equivalent particle size A silver halide photographic material comprising a silver halide emulsion (C) and a tabular silver halide emulsion (D) which is equal to or smaller than the silver halide emulsion (C). 3. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A tabular silver halide emulsion (E) having an average length of dislocation lines of at least 30 nm in at least one silver halide emulsion layer, and an average length of dislocation lines of less than 30 nm; Tabular silver halide emulsion (E)
And a tabular silver halide emulsion (F) equal to or smaller than the above. [Claim 4] A silver halide photographic material having at least one silver halide emulsion layer on a support,
A tabular silver halide emulsion (G) having dislocation lines mainly on the main plane in at least one silver halide emulsion layer (G)
And a tabular silver halide emulsion (H) having a dislocation line only in the fringe portion and having a sphere-equivalent average grain size equal to or smaller than that of the tabular silver halide emulsion (G). Silver halide photographic light-sensitive material. 5. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A tabular silver halide emulsion (I) having at least one silver halide emulsion layer having an average aspect ratio of 8 or more and having 30 or more dislocation lines per grain, and an average aspect ratio of 5 or more and less than 8 And dislocation lines per particle are 3
A silver halide photographic light-sensitive material characterized by comprising a tabular silver halide emulsion (J) having 0 or more grains and having a sphere-equivalent average particle size equal to or smaller than that of the tabular silver halide emulsion (I). material. 6. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A tabular silver halide emulsion (K) having at least one silver halide emulsion layer having dislocation lines introduced therein and having an average sphere-equivalent particle diameter of 0.6 μm or more, and a sphere conversion having introduced dislocation lines therein; A silver halide photographic light-sensitive material comprising a tabular silver halide emulsion (L) having an average particle size of 0.45 µm or more and less than 0.6 µm. 7. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A tabular silver halide emulsion (M) having a coefficient of variation of dislocation line length of less than 25% in at least one silver halide emulsion layer; A silver halide photographic light-sensitive material comprising a tabular silver halide emulsion (N) having a sphere-equivalent average particle size equal to or smaller than that of a tabular silver halide emulsion (M).