JP2003287840A - Silver halide photographic emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent silver halide photographic emulsion having high sensitivity and reduced fog. <P>SOLUTION: In the silver halide photographic emulsion, tabular grains which satisfy the following items (i)-(iv) account for ≥70% (by number) of all grains; (i) silver iodochlorobromide grains having (111) faces as principal planes and having two parallel twin faces; (ii) an equivalent circular diameter of ≥2.5 μm and a grain thickness of ≤0.15 μm; (iii) at least one silver halide epitaxial junction per grain is present selectively on the vertexes of host tabular grains; and (iv) the silver halide epitaxial junction is a protruding junction, ≥60% of the projected area of which exists on the outside of the host tabular grain when seen from a direction perpendicular to the (111) principal planes. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
Reduced silver halide photographic emulsion and halo using the same
The present invention relates to a silver halide photographic light-sensitive material. [0002] [Background Art] Countering the spread of digital cameras in recent years
Above, there is an increasing demand for photographic silver halide emulsions
Strictly, higher sensitivity is required. Especially
Insufficient strobe light, such as the spread of film with screens
High sensitivity that can withstand use even with an inexpensive camera
There is a strong demand for color photographic materials for high-quality photography.
The One of the technologies for improving the sensitivity and image quality of silver halide emulsions
As a tabular grain, and color sensitization with sensitizing dyes
Increased sensitivity, including improved efficiency, improved sensitivity / grain ratio relationship
Good, sharpness due to specific optical properties of tabular grains
Benefits in the industry, such as improved power and covering power
In general, the particle thickness is thin for the same volume.
In other words, tabular grains with a higher aspect ratio are more sensitive
This is advantageous for improving the ratio. The tabular grain sensitization method is epitaxial.
A sensitizing method using bonding is known.
The technology was developed in 08526 and 59-133540.
It is shown. Furthermore, to tabular grains with a high aspect ratio
Application of JP-A-8-69069 and 8-10147
2, 8-101474, 8-101475, 8-171
162, 8-171163, 8-101473, 8-1
01476, 9-211762, 9-211763,
U.S. Pat. Nos. 5,612,176 and 5,614,3
59, 5,629,144, 5,631,
126, 5,691,127, 5,726
No. 007. In particular, JP 2000-32 A.
In the example of No. 196, the epitaxial junction is formed at the particle apex.
Have dislocation lines at the epitaxial junction
The preparation method of large size high aspect ratio tabular grains
It is. Also, US Pat. No. 6,114,105 and JP-A-9
No.-211763 includes grains on the edge principal plane of tabular grains.
High formation of epitaxial junctions on the terrace inside the element
Sensitization technology is shown. However, in these patent application specifications,
Is a feature of the present invention, the equivalent circle equivalent diameter is large and the particle thickness
Is a thin tabular grain with a host at the top of the grain
Formation of epitaxial junctions protruding outside the tabular grains
With high sensitivity and reduced fog
There is no description suggesting that a photographic emulsion can be obtained.
Yes. [0005] The present inventor has pursued high sensitivity.
The equivalent circle diameter is large and the particle thickness is thin.
In silver halide photographic emulsions containing tabular grains,
Worked on tabular grain sensitization method using chiral bonding
However, the above-described conventional technology cannot increase sensitivity and reduce fog.
It became clear that it was enough. The object of the present invention is to reduce the fog with high sensitivity.
Excellent silver halide photographic emulsion and its use
The object is to provide a silver halide photographic light-sensitive material. [0007] [Means for Solving the Problems] The present inventor
Halogenation including tabular grains with large diameter and thin grain thickness
Tabular grains using epitaxial junction in silver emulsion
The following silver halide photographic emulsion
Using it with unexpectedly high sensitivity and reducing fog
I found it for the first time. (1) The following (i) to (iv) are satisfied
Tabular grains account for 70% or more (number ratio) of all grains
A silver halide photographic emulsion characterized by (I) Two parallel twins with the (111) plane as the main plane
Silver iodochlorobromide grains having a surface. (Ii) Equivalent circular equivalent diameter is 2.5 μm or more and particle thickness
0.15 μm or less. (Iii) halogen selectively at the apex of the host tabular grain
At least one silver halide epitaxial junction per grain
Have one. (Iv) The silver halide epitaxial junction is
(111) When viewed from a direction perpendicular to the main plane,
More than 60% of the projected area exists outside the host tabular grain
This is a protruding joint. (2) In the above (iii), the host tabular grains
Silver halide epitaxial contact selectively at the apex
The number of joints is at least 6 per particle.
The silver halide photographic emulsion as described in (1), which is characterized by (3) The particle thickness in (ii) above is 0.10 μm
(1) or (2) characterized by being m or less
The silver halide photographic emulsions listed. (4) Occupy 70% or more (number ratio) of all the particles
Tabular grains further satisfy the following (v)
The halogen according to any one of (1) to (3)
Silver halide emulsion. (V) Silver halide epitaxy in (iv) above
At least one dislocation line in each of the Shall junctions
The (5) Occupy 70% or more (number ratio) of all the particles
The tabular grains further satisfy the following (vi):
The halogen according to any one of (1) to (4)
Silver halide emulsion. (Vi) of the two parallel twin planes in (i) above
The interval is 0.012 μm or less. (6) of two parallel twin planes in (vi) above
The distance is 0.008 μm or less.
The silver halide photographic emulsion as described in (5). (7) At least one silver halide emulsion on the support
In a silver halide photographic light-sensitive material having a layer, the halo
At least one of the silver halide emulsion layers is (1) to (6)
A silver halide photographic emulsion according to any one of the above
And a silver halide photographic light-sensitive material. [0009] DETAILED DESCRIPTION OF THE INVENTION One preferred embodiment of the present invention is:
The following silver halide photographic emulsion is at least 1 on the support:
A photographic light-sensitive material having a layer. That is, 70% of all particles
% Or more (number ratio) with the (111) plane as the main plane,
Equivalent circle equivalent, consisting of silver iodochlorobromide with parallel twin planes
Diameter is 2.5 μm or more and particle thickness is 0.15 μm or less
Selectively halogenated at the apex of the host tabular grains
1 to 6 silver epitaxial junctions per grain
1 to 6 silver halide epitaxial junctions
Each part is viewed from a direction perpendicular to the (111) main plane.
At least 60% of the projected area of each joint is host tabular grain
A projection-like joint existing outside the
At least one silver halide epitaxial junction
The distance between two parallel twin planes is
It is a tabular grain of 0.012 μm or less.
It is a silver halide photographic emulsion. First, in the form of the silver halide emulsion of the present invention,
Describe. In the present invention, tabular grains are two opposite parallels.
This refers to silver halide grains having a (111) major plane.
The tabular grains used in the present invention have one twin plane or
It has two or more parallel twin planes. The twin plane is (11
1) The ions of all lattice points are in mirror image relation on both sides of the surface.
This is the (111) plane. This tabular grain
Is a triangle when the particle is viewed from a direction perpendicular to the principal plane.
Shape, hexagonal shape or round shape with round shape.
Each having an outer surface parallel to each other. The emulsion of the present invention has an adjacent side ratio (maximum side length / maximum side length).
Hexagonal tabular grains with a small side length of 1.5 to 1
It accounts for 100 to 50% of the total particles in the number ratio
preferable. More preferably 100 to 70%, further
Preferably it accounts for 100 to 80%. Emulsion of the present invention
More preferably, the adjacent side ratio (maximum side length / minimum side length)
Hexagonal tabular grains with a ratio of 1.2 to 1
Account for 100 to 50% of the total particles. Even more preferred
100 to 70%, particularly preferably 100 to 70%
It accounts for 80%. The shape of the main plane of the tabular grain is rounded
If the shape is triangular or hexagonal, the side length of the main plane is
Virtual triangles and hexagons formed by extending sides
The length of the side of the shape. Tabular grains other than the above hexagons are mixed
This is not preferable in terms of homogeneity between particles. The emulsion of the present invention contains 70% or more (individual grains).
Number ratio) equivalent circle diameter is 2.5μm or more and particle thickness
Tabular grains of 0.15 μm or less occupy most of the grains
The more preferable it is. More preferably 70% or more of all particles
(Number ratio) equivalent circle equivalent diameter is 2.5 μm or more and particles
It is a tabular grain having a thickness of 0.10 μm or less. Equivalent circle equivalent
Large diameter and thin particle thickness (high aspect ratio)
The larger the number of particles, the more remarkable the effect of the present invention.
That's right. Equivalent circle equivalent of tabular grains contained in the emulsion of the present invention
The range of the diameter is preferably 1.0 μm to 7.0 μm,
More preferably, it is 2.0 μm to 6.0 μm.
Yes. More preferably, it is 2.5 μm to 5.0 μm
The Outside these ranges, the effects of the present invention are difficult to obtain,
It is not preferable. The equivalent circle equivalent diameter in the present invention is a grain.
A straight circle with an area equal to the projected area of the parallel outer surface of the child
Is the diameter. Grain thickness of tabular grains contained in the emulsion of the present invention
The range of 0.03μm to 0.20μm is preferred
More preferably 0.03 μm to 0.15 μm.
preferable. More preferably 0.03 μm to 0.10
μm. Outside these ranges, the effects of the present invention can be obtained.
It is difficult and undesirable. Equivalent circular phase to silver halide grain thickness
The ratio of this diameter is called the aspect ratio. That is, individual ha
Divide the equivalent circle diameter of the projected area of silver halide grains by the grain thickness.
It is a value. The equivalent circle equivalent diameter of tabular grains is, for example,
Take a transmission electron micrograph by the Rica method
Find the diameter of a circle with an area equal to the projected area of the child.
The grain thickness is simply replicated for epitaxial deposition.
It cannot be calculated from the length of the shadow. However
The length of the shadow of the replica before epitaxial deposition
Can be calculated by measuring. Or epitaxy
Even after deposition, the sample coated with tabular grains is cut
You can easily take an electron micrograph of the surface
Yes. The emulsion of the present invention has a distance between two parallel twin planes.
Tabular grains having a particle size of 0.012 μm or less are 70% or more of all grains
It is preferable to occupy (number ratio), occupy more
The more preferable. More preferably, two parallel twin planes
Tabular grains with an interval of 0.008 μm or less are 70% of all grains
It occupies the above (number ratio), and it is preferable to occupy more
Yes. Many tabular grains with small distance between two parallel twin planes
The effect of the present invention becomes more prominent and more preferable. The twin plane is observed using a transmission electron microscope.
obtain. Specifically, the tabular grains are almost parallel to the support.
Create an arrayed sample and cut it with a diamond knife.
By cutting, a section having a thickness of about 0.1 μm is prepared.
By observing the section with a transmission electron microscope,
The twin plane of the particle can be detected. Electron beam twin plane
When passing through, the phase shift occurs in the electron wave.
The existence of will be recognized. In the present invention, the distance between two parallel twin planes is small.
Depending on the case, various methods to form the tabular grains
You can choose. For example, nucleation at 20-40 ° C., pA
Perform at low temperature and high potential around g = 9 or perform oxidation treatment
Preferably using low molecular weight gelatin.
Good. The emulsion of the present invention comprises monodisperse grains.
Is preferred. The grain size (equivalent of all grains) of the emulsion of the present invention
Sphere equivalent diameter) The coefficient of variation of the distribution is 35% to 3%
And more preferably 25 to 3
%, More preferably 20 to 3%. Equivalent spherical phase
The coefficient of variation of this diameter distribution is equivalent to the equivalent sphere of each tabular grain
Divide diameter variation (standard deviation) by average equivalent sphere equivalent diameter
Multiplied by 100. Equivalent of all tabular grains
If the coefficient of variation of the sphere equivalent diameter distribution exceeds 35%,
It is not preferable in terms of homogeneity. Emulsions below 3%
It is difficult to prepare. The equivalent circular equivalent diameter of all the grains of the emulsion of the present invention
The coefficient of variation of the fabric is preferably 40% to 3%
More preferably 30 to 3%, still more preferably
20 to 3%. Coefficient of variation of equivalent circle equivalent diameter distribution
Is the variation in equivalent circle diameter of individual particles (standard deviation)
Difference) divided by the average equivalent circle equivalent diameter multiplied by 100
Is. The coefficient of variation of the equivalent circle equivalent diameter distribution of all particles is
If it exceeds 40%, it is not preferable in terms of homogeneity between particles.
Also, it is difficult to prepare an emulsion of less than 3%. Grain thickness distribution of all tabular grains of the emulsion of the present invention
The coefficient of variation of 25 to 3% is preferred
More preferably 20 to 3%, still more preferably
15 to 3%. What is the coefficient of variation of particle thickness distribution?
Average thickness variation (standard deviation) of various tabular grains
The value divided by the particle thickness is multiplied by 100. Zenpyeong
When the variation coefficient of the particle thickness distribution of the plate particles exceeds 25%, the particles
It is not preferable in terms of homogeneity between the children. Also below 3%
Emulsions are difficult to prepare. The twin planes of all tabular grains of the emulsion of the present invention
The variation coefficient of the interval distribution is 25 to 3%.
Preferably 20 to 3%, more preferably
It is 15 to 3%. Variation of twin plane spacing distribution
The number is the variation in the thickness of the twin plane spacing of individual tabular grains
(Standard deviation) divided by average twin plane spacing multiplied by 100
It is Variation of twin plane spacing distribution of all tabular grains
If the number exceeds 25%, it is preferable in terms of homogeneity between particles.
Yes. Also, it is difficult to prepare an emulsion of less than 3%. Next, the composition and structure of tabular grains used in the present invention.
Is described. Tabular grain halogen used in the present invention
The silver halide composition is silver iodochlorobromide. Basically host tabular grains
Is silver iodobromide or silver iodochlorobromide
A combination of silver chloride, silver chlorobromide or silver iodochlorobromide
It consists of a combination. Tabular grains (host tabular grains and epita
Ratio of the total silver combined with the axial joint)
The silver halide content is preferably 1 mol% or more and 6 mol% or less. Than
Preferably the silver chloride content is 2 mol% or more and 5 mol% or less
The The silver iodide content is preferably 2 mol% or more. Than
Preferably, the silver iodide content is 2 mol% or more and 10 mol% or less.
is there. The host tabular grain of the present invention contains silver iodide.
It is preferable to have an outermost layer. Silver iodide content of outermost layer
Is preferably 3 mol% or more and 30 mol% or less. here
The silver iodide content of the outermost layer is mol% with respect to the silver of the outermost layer.
The The structure inside the outermost layer is optional, but
The silver halide content is basically less than the outermost layer. The outermost layer is good
Preferably 5% in terms of silver based on the total amount of silver in the host tabular grains
20% or less, more preferably 10% or more and 15%.
% Or less. Exceeding this condition causes epitaxial deposition.
The effect of the present invention is that the adhesion is uneven among the grains and the dislocation lines do not enter.
Is difficult to obtain. In the present invention, preferably, all halogens are used.
When the average silver chloride content of silver halide grains is CL mol%
More than 70% of the total projected area has a silver chloride content of 0.7C
L to 1.3CL, particularly preferably
It is in the range of 0.8CL to 1.2CL. Of the present invention
Emulsions are based on uniform epitaxial deposition between grains.
In general, the distribution of silver chloride content between grains is monodispersed. The
In addition, preferably the average silver iodide content of all silver halide grains
70% or more of the total projected area when the rate is I mol%
The silver iodide content is within the range of 0.7I to 1.3I.
Particularly preferably within the range of 0.8I to 1.2I.
is there. Distribution of silver iodide content between grains is monodisperse
This makes the epitaxial deposition uniform between the grains. Each
In order to measure the silver chloride and silver iodide content of
EPMA method (Electron Probe Micro)
o Analyzer method) is effective. Emulsion grains
Prepare a dispersed sample so that it does not come into contact with the
Analyzing X-rays emitted by radiating
Therefore, it is possible to perform elemental analysis of a very small region irradiated with an electron beam.
You can. At this time, the measurement prevents damage to the sample due to the electron beam.
Therefore, it is preferable to carry out cooling at a low temperature. The emulsion of the present invention is 70% or more (number
Ratio) is silver halide selectively at the apex of the host tabular grain
Has at least one epitaxial junction per particle
The In the present invention, an epitaxial junction is a host.
Shaped by epitaxial deposition at the apex of tabular grains
This refers to a protruding joint formed. One grain in the emulsion of the present invention
Have more of this epitaxial junction per child
The more tabular grains occupy, the more preferable the hexagonal host.
Selective silver halide atoms are selectively applied to each of the tops of the tabular grains.
There is a total of 6 pieces per particle for each one of the joints.
Tabular grains account for 70% or more (number ratio) of all grains
Emulsions are particularly preferred. Here, the apex part is the tabular grain.
Centered at one vertex when viewed from a direction perpendicular to the surface
And this vertex and the two sides that make up this vertex are formed
And the length of the shorter side of these two sides
Means a portion in a sector shape with a radius of 1/3 of. Hexagon
Each tabular grain is epitaxial at each of the six vertices
Most of the particles have a total of 6 joints.
However, it is preferable in the present invention. The shape of the main plane of the tabular grain is rounded
In the case of a hexagonal shape, the vertices and sides of the main plane are
Virtual triangles and hexagons formed by extending sides
Let each be a vertex and an edge of the shape. Usually the epita of the present invention
Main plane other than the top of tabular grains
Or an epitaxial junction is formed on a side other than the apex.
It is. In contrast, in the present invention, the main plane other than the apex portion
Or there is an epitaxial junction on the side other than the apex.
Without selective epitaxy on each of the hexagonal vertices
It is characterized by having a joint part. The epitaxial junction is silver chloride or salt odor
Silver chloride or silver iodochlorobromide. Preferably host tabular grain
The silver chloride content is 1 mol% or more higher than that of the child. More preferred
Alternatively, the silver chloride content is 10 mol% or less than the host tabular grains.
High above. However, the silver chloride content of the epitaxial junction is
50 mol% or less is preferable. Epitaxial junction odor
The silver halide content is preferably 30 mol% or more, and 50 mol% or less.
Above is particularly preferred. Epitaxial junction contains silver iodide
In order to maintain the shape of the epitaxial junction,
Preferably, the silver iodide content is 1 mol% or more and 20 mol% or less.
preferable. The amount of silver in the epitaxial junction is the host tabular grain.
It is preferably 1 mol% or more and 10 mol% or less of the silver amount of the child.
More preferably, it is more preferably 2 mol% or more and 7 mol% or less. The emulsion of the present invention is 70% or more of the total grains (number
Ratio) is at least 1 for each of the epitaxial junctions
It preferably consists of tabular grains having a dislocation line,
The more the particles are, the better. The milk of the present invention
Each agent has a network-like dislocation line at the epitaxial junction.
Tabular grains, preferably 70% or more of the total grains
The top (number ratio) is mesh-like at each epitaxial junction.
It is preferably made of tabular grains having dislocation lines. here
And the net-like dislocation lines are not counted as numbers.
A dislocation line in which a plurality of dislocation lines intersect like a mesh.
A flat plate with an epitaxial junction at two or more apexes
In grains, dislocations are not necessarily at each epitaxial junction
The line need not be present. At least one vertex
One dislocation line at the combined epitaxial junction, preferably
Is preferable as long as it contains network dislocation lines.
Corresponds to a taxi emulsion. Preferably at the apex
70% or more (number ratio of joints) of the PITAXIAL joint
Includes network-like dislocation lines. 70% of all particles in the present invention
Above (number ratio) is dislocation lines except for epitaxial junctions
Is preferably absent. Dislocation lines are epitaxial
Epitaxial to provide preferential deposition position of deposition
The dislocation lines other than the junction are the epitaxy of the present invention.
This inhibits the formation of tabular grains. Preferably 70 of all particles
% Or more (number ratio) indicates zero dislocation lines. In this case,
Excluding Pitachial joint. Most preferably total projected area
90% or more of these have zero dislocation lines. Dislocation lines of tabular grains
Are described in, for example, J.A. F. Hamilton, Photo. Sc
i. Eng. 11, 57, (1967) and T.W. Shi
ozawa, J .; Soc. Photo. Sci. Japan
n, 35, 213, (1972).
Observe by direct method using a scanning electron microscope
You can. That is, dislocation lines are generated from the emulsion to the grains.
Halogen extracted with care not to apply too much pressure
Electron beam with silver halide particles placed on mesh for electron microscope observation
Cool the sample to prevent damage (printout, etc.)
Observe by the transmission method in the rejected state. At this time, the thickness of the particles
The thicker the thickness, the more difficult it is to transmit the electron beam.
(200 kV or more for particles having a thickness of 0.25 μm)
It is possible to observe more clearly using the electron microscope
Yes. From a photograph of the particles obtained by such a method,
About each particle when viewed from the direction perpendicular to the main plane
The position and number of dislocation lines can be obtained. The emulsion of the present invention has a vertex portion of the host tabular grain.
1 grain of silver halide epitaxial junction selectively
At least one per silver halide epitaxy
Whether each of the joints is perpendicular to the (111) main plane
When viewed from the host plane, more than 60% of the projected area of each joint is
Tabular grains that are protrusion-like joints that exist outside the tabular grains
Occupying 70% or more (number ratio) of all particles,
More particles are preferred. Also, the top of the host tabular grain is particularly preferable.
Select a silver halide epitaxial junction selectively at the point.
6 grains per grain, the silver halide epitaxial contact
Each joint is viewed from a direction perpendicular to the (111) main plane.
At least 60% of the projected area of each joint is host tabular grain
Tabular grains, which are protrusion-like joints existing outside, are all grains.
The emulsion occupies 70% or more (number ratio). “When viewed from a direction perpendicular to the main plane,
60% or more of the projected area is outside the host tabular grain
`` Present '' means a step on the main plane at the apex of the host tabular grain.
It does not epitaxially join in the shape of a hill, but as shown in (Fig. 1)
Epitaxially bonding by protruding in the lateral direction of tabular grains
And is defined as follows: A: Epitaxial contact when viewed from a direction perpendicular to the main plane
If the projected area of the joint overlaps with the apex of the host tabular grain
Area of no part (shaded area in Fig. 1) B: Epitaxial contact when viewed from a direction perpendicular to the main plane
Overlapping the top of the host tabular grain in the projected area of the joint
Area of the part (blacked area in Fig. 1) The tabular grains of the present invention have A / (A + B) ≧ 0.6
At least one epitaxial junction per particle
One is provided, and six is particularly preferred. Keep the above shape after epitaxial deposition
If not controlled, epitaxial deposition is rearranged.
As a result, the dislocation line disappears. The epitaxial junction form is, for example, a replica.
It can be observed by a method electron micrograph. Less in the present invention
For each of 100 grains or more, each epitaxial contact
The conformation is observed and the proportion of the particles is determined. The epitaxy of the present invention satisfying the above conditions
The tabular emulsion can reduce the pBr of the emulsion.
The Here, pBr is the logarithm of the reciprocal of the bromine ion concentration.
The It became possible to lower pBr to 3.5 or less
Thus, the storage stability can be remarkably improved. further
Shooting feeling built with silver iodobromide as a basic component
The problem of processing dependence that can be incorporated into optical materials is solved.
I can decide. More preferably, the emulsion of the present invention has a p at 40 ° C.
Br is 3.0 or less, particularly preferably 2.5 or less.
is there. The above-described epitaxial milk of the present invention is described below.
Preparation of host tabular grains and process
Explain in detail, divided into two preparation of the Pitachial joint
The First, for preparing the epitaxial emulsion of the present invention.
Necessary host tabular grains will be described in detail. The host of the present invention
The distribution of silver iodide in tabular grains
The above multi-structured particles are preferred. Silver iodide here
The structure has a distribution of silver iodide between each structure.
The content is 0.5 mol% or more, more preferably 1 mol% or more
Means different. In the present invention, the host
The “outermost layer” of a tabular grain is the majority of the distribution of silver iodide.
The outermost layered phase of the heavy structure. The structure regarding the distribution of silver iodide is basically
Specifically, it can be calculated from the prescription value in the particle preparation process.
You can. Change in silver iodide content at the interface between structures
May change suddenly or slowly
obtain. For these confirmations, consider the measurement accuracy in the analysis.
It is necessary to consider, but the EPMA method mentioned above is effective.
The Using this method, tabular grains were viewed from the direction perpendicular to the main plane.
In this case, the silver iodide distribution in the grain can be analyzed.
Therefore, use a sample cut into ultrathin sections with a microtome.
Analysis of silver iodide distribution in the cross section of tabular grains
Can. In the present invention, the host tabular grain is the outermost layer.
The silver iodide content is 3 to 30 mol%, 10 to 2
It is preferably 0 mol%. Outermost layer is based on total silver
5 to 20%, more preferably 10 to 1
5%. Here, the ratio of the outermost layer is the host tabular grain tone
Against the amount of silver used to obtain the final grain in the manufacturing process
The ratio of the amount of silver used for the preparation of the outermost layer. Silver iodide
Content is the outermost layer relative to the amount of silver used to prepare the outermost layer.
This means the percentage of the molar ratio of silver iodide used in the preparation.
The cloth may be uniform or non-uniform. Of silver iodide content
If the distribution is non-uniform, the amount of silver iodide is the average in the outermost layer
Value. Providing the outermost layer containing silver iodide is an epitaxy
For preventing dissolution of host tabular grains after the formation of the solder joint
Useful. The preparation of the host tabular grains is basically nucleated.
It consists of a combination of three steps: ripening, ripening and growth.
In the nucleation process, U.S. Pat. No. 4,713,320
And methionine described in US Pat. No. 4,942,120
Use low gelatin content, US Pat. No. 4,9
Nucleation with high pBr as described in 14,014,
Nucleation is performed in a short time as described in JP-A-2-222940
In the nucleation process of the particles used in the present invention,
Is extremely effective. Particularly preferably in the present invention.
Low molecular weight oxidized gelatin at a temperature of 20 ° C to 40 ° C
Under stirring in the presence of silver nitrate aqueous solution and halogen aqueous solution and low
Add molecular weight oxidized gelatin within 1 minute
is there. At this time, the pBr of the system is preferably 2 or more, and the pH is 7
The following is preferred. The concentration of silver nitrate aqueous solution is 0.6 mol / L
The following concentrations are preferred. Using the above nucleation method
The formation of the epitaxial emulsion of the present invention becomes easier. In the aging process, US Pat.
Performed in the presence of a low concentration base described in No. 4,453
The high pH described in US Pat. No. 5,013,641
Is performed in the ripening process of the tabular grain emulsion of the present invention.
Can be used. US Pat. No. 5,14
No. 7,771, No. 5,147,772, No. 5,1
47,773, 5,171,659, 5,
No. 210,013 and No. 5,252,453
An aging step of the polyalkylene oxide compound described
Alternatively, it can be added in a later growth step. The present invention
The aging step is preferably 50 ° C. or higher and 80 ° C. or lower.
At a temperature of PBr immediately after nucleation or during ripening
Is preferably lowered to 2 or less. From just after nucleation
Additional gelatin is preferably added by the end of aging
The Particularly preferred gelatin is 95% amino group or more.
It has been modified to liquefy or trimellitize. This
By using these gelatins, the epitaxy of the present invention
The preparation of the emulsion is facilitated. In the growth process of the present invention, US Pat.
4,672,027 and 4,693,964
A silver nitrate aqueous solution and a halogen aqueous solution containing bromide
It is preferable to add the silver iodide fine grain emulsion simultaneously.
It is done. The silver iodide fine grain emulsion should be substantially silver iodide.
Silver bromide and / or as long as it can be mixed crystals
It may contain silver chloride. Preferably 100% iodide
Silver. Silver iodide has a β- and γ-form in its crystal structure.
As described in US Pat. No. 4,672,026.
Thus, there can be an α-form or an α-form-like structure. The present invention
There is no particular limitation on the crystal structure of
A mixture of γ-form and more preferably β-form is used.
US Pat. No. 5,004,679 for silver iodide fine grain emulsion
It may be formed just before the addition described in
Any of those subjected to the water washing step may be used. Silver iodide fine grains
The emulsion is described in U.S. Pat. No. 4,672,026.
It can be easily formed by a method. Keep pI value constant during grain formation
The silver salt aqueous solution and iodide salt aqueous solution
The bull jet addition method is preferred. Where pI is the I- of the system
It is the logarithm of the reciprocal of the ion concentration. Temperature, pI, pH, z
Types and concentrations of protective colloids such as latin, silver halide
The presence / absence, type, concentration, etc. of the solvent are not particularly limited, but the particles
Is less than 0.1 μm, more preferably 0.07 μm.
m or less is convenient for the present invention. Particles because they are fine particles
The shape cannot be completely specified, but the particle size distribution varies
The coefficient is preferably 25% or less. Especially in the case of 20% or less
The effect of the present invention is remarkable. Here of the silver iodide fine grain emulsion
Size and size distribution of silver iodide fine particles by electron microscope
Put on the mesh for observation, not the carbon replica method
Directly observed and determined by the transmission method. This is a particle size
In the observation by the carbon replica method,
This is because the measurement error increases. Particle size is observed
Defined as the diameter of a circle with a projected area equal to the projected particle
The This same projected area for the particle size distribution
Obtained using the circle diameter. The most effective iodide in the present invention
Silver fine particles have a particle size of 0.06 μm or less and 0.02 μm
Above, the variation coefficient of particle size distribution is 18% or less
is there. After the above grain formation, preferably US Pat.
Normal water washing and p described in No. 2,614,929
For concentration adjustment of protective colloids such as H, pI and gelatin
The concentration of silver iodide contained in each is adjusted. pH is 5 or more and 7
The following is preferred. pI value is the lowest solubility of silver iodide
Set pI value or higher pI value
Is preferred. The protective colloid agent has an average molecular weight of 10
About 10,000 ordinary gelatin is preferably used. Average
Low molecular weight gelatin with a molecular weight of 20,000 or less is also preferably used
The Also, use a mixture of gelatins with different molecular weights.
Sometimes it is convenient. Gelatin per kg of emulsion
The amount is preferably 10 g or more and 100 g or less. Than
Preferably they are 20g or more and 80g or less. 1kg of emulsion
The amount of silver in terms of silver atoms is preferably 10 g or more and 100
g or less. More preferably, it is 20g or more and 80g or less
is there. The silver iodide fine grain emulsion is usually dissolved and added in advance.
However, it is necessary to sufficiently increase the stirring efficiency of the system at the time of addition.
There is. Preferably, the stirring speed is set higher than usual.
Determined. Add antifoaming agent to prevent foam generation during stirring.
Is effective. Specifically, US Pat. No. 5,27.
Defoaming agent described in Examples of No. 5,929 is used
It is done. Most preferably used in the growth process of the present invention.
The method described in JP-A-2-188874 can be used.
is there. Silver bromide or silver iodobromide prepared just before the addition
Is a continuous silver iodochlorobromide emulsion during tabular grain growth
Add and dissolve the ultrafine grain emulsion to grow tabular grains
The Powerful external mixer for preparing ultrafine emulsions
It has stirring ability, and the silver nitrate aqueous solution and halo are added to the mixer.
Gen aqueous solution and gelatin are added. Gelatin is silver nitrate
Pre- or direct with aqueous solution and / or halogen aqueous solution
It can be added before mixing and the gelatin aqueous solution alone
It can also be added by itself. Gelatin has normal molecular weight
Smaller than that is preferably 10,000 to 5000
0 is particularly preferred. Amino group is phthalated or succinylated
Or gelatin modified by 90% or more for trimellitization
And / or oxidation treatment with reduced methionine content
Latin is particularly preferably used. Using this method
This facilitates the preparation of the epitaxial emulsion of the present invention.
The In the present invention, the host tabular grains face each other.
(111) The side connecting the main planes is 75% or more of all sides
It is especially preferred that the bottom is composed of (111) faces
Yes. Here, not more than 75% of all sides are (111) planes.
Is composed of more than 25% of all sides
That there are crystallographic faces other than the (111) face
It is. It is usually understood that the plane is the (100) plane
Yes, but the other side, ie (110) plane and more
The case of a high index surface may also be included. In the present invention, all
When 70% or less of the side surface is composed of (111) surfaces
The effect is remarkable. Less than 75% of all sides are composed of (111) planes.
Whether or not it has been made, its tabular grain shadow was applied
Easy to identify from electron micrographs using the carbon replica method
I can decline. Usually 75% or more of the side faces are composed of (111) faces.
In the case of hexagonal tabular grains, (11
1) The six sides directly connected to the main plane are different.
The (111) main plane is connected at an acute angle and an obtuse angle. one
On the other hand, 75% or less of all sides are composed of (111) planes
In the case of hexagonal tabular grains, (111)
The six side faces that are directly connected to the face are relative to the (111) principal plane
All connected at an obtuse angle. Shadowing below 50 ° C
The obtuse angle of the side with respect to the main plane
A sharp angle can be determined. Preferably 30 ° or less 10 ° or more
By shadowing at an angle of
This is easy. Furthermore, the ratio of the (111) plane to the (100) plane
There is a method using adsorption of a sensitizing dye as a method for obtaining the rate.
It is effective. The Chemical Society of Japan, 1984, Volume 6, Page 94
(111) plane using the technique described in 2-947
And (100) plane ratio can be obtained quantitatively.
Using the ratio and the equivalent circle diameter and thickness of the tabular grains described above
Calculate the ratio of (111) planes on all sides
You can. In this case, the tabular grain has the equivalent circle diameter and thickness.
Is assumed to be a cylinder. This assumption makes the total table
The ratio of the side surface to the area can be obtained. The above
Increase the ratio of the (100) plane obtained using adsorption of sensitizing dye
The value divided by the ratio of the side mentioned above multiplied by 100 is all sides
(100) plane ratio. 100 to that value
The ratio of the (111) plane in all sides can be found
It becomes. In the present invention, (111) in all aspects
It is more preferable that the surface ratio is 65% or less. In the present invention, all sides of the host tabular grain emulsion
Explains how to make 75% or less of the surface (111) surface
To do. Most commonly, the side of the host tabular grain emulsion
The ratio of the (111) plane is the pBr at the time of preparing the tabular grain emulsion.
Can be determined. Preferably, the amount of silver required to form the outermost layer is 3
Addition of 0% or more reduces the ratio of the (111) side surface.
In other words, pB that increases the ratio of the (100) side surface
Set to r. More preferably the amount of silver required to form the outermost layer
Addition of more than 50% of the (111) face ratio of the side surface decreases
PBr is set. Alternatively, after the total amount of silver has been added,
Set pBr so that the ratio of the (100) side surface increases.
Increase the ratio by aging and aging
It is also possible. The ratio of the (100) side surface is increased.
PBr is a protective roller for system temperature, pH, gelatin, etc.
Id agent type, concentration, presence or absence of silver halide solvent, type,
The value can vary widely depending on the concentration. Usually preferred
Specifically, pBr is 2.0 or more and 5 or less. More preferred
Is pBr2.5 or more and 4.5 or less. However,
As described above, the value of this pBr is, for example, a silver halide solution.
It can be easily changed by the presence of an agent or the like. Used in the present invention
US Patent No.
No. 3,271,157, No. 3,531,286, No.
No. 3,574,628, JP-A-54-1019,
(A) Organic Thioe described in No. 54-158917
-Tels, JP-A-53-82408, 55-777
(B) Thio described in 37, 55-2982, etc.
Urea derivatives, described in JP-A-53-144319
(C) a titanium sandwiched between oxygen or sulfur atoms and nitrogen atoms
Silver halide solvent having ocarbonyl group, JP-A-54
(D) imidazoles described in No. -100177
(E) sulfite, (f) ammonia, (g) thiocyanate
And the like. Particularly preferred solvents are thiocyanate.
And ammonia and tetramethylthiourea. Ma
The amount of solvent used varies depending on the type.
In the case of thiocyanate, the preferred amount is silver halide 1
1 x 10 per mole^-Four1 x 10 moles or more^-2Less than or equal to
The Change the face index of the side face of the tabular grain emulsion.
Refer to European Patent No. 515894A1 as a method.
Can. US Pat. No. 5,252,453
The polyalkylene oxide compounds described in
You can also. US Pat. No. 4,680, an effective method.
No. 254, No. 4,680, 255, No. 4, 68
Recorded in 0,256 and 4,684,607
The listed surface index modifiers can be used. For normal photos
Spectral sensitizing dyes are also used as surface index modifiers
Can. In the present invention, the host tabular grains have dislocation lines.
It is preferable not to have. Nucleation and maturation detailed above
Dislocation lines by combining the growth and growth processes
Can be eliminated. Necessary for the preparation of the epitaxial emulsion of the present invention.
The detailed epitaxial junction will be described in detail. Epitaxy
Even if the deposition occurs immediately after the formation of the host tabular grains
After the formation of host tabular grains, after normal desalting
You may go to Preparation of the epitaxial emulsion of the present invention
Select pH, pAg, gelatin type and concentration, viscosity
To do. Especially pH is important, preferably 4 or more and 6 or less
It is. The gelatin used in the present invention has the following various modifications.
It may be decorated. For example, modifying the amino group
Phthalated gelatin, succinylated gelatin, trimelli
Gelatin, pyromellitic gelatin, carboxyl group
Modified esterified gelatin, amidated gelatin, immi
Methionine, a formylated gelatin modified with a dazole group
Oxidized gelatin with reduced groups and increased reduction treatment
Examples include gelatin. On the other hand, other hydrophilic colloids are also used.
be able to. For example, gelatin derivatives, gelatin and others
Graft polymer, albumin, casein
Protein such as: hydroxyethyl cellulose, carbo
Xymethylcellulose, cellulose sulfates
Udon cellulose derivatives, sodium alginate, starch derivatives
Sugar derivatives such as: polyvinyl alcohol, polyvinyl
Alcohol partial acetal, poly-N-vinylpyrrolide
, Polyacrylic acid, polymethacrylic acid, polyacrylic
Amide, polyvinyl imidazole, polyvinyl pyrazo
Various synthetic hydrophilics such as mono- or copolymers such as
Can be used. As gelatin
In addition to lime-processed gelatin, acid-processed gelatin and Bull.
Soc. Sci. Photo. Japan. No. 16.
Enzymatically treated gelatin as described in P30 (1966)
Gelatin hydrolyzate or enzyme
Decomposition products can also be used. Site designation of epitaxial junction of the present invention
A sensitizing dye is used as the agent. Select the amount and type of dye used
Select the epitaxial deposition position.
Can be trawled. The dye has a saturation coverage of 50
It is preferable to add from 90% to 90%. Color used
Cyanine dyes, merocyanine dyes, complex cyanides
Dye, complex merocyanine dye, holopolar cyanine
Dyes, hemicyanine dyes, styryl dyes and hemioki
Sonol dyes are included. A particularly useful dye is cyani
It is a dye belonging to the dye. These dyes include bases
Of nuclei commonly used in cyanine dyes as sexual heterocyclic nuclei
Either can be applied. That is, for example, pyrroline
Nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxy
Sazole nucleus, thiazole nucleus, selenazole nucleus, imidazo
Nuclei, tetrazole nuclei, pyridine nuclei;
Nuclei fused with cyclic hydrocarbon rings; and aromatics in these nuclei
A nucleus fused with a hydrocarbon ring, ie, for example, indolenine
Nucleus, benzoindolenin nucleus, indole nucleus, benzooxy
Sador nucleus, naphthoxazole nucleus, benzothiazole
Nucleus, naphthothiazole nucleus, benzoselenazole nucleus, ben
A zoimidazole nucleus or a quinoline nucleus can be applied. these
The nucleus may have a substituent on the carbon atom. These sensitizing dyes may be used alone.
However, combinations of these may be used, and combinations of sensitizing dyes
Is often used for the purpose of supersensitization. That generation
Examples are U.S. Pat. Nos. 2,688,545 and 2,973.
No. 7,229, No. 3,397,060, No. 3,5
22,052, No. 3,527,641, No. 3,
No. 617,293, No. 3,628,964, No.
3,666,480, 3,672,898,
No. 3,679,428, No. 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
No. 7, British Patent No. 1,344,281, No. 1,50
7,803, Japanese Examined Sho 43-4936, 53-12
No. 375, JP-A 52-110618, 52-10
No. 9925. Spectral sensitizing effect itself with sensitizing dye
Dyes that do not absorb or that do not substantially absorb visible light
Quality and supersensitizing substances added simultaneously or separately.
You may add. The outermost surface of the host tabular grain during adsorption of the sensitizing dye
The silver iodide content of the extreme surface layer of the layer is higher than that of the outermost layer.
It is preferable to prepare an epitaxial emulsion. Intensifying color
Prior to the addition of elemental iodine is added.
The In the present invention, the aforementioned AgI fine grain emulsion is added.
To increase the silver iodide content on the surface of the host tabular grains
Is most preferably used. This makes silver iodide between grains
The distribution of the content becomes uniform and the adsorption of the sensitizing dye becomes uniform.
This makes it possible to prepare the epitaxial emulsion of the present invention.
Become. The amount of iodine ion or silver iodide added is
The amount of silver in the tabular grains is 1 x 10 per mole.^-FourTo 1x
10^-2The molar range is preferably 1 × 10^-3To 5 × 10^-3
A molar range is particularly preferred. The method for forming the epitaxial junction is halogen.
Solutions containing ions and AgNO_ThreeWith simultaneous addition of solution containing
May be added separately, and the particle size is smaller than the host tabular grains
Addition of AgCl fine particles, AgBr fine particles, AgI fine particles
Or added in combination with the addition of mixed crystal particles.
May be formed. AgNO_ThreeWhen adding a solution
The addition time is preferably 30 seconds or more and 10 minutes or less.
In particular, it is particularly preferably from 1 minute to 5 minutes. Epita of the present invention
To form a chiral emulsion, the silver nitrate solution to be added
Concentration is 1.5 mol / liter (hereinafter "L" for liter)
The following concentrations are preferred, particularly 0.5 mol /
A concentration of L or less is preferred. At this time, stirring in the system is efficient.
It is necessary to carry out and it is preferable that the viscosity in the system is low. The amount of silver in the epitaxial junction is the host plate.
It is 1 mol% or more and 10 mol% or less of the silver amount of the particles
Preferably, 2 mol% or more and 7 mol% or less are more preferable.
If the amount is too small, an epitaxial emulsion cannot be prepared.
If too much, it becomes unstable. The pBr at the time of forming the epitaxial junction is
3.5 or more is preferable, and 4.0 is particularly preferable. Epita
The temperature during the formation of the axial junction is (111) the main plane
When viewed from the vertical direction, the outer side of the host tabular grain is stretched greatly.
To form protruding protruding epitaxial junctions
The lower the temperature, the better. Specifically, 30 ° C to 45 ° C
It is preferably carried out at 30 ° C.
Perform at or below ℃. Important is the host plate and epitaxial
Epitaxy while preventing melting of the joint itself
Forming a joint part. Before the formation of the epitaxial junction, it will be described later.
Add anti-fogging agent and / or stabilizer to
It is also preferable in the present invention to prevent dissolution of plate particles. Furthermore, after the formation of the epitaxial junction
Sensitizing dye and / or antifoggant described later
And / or adding stabilizers is also epitaxy
This is preferable in the present invention in terms of maintaining the shape of the joint portion. In the present invention, the epitaxial junction is formed.
Is preferably doped with a 6-cyano metal complex.
Among the 6 cyano metal complexes, iron, ruthenium, osmiu
Contains cobalt, cobalt, rhodium, iridium or chromium
Those that do are preferred. Addition amount of metal complex is halogenated
Silver (all silver combined with host and epitaxial junctions)
Amount) 10 per mole^-9Thru 10^-2This is a range of moles
And preferably 10 per mole of silver halide.^-81
0^-FourMore preferably, it is in the molar range. Metal complex
Can be added dissolved in water or organic solvent
The The organic solvent is preferably miscible with water. Yes
Examples of organic solvents include alcohols, ethers, glycosyl
, Ketones, esters, and amides
The The metal complex is represented by the following formula (I):
The 6-cyano metal complex is particularly preferred. 6 cyano metal complex
High-sensitivity photosensitive material by using emulsion using
Even when the photosensitive material is stored for a long period of time.
The effect of suppressing the occurrence of cracking is obtained. (I) [M (CN)₆]^n- (Wherein M is iron, ruthenium, osmium, cobalt,
Rhodium, iridium or chrome, n is 3 or
Is 4. ). Specific examples of 6-cyano metal complexes are shown below. (I-1) [Fe (CN)₆]^Four- (I-2) [Fe (CN)₆]^3- (I-3) [Ru (CN)₆]^Four- (I-4) [Os (CN)₆]^Four- (I-5) [Co (CN)₆]^3- (I-6) [Rh (CN)₆]^3- (I-7) [Ir (CN)₆]^3- (I-8) [Cr (CN)₆]^Four- The counter cation of the 6 cyano complex is miscible with water.
It is easy to use and is suitable for silver halide emulsion precipitation.
It is preferable to use ON. Examples of counter ions include Al
Potassium metal ions (eg, sodium ion, potassium ion)
, Rubidium ion, cesium ion, lithium ion
), Ammonium ions and alkylammonium
Ions are included. In the present invention, water washing is epitaxial precipitation.
It can be done either before or after wearing. Washing temperature is eye
You can choose according to your needs, but choose between 5 ℃ and 50 ℃
Yes, but at the apex of the host particle before epitaxial deposition
Or melting (111) perpendicular to the main plane
Epita protruding outside the host tabular grain when viewed from the direction
It is 40 ° C or less in terms of maintaining the form of the axial joint.
It is preferable. You can choose the pH for washing depending on the purpose
It is preferable to select between 2-10. More preferably
It is the range of 3-8. Select pAg for washing according to purpose
However, it is preferable to select between 5 and 10. How to wash and
Noodle washing method, dialysis method using semipermeable membrane, centrifugation
Method, coagulation sedimentation method, ion exchange method
be able to. In the case of coagulation sedimentation, use of sulfate
Method, using organic solvent, using water-soluble polymer
Method, method using gelatin derivatives, etc.
Yes. When washing is performed before epitaxial deposition
The top of the host tabular grains dissolves during washing.
The host plane when viewed from the direction perpendicular to the (111) main plane
Protruding epitaxy projecting greatly outside the plate particles
It may be difficult to form a glue joint. If you do,
Add silver iodobromide (or silver bromide) before deposition
To repair the apex of the dissolved host tabular grains
It is preferable to perform epitaxial deposition later. The emulsion of the present invention is formed after epitaxial deposition.
It is preferable to perform sensitization. Preferably implemented in the present invention.
One of the chemical sensitizations is chalcogen sensitization and noble metal sensitization.
Germany or combination, James (TH James
s) by The Photographic Process, 4th edition,
Published by Macmillan, 1977, (TH James,
The Theory of the Photogr
aphic Process, 4th ed, Macm
illan, 1977) as described on pages 67-76.
Can be performed using active gelatin, and
-Ache Disclosure, 120, 1974 4
Mon, 12008; Research Disclosure, 34
Volume, June 1975, 13452, US Pat. No. 2,64
No. 2,361, No. 3,297,446, No. 3,7
No. 72,031, No. 3,857,711, No. 3,9
01,714, 4,266,018, and
3,904,415 and British Patent 1,31
PAg 5-10, pH 5-5 as described in US Pat.
8 and temperature 30-80 ° C., sulfur, selenium, tellurium
Gold, platinum, palladium, iridium
It can be a plurality of combinations of sensitizers. For precious metal sensitization
Gold, platinum, palladium, iridium and other precious gold
Metal salts can be used, especially gold sensitization and parasiu
Both sensitization and a combination of both are preferred. In case of gold sensitization
Chloroauric acid, potassium chloroaurate, potassium
-Publics such as lithiocyanate, gold sulfide, gold selenide
Known compounds can be used. Palladium compounds are
Palladium divalent salt or tetravalent salt is meant. preferable
The palladium compound is R₂PdX₆Or R₂PdX_FourIn the table
I will. Where R is a hydrogen atom, an alkali metal atom or
Represents an ammonium group. X represents a halogen atom
Represents a chlorine, bromine or iodine atom. Specifically, K₂PdCl_Four, (NH_Four)₂P
dCl₆, Na₂PdCl_Four, (NH_Four)₂PdCl_Four, Li
₂PdCl_Four, Na₂PdCl₆Or K₂PdBr_FourPreferred
That's right. Gold and palladium compounds are thiocyanic acid
Preferably in combination with salt or selenocyanate
Yes. Hypo, thiourea based sulfur sensitizers
Compounds, rhodanine compounds and US Pat. No. 3,857,
No. 711, No. 4,266,018 and No. 4,0
Using sulfur-containing compounds described in No. 54,457
Can. Chemistry in the presence of so-called chemical sensitization aids
It can also be sensitized. Useful chemical sensitization aids include aza
Like indene, azapyridazine, azapyrimidine,
Suppresses fog and increases sensitivity in the process of chemical sensitization
Known compounds are used. Chemical sensitization aid
Examples of modifiers are disclosed in U.S. Pat. No. 2,131,038.
3,411,914, 3,554,757, special
Kaisho 58-126526 and Duffin "photographic emulsion"
Chemistry ", pages 138-143. The emulsion of the present invention is preferably used in combination with gold sensitization.
Good. As a preferred amount of gold sensitizer, 1 mol of silver halide
1 × 10 per le^-Four~ 1x10^-7Mole and even more preferred
What is new is 1 × 10^-Five~ 5x10^-7Is a mole. Parajiu
The preferred range of silver compounds is 1 per mole of silver halide.
× 10^-3To 5 × 10^-7Is a mole. Thiocyanate
Alternatively, the preferred range of selenocyan compounds is halogen
5 x 10 per mole of silver halide^-2To 1 × 10^-6In moles
The In the silver halide grains used in the present invention,
The preferred amount of sulfur sensitizer used is silver halide 1
1 x 10 per mole^-Four~ 1x10^-7Mole and even better
The best is 1 × 10^-Five~ 5x10^-7Is a mole. As a preferred sensitizing method for the emulsion of the present invention,
There is selenium sensitization. In selenium sensitization, a known defect
Using stable selenium compounds, specifically colloidal metals
Selenium, selenoureas (for example, N, N-dimethyl)
Selenourea, N, N-diethylselenourea), selenoke
Selenium compounds such as tons and selenoamides are used.
be able to. Selenium sensitization is sulfur sensitization or noble metal sensitization
It is better to use it in combination with feeling or both
There is a case. In tellurium sensitization, unstable tellurium compounds
JP-A-4-224595, 4-2713
No. 41, No. 4-3333043, No. 5-303157
No. 6-27573, No. 6-175258, No. 6
-180478, 6-208184, 6-20
8186, 6-317867, 7-14057
No. 9, No. 7-301879, No. 7-301880
The unstable tellurium compounds described in
it can. Specifically, phosphine tellurides (for example,
Normal butyl-diisopropylphosphine tellurium
, Triisobutylphosphine telluride, trinormal
Butoxyphosphine telluride, triisopropylphosphine
Intellide), diacyl (di) tellurides (for example,
Bis (diphenylcarbamoyl) ditelluride, bis (N
-Phenyl-N-methylcarbamoyl) ditelluride, bi
(N-phenyl-N-methylcarbamoyl) tellurium
Bis (N-phenyl-N-benzylcarbamoyl)
Telluride, bis (ethoxycarbonyl) telluride), te
Luroureas (for example, N, N'-dimethylethylenetel
Rourea), telluramides, telluroesters, etc.
It only has to be. Preferably phosphine tellurides and diacids
Ru (di) tellurides. In the present invention, the temperature for chemical sensitization
40-50 ° C when viewed from the (111) main plane
Epitaxial junction protruding outside the host tabular grain
It is preferable at the point which keeps this form. For the same reason,
Add a compound that acts as a solvent, such as an oxocyanate
Use only the minimum necessary amount within the above range.
preferable. The photographic emulsion used in the present invention contains a photosensitive material.
Prevents fogging during the production process, storage, or photo processing
To stop or stabilize photographic performance,
Compounds can be included. Ie thiazole
Such as benzothiazolium salt, nitroimidazole
, Nitrobenzimidazoles, chlorobenzimi
Dazoles, bromobenzimidazoles, mercapto
Thiazoles, mercaptobenzothiazoles, merca
Putobenzimidazoles, mercaptothiadiazoles
, Aminotriazoles, benzotriazoles, di
Trobenzotriazoles, mercaptotetrazoles
(Especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; examples
For example, a thioketo compound such as oxadrine thione;
Zaindenes, such as triazaindenes, tetraa
Zaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Tetraazaindenes), Pentaazaindene
Known as antifoggants or stabilizers, such as
Many compounds can be added. For example, US patents
3,954,474, 3,982,947,
Use the one described in Japanese Patent Publication No. 52-28660.
You can. One preferred compound is disclosed in JP-A-63-21.
There are compounds described in No. 2932. Antifogging agent
And stabilizers before and during particle formation, after particle formation,
Washing process, dispersion after washing, epitaxial formation, chemical
Before sensitization, during chemical sensitization, after chemical sensitization, before application
Depending on the purpose, it can be added at any time. During emulsion preparation
Adds to the original effect to prevent fogging and stabilize
In addition to controlling the crystal wall of the particles, reducing the particle size
Reduce particle solubility, control chemical sensitization
Can be used for various purposes such as controlling the arrangement of dyes.
Yes. When preparing the emulsion of the present invention, for example, during grain formation,
During epitaxial formation, desalting process, chemical sensitization, before coating
The presence of a metal ion salt is preferred depending on the purpose.
That's right. When doping a particle, the surface of the particle during particle formation
Particle formation when used as a chemical sensitizer or as a chemical sensitizer
Thereafter, it is preferably added before the completion of chemical sensitization. Whole particles
When doping the body and only the core part of the particle or
You can also choose the method of doping only the shell part. For example, Mg,
Ca, Sr, Ba, Al, Sc, Y, La, Cr, M
n, Fe, Co, Ni, Cu, Zn, Ga, Ru, R
h, Pd, Re, Os, Ir, Pt, Au, Cd, H
g, Tl, In, Sn, Pb, Bi can be used.
The These metals are ammonium salts, acetates, nitrates,
Sulfate, phosphate, hydrate or hexacoordination complex salt, tetracoordination complex
A salt form that can be dissolved during particle formation, such as salt.
Can be added. For example, CdBr₂, CdCl₂, Cd
(NO_Three)₂, Pb (NO_Three)₂, Pb (CH_ThreeCOO)₂,
K_Three[Fe (CN)₆], (NH_Four)_Four[Fe (C
N)₆], K_ThreeIrCl₆, (NH_Four)_ThreeRhCl₆, K_FourR
u (CN)₆Can be given. As a ligand for coordination compounds
Halo, ako, cyano, cyanate, thiocyanate,
Such as nitrosyl, thionitrosyl, oxo, carbonyl
You can choose from These are one kind of metal compound
2 or 3 or more types may be combined
May be used. The metal compound is water or methanol, aceto
It is preferable to add it in a suitable organic solvent such as
That's right. Hydrogen halide aqueous solution to stabilize the solution
(Eg HCl, HBr) or halogenated alk
(For example, KCl, NaCl, KBr, NaBr)
The method of adding can be used. Also acid if necessary
・ Alkali may be added. Metal compounds form particles
Even if it is added to the previous reaction vessel, it should be added in the middle of particle formation
You can also. In addition, water-soluble silver salt (for example, AgNO_Three)is there
Or an aqueous alkali halide solution (for example, NaCl, K
Br, KI) added continuously during silver halide grain formation
It can also be added. Further water-soluble silver salt, halogenated
Prepare a solution independent of the alkali at an appropriate time during particle formation
You may add continuously in a period. Furthermore, various addition methods
It is also preferable to combine them. The silver halide photographic emulsion of the present invention has a grain shape.
Applying reduction sensitization during or after grain formation
At least include particles with a hole capture zone in the host part.
Preferably. The hole capture zone is the so-called positive
Positives that occur in pairs with holes, for example, photoelectrons generated by photoexcitation
It refers to a region having a function of capturing holes. like this
As a method of providing a positive hole capture zone, a dopant is used.
However, in the present invention, intentional reduction sensitization is used.
It is desirable to provide them. The method of reduction sensitization is halogeno
A method of adding a reduction sensitizer to a silver halide emulsion, called silver ripening
Grown or matured in a low pAg atmosphere with pAg 1-7
Method, high pH atmosphere called pH ripening, pH 8-11
You can choose between growing or maturing methods
Yes. Two or more methods can be used in combination. In the present invention, intentional reduction sensitization means reduction.
Halogenation of hole-capturing silver nuclei by adding original sensitizers
Operation that is introduced into part or all of the silver halide grains
The Hole-capturing silver nuclei are small silver nuclei with little development activity.
This means that the silver nuclei prevent recombination loss during the exposure process.
In addition, the sensitivity can be increased. The method of adding a reduction sensitizer is a reduction sensitization method.
This is a preferable method in that the bell can be finely adjusted. reduction
Examples of the sensitizer include stannous salt, ascorbic acid and
And its derivatives, amines and polyamines, hydrazides
Derivatives, formamidinesulfinic acid, silane compounds
And borane compounds are known. Used in the present invention
These reduction sensitizers can be selected and used for reduction sensitization.
Can also be used in combination of two or more compounds
The Reduction sensitizers include stannous chloride, thiourea dioxide,
Dimethylamine borane, ascorbic acid and its derivatives
The body is a preferred compound. The amount of reduction sensitizer added is emulsion.
It is necessary to select the amount of addition because it depends on the manufacturing conditions.
10 per mole of silver halide^-7-10^-3Suitable range of mole
It is. The reduction sensitizer is, for example, water or alcohol
, Glycols, ketones, esters, amides
It is dissolved in such an organic solvent and added during grain growth. Acid for silver during the production process of the emulsion of the present invention
It is preferable to use an agent. What is an oxidizing agent for silver?
Acts on metallic silver and converts it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very fine silver particles by-produced during chemical sensitization
A compound capable of converting to silver ions is effective. here
The silver ions produced in
It may form a slightly soluble silver salt in water such as silver or silver selenide
It is also possible to form a readily soluble silver salt in water such as silver nitrate.
Yes. The oxidizing agent for silver is organic, even if it is inorganic.
There may be. Examples of inorganic oxidizing agents include ozono
, Hydrogen peroxide and its adducts (eg NaBO₂
・ H₂O₂・ 3H₂O, 2NaCO_Three・ 3H₂O₂, Na_FourP₂
O₇・ 2H₂O₂2Na₂SO_Four・ H₂O₂・ 2H₂O)
Oxalates (eg K₂S₂O₈, K₂C₂O₆, K₂P₂
O₈), Peroxy complex compounds (for example, K₂[Ti (O
₂) C₂O _Four] 3H₂O, 4K₂SO_Four・ Ti (O₂) OH
・ SO_Four・ 2H₂O, Na_Three[VO (O₂) (C₂H_Four)₂]
・ 6H₂O), permanganate (eg KMnO)_Four),
Chromate (eg K₂Cr₂O₇) Like oxygen acid
Salts, halogen elements such as iodine and bromine, perhalogenates
(For example, potassium periodate), high valent metal salts
(Eg, potassium hexacyanoferric acid) and thio
There is a sulfonate. Further, as an organic oxidizing agent, p-quinone
Quinones, such as peracetic acid and perbenzoic acid.
Oxides, compounds that release active halogens (eg N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example. The preferred oxidizing agent used in the present invention is:
Ozone, hydrogen peroxide and its adducts, halogen elements,
Inorganic oxidants of thiosulfonates and organic acids of quinones
Agent. Combined reduction sensitization and silver oxidizing agent
This is a preferred embodiment. Reduction using oxidant
How to apply sensitization, vice versa, or both
It can be used by selecting from the methods that exist. This
These methods can be chosen in both the particle formation process and the chemical sensitization process.
Can be used. Using the silver halide emulsion obtained in the present invention
The light-sensitive material produced in this way is at least one layer on a support.
A silver halide emulsion layer should be provided, but it is preferred.
Or a blue color sensitive layer, a green color sensitive layer, or a red color sensitive layer on the support.
At least one silver halide emulsion layer is provided.
Of blue, green, and red color layers.
At least one is composed of two or more layers with different sensitivities
Has been. Silver halide emulsion layer and non-light-sensitive layer
There are no particular restrictions on the number and layer order. A typical example is
On the support, the color sensitivity is substantially the same, but the photosensitivity is different.
A few color sensitive layers consisting of multiple silver halide emulsion layers
A silver halide photographic light-sensitive material having at least one,
The photosensitive layer is sensitive to blue light, green light, and red light.
A unit photosensitive layer with chromaticity and a multilayer silver halide
In general, a unit photographic photosensitive layer is used in a large photographic photosensitive material.
Rows are red-sensitive layer, green-sensitive layer, blue-sensitive in order from the support side
It is installed in the order of the color layer. However, depending on the purpose,
Different photosensitivity layers in the same color-sensitive layer
The order of installation can be taken as if sex layers were sown. Between and above the silver halide light-sensitive layers described above
Provide a non-photosensitive layer such as an intermediate layer for each layer on the upper and lower layers.
Also good. In the intermediate layer, JP-A 61-43748 is disclosed.
Nos. 59-113438, 59-113440
No. 61-20037, 61-20038
Couplers and DIR compounds as listed
Well, it contains anti-color mixing agents as usual
Also good. A plurality of halogens constituting each unit photosensitive layer
For silver halide emulsion layers, see German Patent 1,121,470.
Is highly sensitive as described in British Patent No. 923,045
A two-layer structure consisting of an emulsion layer and a low sensitivity emulsion layer is preferably used.
You can. Normally, the photosensitivity decreases gradually toward the support.
It is preferable to arrange so that
A non-photosensitive layer may be provided between the layers. Also,
JP-A-57-112751 and 62-200350
No. 62-206541, 62-206543
Low sensitivity milk on the side away from the support as described in
A high-sensitivity emulsion layer may be installed on the side close to the agent layer and support.
Yes. As a specific example, from the side farthest from the support,
For example, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer
(BH) / High-sensitivity green photosensitive layer (GH) / Low-sensitivity green photosensitive layer
Layer (GL) / high sensitivity red light sensitive layer (RH) / low sensitivity red light sensitive
Order of functional layer (RL) or BH / BL / GL / GH / R
H / RL order or BH / BL / GH / GL / RL /
It can be installed in the order of RH. Also described in Japanese Patent Publication No. 55-34932.
As shown, blue sensitivity from the farthest side from the support
It can also be arranged in the order of layer / GH / RH / GL / RL
The JP-A-56-25738 and 62-
As described in 63936.
Blue-sensitive layer / GL / RL / GH / RH from the farthest side
It is also possible to install in this order. Also described in Japanese Examined Patent Publication No. 49-15495.
As the upper layer, the most sensitive silver halide emulsion
Silver halide emulsions with lower photosensitivity for layers and middle layers
Silver halide milk whose layer and lower layer have lower photosensitivity than the middle layer
The agent layer is arranged, and the photosensitivity is gradually lowered toward the support.
An array composed of three layers with different photosensitivity
The When composed of three layers with different sensitivities
However, it is described in JP-A-59-202464.
In the same color-sensitive layer, from the side away from the support
Arrange in order of medium sensitivity emulsion layer / high sensitivity emulsion layer / low sensitivity emulsion layer
May be. In addition, high sensitivity emulsion layer / low sensitivity emulsion layer / medium
Sensitive emulsion layer or low sensitivity emulsion layer / medium sensitivity emulsion layer / high
They may be arranged in the order of the sensitivity emulsion layer. The layer using the emulsion of the present invention is a low-sensitivity emulsion.
Any of a layer, a medium sensitivity emulsion layer and a high sensitivity emulsion layer may be used. Book
The layer using the emulsion of the invention may be any color sensitive layer.
Yes. In addition, the emulsion of the present invention is divided into a plurality of layers having different sensitivities.
May be included, or may be included in multiple color sensitive layers
Yes. Silver halide emulsion without epitaxial junction
As JP-A-11-174606, 11-29
Dislocation lines are contained in the fringe part described in 5832
Tabular grain emulsions are preferably used. With this usage
While improving the performance of photosensitive materials, it reduces the amount of silver applied
It is possible to Emulsion silver used in each emulsion layer
(Mass in silver atoms) is preferably 0.3 to 3 g
/ M²And more preferably 0.5 to 2 g / m²In
The In the case of four or more layers, the arrangement is changed as described above.
It's okay. As described above, the purpose of each photosensitive material
Various layer configurations and arrangements can be selected according to the above. The photosensitive material according to the present invention includes the above-mentioned various types.
Other additives, but other than these,
Various additives can be used. These additives are more specifically researched.
Disclosure Item 17643 (1978)
December), Item 18716 (1979 1
January) and Item 308119 (1989)
December), and the corresponding locations are listed in the table below.
Shown together. [0107]     Additive type RD17643 RD18716 RD308119    1 Chemical sensitizer page 23 page 648 right column page 996    2 Sensitivity increasing agent Same as above    3 Spectral sensitizer, pages 23 to 24, page 648, right column to 996, right to 998, right       Supersensitizer 649, right column on page 649    4 Brightener 24 pages 647 right column 998 right    5 Antifoggant, 24-25 pages 649, right column 998 right-1000 right       And stabilizer    6 Light absorber, pages 25-26, page 649, right column-1003 left-1003 right       Filter dye, page 650, left column       UV absorber    7 Stain inhibitor Page 25 Right column 650 Left to right column 1002 Right    8 Dye image stabilizer 25 page 1002 right    9 Hardener page 26 page 651 left column 1004 right to 1005 left   10 Binder page 26 Same as above 1003 right to 1004 right   11 Plasticizer, Lubricant 27 pages 650 right column 1006 left to 1006 right   12 Application aid, pages 26-27 Same as above 1005 left-1006 left       Surfactant   13 Static 27 pages Same as above 1006 Right to 1007 Left       Anti-blocking agent   14 Matting agent 1008 left to 1009 left Also, photographic properties with formaldehyde gas
In order to prevent degradation of performance, U.S. Pat. No. 4,411,98
Formua described in No. 7 and No. 4,435,503
A compound that reacts with aldehyde to be immobilized can be used as a photosensitive material.
It is preferable to add. In the present invention, various color couplers are used.
An example of this can be found in the previous research disc.
Roger No. 17643, VII-C to G, and N
o. 307105, described in patents described in VII-CG
Has been. As the yellow coupler, for example,
Allowed 3,933,501, 4,022,620
No. 4,324,024 No. 4,401,75
No. 2, No. 4,248,961, JP-B 58-107
No. 39, British Patent No. 1,425,020, No. 1,4
76,760, US Pat. No. 3,973,968, the same
No. 4,314,023, No. 4,511,649,
Preferred are those described in European Patent No. 249,473A, etc.
That's right. As a magenta coupler, 5-pyrazolone
And pyrazoloazole-based compounds are preferred.
Allowed 4,310,619, 4,351,897
No., European Patent No. 73,636, US Patent No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (1984, 6
Moon), JP-A-60-33552, Research Disc
Roger No. 24230 (June 1984), JP
60-43659, 61-72238, 60-
35730, 55-118034, 60-18
No. 5951, US Pat. No. 4,500,630, No.
No. 4,540,654, No. 4,556,630, country
Particularly preferred are those described in International Publication WO88 / 04795.
That's right. Examples of cyan couplers include phenolic and cyan couplers.
Naphthol couplers, US Pat. No. 4,0
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No.
2,369,929, 2,801,171,
Nos. 2,772,162, 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent
121,365A, 249,453A, US
Patents 3,446,622 and 4,333,999
Nos. 4,775,616, 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212, 4,296,
No. 199, JP-A 61-42658, etc.
preferable. Typical of polymerized dye-forming couplers
Examples are U.S. Pat. Nos. 3,451,820 and 4,084.
No. 0, 211, No. 4,367, 282, No. 4, 4
09,320, 4,576,910, British patent
No. 2,102,137, European Patent No. 341,188A
In the issue. Couplers in which coloring dyes have appropriate diffusibility
US Patent 4,366,237, British Patent
No. 2,125,570, European Patent No. 96,570,
Those described in West German Patent (Public) No. 3,234,533
Is preferred. Color for correcting unwanted absorption of coloring dyes
Coupler is a Research Disclosure No.
No. 17643, VII-G, No. 307105 VII-G
, U.S. Pat. No. 4,163,670, JP-B 57-3
No. 9413, US Pat. No. 4,004,929, No.
No. 4,138,258, British Patent No. 1,16,368
The thing described in is preferable. U.S. Pat.
Fluorescence emitted during coupling described in No. 4,181
Couplers that correct unnecessary absorption of coloring dyes with dyes,
The developing agent described in US Pat. No. 4,777,120
A dye precursor group capable of forming a dye in response to a leaving group
It is also preferable to use a coupler having Photographically useful residues associated with coupling
Compounds that release can also be preferably used in the present invention.
The DIR coupler that releases the development inhibitor is the RD1 described above.
7643, VII-F and No. 307105, VII −
Patents described in Section F, JP-A-57-151944,
57-154234, 60-184248,
63-37346, 63-37350, US Patent
Nos. 4,248,962 and 4,782,012
Those described are preferred. Nucleating agent or development acceleration in the form of an image during development
As a coupler for releasing the agent, British Patent No. 2,09
7,140, 2,131,188, JP 59
-157638, 59-170840
Is preferred. JP-A-60-107029, the same as above.
60-252340, JP-A-1-44940, 1
-Redox with an oxidized form of the developing agent described in No. -45687
Depending on the reaction, fogging agent, development accelerator, silver halide dissolved
Also preferred are compounds that release agents and the like. In addition, it can be used for the light-sensitive material of the present invention.
Possible compounds include US Pat. No. 4,130,427.
Competitive couplers described in US Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
Multi-equivalent couplers described in No. 618, etc., JP-A-60-18
DI described in No. 5950, JP-A No. 62-24252, etc.
R redox compound release coupler, DIR coupler release
Coupler, DIR coupler release redox compound
Is a DIR redox release redox compound, European Patent No.
173,302A and 313,308A
A coupler that releases a dye that recovers color after release, RD. No. 1
1449, 24241, JP-A-61-2012247
Bleach accelerator releasing couplers described in US Pat.
Patent application title: Ligand-releasing coupler described in Japanese Patent No. 55,477
A leuco dye releasing agent described in JP-A-63-75747
Fluor, described in US Pat. No. 4,774,181
Examples include couplers that release a dye. There are various known couplers used in the present invention.
It can be introduced into the light-sensitive material by the dispersion method. Oil-in-water dispersion
Examples of high boiling solvents used in the process are, for example, U.S. Pat.
No. 2,322,027. Boiling point at normal pressure used in oil-in-water dispersion method
Specific examples of high-boiling organic solvents having a boiling point of 175 ° C. or higher include
Talates (eg, dibutyl phthalate, disi
Chlohexyl phthalate, di-2-ethylhexyl phthalate
Rate, decyl phthalate, bis (2,4-di-ter
t-Amylphenyl) phthalate, bis (2,4-di-)
tert-amylphenyl) isophthalate, bis
(1,1-diethylpropyl) phthalate); phosphoric acid or
Or esters of phosphonic acid (e.g.
Sulfate, tricresyl phosphate, 2-ethyl
Xyldiphenyl phosphate, tricyclohexyl phosphate
Sulfate, tri-2-ethylhexyl phosphate,
Tridodecyl phosphate, tributoxyethyl phosphate
, Trichloropropyl phosphate, di-2-e
Tilhexyl phenylphosphonate); benzoic acid ester
(E.g. 2-ethylhexyl benzoate, dode
Silbenzoate, 2-ethylhexyl-p-hydroxy
Cybenates); amides (eg, N, N-die)
Ludodecanamide, N, N-diethyllaurylamide,
N-tetradecylpyrrolidone); alcohols or alcohols
Enols (eg, isostearyl alcohol, 2,
4-di-tert-amylphenol); aliphatic carbo
Acid esters (eg, bis (2-ethylhexyl)
Sebacate, dioctyl azelate, glycerol tri
Butyrate, isostearyl lactate, trioctyl
Citrate); aniline derivatives such as N, N-dibu
Til-2-butoxy-5-tert-octylanily
Hydrocarbons (eg paraffin, dodecylben)
Zen, diisopropylnaphthalene)
Yes. As the auxiliary solvent, for example, the boiling point is about 30 ° C.
Above, preferably above 50 ° C and below about 160 ° C organic
Solvents can be used, and typical examples include, for example, ethyl acetate.
Butyl acetate, ethyl propionate, methyl ethyl ketone
T, cyclohexanone, 2-ethoxyethyl acetate
And dimethylformamide. Latex dispersion process steps, effects and impregnation
Specific examples of latexes for use are, for example, U.S. Pat. No. 4,19.
9,363, West German Patent Application (OLS) No. 2,541
274 and 2,541,230.
ing. In the color light-sensitive material of the present invention, phenethyl is used.
Alcohol, JP-A 63-257747, 62-
Described in No. 272248 and JP-A-1-80941
Of, for example, 1,2-benzisothiazoline-3-
N-butyl-p-hydroxybenzoate, phenol
4-chloro-3,5-dimethylphenol, 2-
Phenoxyethanol, 2- (4-thiazolyl) benzo
Add various preservatives or antifungal agents such as imidazole
It is preferable to add. The present invention can be applied to various photosensitive materials.
However, it is preferable to apply to various color photosensitive materials.
That's right. For example, color negatives for general use or movies
Color reversal fill for rum, slide or TV
Color paper, color positive film and color
A reversal paper can be cited as a representative example. Main departure
Akira is especially preferred for color duplication films
it can. Suitable supports that can be used in the present invention are, for example,
RD. No. 17643, page 28, ibid.
18716, page 647, right column to page 648, left column, and
No. 307105, page 879. The light-sensitive material of the present invention has an emulsion layer side.
The total thickness of all hydrophilic colloid layers is 28 μm or less
Is preferably 23 μm or less, more preferably 18 μm.
m or less is more preferable, and 16 μm or less is particularly preferable.
In addition, membrane swelling speed T_1/2Is preferably 30 seconds or less, 20 seconds
The following is more preferable. The film thickness here is 25 ° C relative humidity
It means the film thickness measured under 55% humidity control (2 days). Ma
Membrane swelling speed T_1/2Is a hand known in the art.
For example, A Green
(A. Green) et al.
Ens and Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129
Use a spherometer of the type described in
Can be measured. T_1/2Is a color developer 30
9 of the maximum swollen film thickness reached when treated at 3 ° C for 3 minutes and 15 seconds
0% is assumed to be a saturated film thickness, until it reaches 1/2 of the saturated film thickness
Is defined as the time. Film swelling speed T_1/2As a binder
Add hardener to gelatin or time after coating
It can be adjusted by changing the conditions. The light-sensitive material of the present invention has an emulsion layer side.
On the opposite side, hydrophilicity with a total dry film thickness of 2 μm to 20 μm
It is preferable to provide a colloid layer (called back layer)
Yes. The back layer includes, for example, the above-described light absorber and fibre.
Luther dye, UV absorber, antistatic agent, dura
Agent, binder, plasticizer, lubricant, coating aid, surface activity
It is preferable to contain an agent. Swell rate of this back layer
Is preferably 150 to 500%. The color photographic light-sensitive material according to the present invention is
RD. No. 17643, pp. 28-29, ibid.
No. 18716, page 651, left column to right column; 30
7105, pages 880-881 in the usual manner
Therefore, it can be developed. Coloring used in the development processing of the light-sensitive material of the present invention
The developer is preferably an aromatic primary amine color developer
It is an alkaline aqueous solution mainly composed of a medicine. This color development
Aminophenol compounds are also useful as image agents.
However, p-phenylenediamine compounds are preferably used.
As a typical example, 3-methyl-4-amino-
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl
Tyl-4-amino-N-ethyl-N-β-methanesulfo
N-amidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, and these
Sulfate, hydrochloride or p-toluenesulfonate
Is mentioned. Among these, in particular, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylanily
Sulfate is preferred. These compounds can be used depending on the purpose.
More than one species can be used in combination. The color developer is, for example, an alkali metal charcoal.
PH buffering agents such as acid salts, borates or phosphates,
Chloride salt, bromide salt, iodide salt, benzimidazole
Benzothiazoles or mercapto compounds
Such development inhibitors or antifogging agents are generally included.
is there. If necessary, hydroxylamine, diethyl
Hydroxylamine, sulfite, N, N-biscarbo
Hydrazines such as xylmethylhydrazine, phenyl
Micarbazides, triethanolamine, catechols
Various preservatives such as sulfonic acids; ethylene glycol, di
Organic solvents such as ethylene glycol; benzyl alcohol
, Polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines; dye-forming couplers, competition
Couplers such as 1-phenyl-3-pyrazolidone
Auxiliary developing agent; Viscosifier; Aminopolycarboxylic acid, amino
Nopolyphosphonic acid, alkylphosphonic acid, phosphonocar
Use various chelating agents as represented by boric acid
Can do. Examples of chelating agents include ethylene dia
Mine tetraacetic acid, nitrile triacetic acid, diethylenetriamine five
Acetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyl
Louisinodiacetic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, nitrilo-N, N, N-trimethylene
Sphonic acid, ethylenediamine-N, N, N, N-tetra
Methylenephosphonic acid, ethylenediamine-di (o-hydride)
Roxyphenylacetic acid) and their salts are typical examples.
I can make it. In addition, when performing the inversion process, normally black
Color development is performed after white development. In this black and white developer
For example, dihydroxybens such as hydroquinone
Zens such as 1-phenyl-3-pyrazolidone
Such as 3-pyrazolidones or, for example, N-methyl-
Publicity of aminophenols such as p-aminophenol
Use known black and white developing agents alone or in combination
be able to. P of these color developers and black-and-white developers
H is generally 9-12. Also this
The replenishment amount of these developers is the color photographic material to be processed.
Generally, 3L or more per square meter of photosensitive material
The bromide ion concentration in the replenisher is reduced.
50 milliliters (hereinafter referred to as milliliters)
Also expressed as “mL”. ) You can also: Supplement
When reducing the amount of charge, the contact area of the treatment liquid with air should be
Prevents liquid evaporation and air oxidation by reducing the size.
It is preferable. Area of contact between photographic processing solution and air in processing tank
Can be expressed by the aperture ratio defined below. Immediately
The Opening ratio = [contact area between treatment liquid and air (cm²)] ÷ [Process
Capacity of scientific liquid (cm^Three]] The opening ratio is preferably 0.1 or less.
More preferably, it is 0.001-0.05.
As a method of reducing the aperture ratio in this way,
For example, a shield such as a floating lid is provided on the photographic processing liquid surface.
In addition to the method described above, the method described in JP-A-1-82033 is acceptable.
A method using a moving lid, described in JP-A-62-216050
And a slit developing method. Open
Reducing the ratio is the work of both color development and black-and-white development.
As well as subsequent processes such as bleaching and bleaching.
Applicable in all processes of wearing, fixing, washing and stabilization
It is preferable. Also, accumulation of bromide ions in the developer
Reducing the replenishment amount by using means to suppress
You can also. The color development processing time is usually between 2 and 5 minutes.
Set at high temperature, high pH, and high color developing agent
By using it for concentration, the processing time is further shortened.
You can also The photographic emulsion layer after color development is usually bleached.
It is. The bleaching process may be performed simultaneously with the fixing process.
(Bleaching and fixing treatment) may be performed individually. Further processing
In order to speed up the process, a bleach-fix process is performed after the bleach process.
It may be a rational method. In addition, two continuous bleach-fixing baths
Processing, fixing processing before bleach-fixing processing,
Depending on the purpose, it is also possible to perform bleaching after bleach-fixing.
Can be implemented arbitrarily. As a bleaching agent, for example, iron (III)
Polyvalent metal compounds such as peracids (especially sodium persulfate
Is suitable for color negative films for movies), quinones,
Toro compounds are used. Typical bleaching agents include iron (I
II) organic complex salts such as ethylenediaminetetraacetic acid, di
Ethylenetriaminepentaacetic acid, cyclohexanediamine-4
Acetic acid, methyliminodiacetic acid, 1,3-diaminopropane
Such as tetraacetic acid, glycol ether diamine tetraacetic acid
Complex salts with minopolycarboxylic acids or, for example,
Complex salts with acid, tartaric acid, malic acid can be used
The Of these, ethylenediaminetetraacetic acid iron (III) complex
Salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt
Aminopolycarboxylic acid iron (III) complex salts including
It is preferable from the viewpoint of rapid processing and prevention of environmental pollution. further,
Aminopolycarboxylic acid iron (III) complex salt
Are also particularly useful in bleach-fixing solutions. These a
Bleaching solution or drift using iron (III) complex salt of minopolycarboxylate
The pH of the white fixer is usually from 4.0 to 8, but the processing is quick
It can also be processed at a lower pH for conversion. In bleaching solutions, bleach-fixing solutions and their pre-baths
If necessary, a bleaching accelerator can be used.
Specific examples of useful bleach accelerators are described in the following specification:
For example: US Pat. No. 3,893,858, West Germany
Patent Nos. 1,290,812 and 2,059,988
, JP-A-53-32736, 53-57831
No., 53-37418, 53-72623,
53-95630, 53-95311, 53-
104232, 53-124424, 53-1.
41623, 53-18426, Research D
Closure No. No. 17129 (July 1978)
Having a mercapto group or disulfide group as described in
Compound: thiazolid described in JP-A No. 51-140129
Derivatives: Japanese Examined Patent Publication No. 45-8506, Japanese Unexamined Patent Publication No. 52-20
No. 832, No. 53-32735, US Pat. No. 3,70
A thiourea derivative described in US Pat. No. 6,561, West German Patent 1,
127,715, described in JP-A-58-16235
Iodide salt; West German Patent No. 966,410, No. 2,74
Polyoxyethylene compounds described in No. 8,430;
A polyamine compound described in JP-A-45-8836;
Other JP-A-49-40943, 49-59644,
53-94927, 54-35727, 55
-26506 and 58-163940
Bromide ions can be used. Among them, mercap
A compound having a thio group or a disulfide group has an accelerating effect
Preferred from a large standpoint, especially US Pat. No. 3,893,8
58, West German Patent 1,290,812, JP 53
The compound described in -95630 is preferable. In addition, the United States
The compounds described in Japanese Patent No. 4,552,884 are also preferred.
Yes. These bleach accelerators may be added to the light-sensitive material. Shoot
When bleach-fixing color light-sensitive materials for shadows, these
Bleach accelerators are particularly effective. In the bleaching solution and bleach-fixing solution, in addition to the above compounds
To contain organic acid for the purpose of preventing bleach stain
It is preferable. Particularly preferred organic acids are acid dissociation constants.
A compound having (pKa) of 2 to 5, specifically,
For example, acetic acid, propionic acid, hydroxyacetic acid
Can do. Fixing agents used for fixing solutions and bleach-fixing solutions;
For example, thiosulfate, thiocyanate, thioe
List of ether compounds, thioureas, and large amounts of iodide salts
be able to. Of these, the use of thiosulfate is common
In particular, ammonium thiosulfate is the most widely used
Yes. Also, thiosulfate and, for example, thiocyanate,
A combined use of a thioether compound and thiourea is also preferred. Constant
Preservatives for landing and bleach-fixing solutions include sulfites and bisulfites.
Acid salt, carbonyl bisulfite adduct or European Patent No. 2
94,769A is preferred sulfinic acid compound
Yes. In addition, fixing solutions and bleach-fixing solutions have the purpose of stabilizing the solutions.
Of various aminopolycarboxylic acids and organic phosphonic acids
Addition is preferred. In the present invention, a fixing solution or a bleach-fixing solution.
Has a pKa of 6.0 to 9.0 for pH adjustment.
Products, preferably imidazole, 1-methylimidazole
1-ethylimidazole, 2-methylimidazole
0.1-10 mol / L of imidazole such as
It is preferable. The total time of the desilvering process is the result of desilvering failure.
It is preferable that the length is as short as possible. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Also processing temperature
Is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferred temperature range, the desilvering rate is improved and
Stain generation after treatment is effectively prevented. In the desilvering process, stirring is as strong as possible.
It is preferable that Specific method of strengthening stirring
As a photosensitive material described in JP-A-62-183460.
A method in which a jet of processing liquid collides with the emulsion surface
Use the rotating means in No. 62-183461 to increase the stirring effect
The method to get off is mentioned. Furthermore, a wire provided in the liquid
Move photosensitive material while contacting par blade and emulsion surface
And more stirring effect by making the emulsion surface turbulent
Increase the circulation flow rate of the entire processing solution
Method. Such a stirring improving means is bleaching
Effective in any of solution, bleach-fixing solution and fixing solution
The Stirring is improved by bleaching agent and fixing agent in emulsion film.
To speed up the supply of silver and consequently increase the desilvering speed
It is done. Also, the above stirring improvement means uses a bleach accelerator.
It is more effective when the
Or to eliminate fixing problems with bleach accelerators
Can do. Automatic used for development of the light-sensitive material of the present invention
Developing machines are disclosed in JP-A-60-191257 and 60-19.
Photosensitive materials described in Nos. 1258 and 60-191259
It is preferable to have a conveying means. The above-mentioned JP-A-6
Such a carrier as described in 0-191257
The stage significantly reduces the amount of processing solution brought from the pre-bath to the post-bath.
Therefore, the effect of preventing the performance deterioration of the processing liquid is high. like this
The main effects are shortening of processing time and replenishment of processing solution in each process
This is particularly effective for reducing the amount. The silver halide color photographic light-sensitive material of the present invention
After desilvering, it is recommended to go through water washing and / or stabilization process.
It is common. The amount of water washed in the washing process is a characteristic of the photosensitive material.
(For example, depending on the material used such as coupler), application,
Furthermore, for example, the washing water temperature, the number of washing tanks (number of stages),
Depending on replenishment methods such as counterflow and forward flow, and other various conditions
Can be set widely. Of these, the multistage countercurrent method
The relationship between the number of washing tanks and the amount of water is Journal of
  the Society of Motion Pi
cute and Television Engi
neers vol. 64, p. 248-253 (1955
In May). [0144] According to the multistage countercurrent system described in the above document,
Although the amount of washing water can be greatly reduced, the water in the tank
Increased residence time causes bacteria to propagate and
There arises a problem that the play material adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, such a problem.
As a solution to the problem, described in JP-A-62-288838
Reduces calcium and magnesium ions
The method can be used very effectively. In addition,
For example, isothiazolonation described in No. 57-8542
Compounds, siabendazoles, chlorinated isocyanuric acid
Chlorine disinfectants such as sodium, etc.
Horiguchi Hiroshi “Non-Triazole”
Science (1986) Sankyo Publishing, Hygienic Technology Society
Sterilization, sterilization and fouling technology "(1982) Japan Industrial Technology Association, Japan
This edition of the Society for Antibacterial and Antifungal Studies, “Encyclopedia of Antibacterial and Antifungal Agents” (1986)
The described fungicides can also be used. P of washing water in the processing of the light-sensitive material of the present invention
H is 4-9, preferably 5-8. Washing water temperature and
Depending on the characteristics and application of the photosensitive material,
Generally, it can be set, but in general, it is 20 seconds to 1 at 15 to 45 ° C.
0 minutes, preferably 25-40 ° C for 30 seconds to 5 minutes
Selected. Further, the light-sensitive material of the present invention can be used in place of the above water washing.
Alternatively, it can be treated directly with a stabilizing solution. this
In such stabilization treatment, JP-A-57-8543
No. 58-14834, 60-220345
All known methods described can be used. Furthermore, following the water washing treatment, further stabilization
Sometimes it is processed. An example of this is color photography for photography.
Dye stabilizers and surface activity used as the final bath of materials
Mention may be made of a stabilizing bath containing a sexing agent. Dye stability
Examples of the agent include formalin and glutaraldehyde.
Aldehydes, N-methylol compounds, hex
Samethylenetetramine or aldehyde sulfite addition
You can list things. In this stable bath,
Toning agents and fungicides can be added. The above-mentioned washing and / or replenishment of stabilizing solution
-The bar flow solution can be reused in other processes such as the desilvering process.
It can also be used. For example, processing using an automatic processor
In the case where each of the above processing liquids is concentrated by evaporation
It is preferable to correct the concentration by adding water. The silver halide color photographic light-sensitive material of the present invention
In order to simplify and speed up processing,
It may be built in. To incorporate, color developing agent
It is preferable to use various precursors. For example, rice
Indoaniline system described in Japanese Patent No. 3,342,597
Compound, for example, 3,342,599, Research
・ Disclosure No. 14,850 and No.
No. 15,159, Schiff base type compounds, 1
Aldol compounds described in US Pat. No. 3,924, US Pat.
719,492, a metal salt complex described in JP-A-53-1
Examples include urethane compounds described in No. 35628
it can. The silver halide color light-sensitive material of the present invention is
If necessary, various types of 1-
Phenyl-3-pyrazolidones may be incorporated. Typical
Examples of such compounds are disclosed in, for example, JP-A-56-64339.
57-144547 and 58-115438
It is described in. The various processing solutions in the present invention are 10 ° C. to 5 ° C.
Used at 0 ° C. Usually a temperature between 33 ° C and 38 ° C
Is standard, but at higher temperatures, the process is accelerated and processed.
To improve the image quality and process
An improvement in the stability of the liquid can be achieved. The silver halide photosensitive material of the present invention is
U.S. Pat. No. 4,500,626, JP-A-60-133
449, 59-218443, 61-2380
56, European Patent No. 210,660A2, etc.
The present invention can also be applied to photothermographic materials. Further, the silver halide color photographic feeling of the present invention is used.
The optical materials are Japanese Patent Publication No. 2-32615 and Japanese Utility Model Publication 3-397.
Film unit with lens described in No. 84 etc.
When applied to the
The [0153] Examples of the present invention will be described below. However, this implementation
It is not limited to examples. [0154] (Example 1) (Preparation of emulsion) (Host tabular emulsion A) 1.0 g of KBr, ordinary alk
Water containing 4.5g of reprocessed gelatin (average molecular weight 100,000)
1200 mL of the solution was kept at 35 ° C. and stirred (1st solution
Preparation). Ag-1 aqueous solution (AgNO in 100 mL_ThreeThe
37 mL containing 1.7 g) and X-1 aqueous solution (100
Double 37 mL) (containing 5.3 g of KBr in mL)
Added by jet method over 20 seconds at constant flow rate
(Addition 1). Add an aqueous solution containing 6.6 g of KBr and warm
The temperature is raised to 75 ° C. and after a aging process of 12 minutes, G-
1 aqueous solution (containing 20 g of the above gelatin in 100 mL)
135 ml) was added. Next, an aqueous solution Ag-2 (A in 100 mL)
gNO_Three20.8g) and X-2
Aqueous solution (containing 14.6 g of KBr in 100 mL)
131) Accelerate the flow rate of 131 mL by the double jet method.
For 32 minutes (addition 2). Subsequently, an aqueous solution Ag-3 (in 100 mL)
AgNO_Three533 mL) and X-3 water
Solution (containing 22.4 g of KBr in 100 mL)
45 minutes while accelerating flow rate with double jet method
Added. At this time, X-3 aqueous solution is added in the reaction vessel.
The silver potential of the bulk emulsion solution of 0 mV (saturated calomel
(Addition 3). Next, the temperature was lowered to 40 ° C., and an Ag-4 aqueous solution
(AgNO in 100 mL_ThreeContaining 32 g) 112
mL and X-4 aqueous solution (19. KBr in 100 mL.
7g and 3.8g KI))
At a constant flow rate over 6 minutes. At this time, X
-4 Aqueous solution is added to the bulk emulsion solution in the reaction vessel.
To maintain the position at +80 mV (saturated calomel electrode)
(Addition 4). Thereafter, according to a normal flocculation method.
Followed by water, NaOH,
Latin was added, pH 5.8 at 56 ° C., pAg 8.8,
115g of silver equivalent per kg of emulsion, gelatinous
The amount was adjusted to 90 g. The resulting emulsion is a whole grain
The main plane in which 98% or more (particle number ratio) of the children are parallel is (11
1) An emulsion composed of tabular grains of silver iodobromide as a plane,
The average equivalent sphere diameter was 1.2 μm (the following host flats)
The same was true for the plate emulsion). The average equivalent circle equivalent diameter is
2.85 μm, average particle thickness was 0.142 μm
(The same was true for host tabular emulsions B and C). (Host tabular emulsion B) Host tabular emulsion
In A, nucleation was changed as follows, and aging conditions were changed
Adjust (final grain shape matched to host tabular emulsion A)
Except for the above, it was prepared in the same manner as the host tabular emulsion A. In (1st liquid preparation), 0.3 g of KBr 1.0 g
To an alkali-treated gelatin with an average molecular weight of 100,000
Changed to 15,000 alkali-treated gelatin, temperature 35
Instead of 0 ° C., it was kept at 30 ° C. (Host tabular emulsion C) Host tabular emulsion
In A, nucleation was changed as follows, and aging conditions were changed
Adjust (final grain shape matched to host tabular emulsion A)
Except for the above, it was prepared in the same manner as the host tabular emulsion A. (1st
Liquid preparation), KBr 1.0g was changed to 0.3g
And an alkali-treated gelatin having an average molecular weight of 100,000
5,000 oxidized gelatin (acidified methionine with hydrogen peroxide
To gelatin with an average molecular weight of 15,000)
The temperature was kept at 30 ° C instead of 35 ° C. (Host tabular emulsion D) Host tabular emulsion
A is the same as host tabular emulsion A except for the following changes.
Prepared. In (Addition 3), the silver potential is kept at 0 mV.
Instead, the addition was made at -40 mV. Obtained
Average equivalent circle diameter of particles is 3.15 μm, average particle thickness
Was 0.116 μm (host tabular emulsions E and F were also
The same). (Host tabular emulsion E) Host tabular emulsion
In D, change the nucleation as follows and change the aging conditions
Adjust (final grain shape matched to host tabular emulsion D)
Except for the above, it was prepared in the same manner as host tabular emulsion D. (1st
Liquid preparation), KBr 1.0g was changed to 0.3g
And an alkali-treated gelatin having an average molecular weight of 100,000
Change it to 5,000 alkali-treated gelatin and replace it with 35 ℃
Instead, it was kept at 30 ° C. (Host tabular emulsion F) Host tabular emulsion
In D, change the nucleation as follows and change the aging conditions
Adjust (final grain shape matched to host tabular emulsion D)
Except for the above, it was prepared in the same manner as the host tabular emulsion D. (1st
Liquid preparation), KBr 1.0g was changed to 0.3g
And an alkali-treated gelatin having an average molecular weight of 100,000
5,000 oxidized gelatin (acidified methionine with hydrogen peroxide
To gelatin with an average molecular weight of 15,000)
The temperature was kept at 30 ° C instead of 35 ° C. (Host tabular emulsion G) Host tabular emulsion
D is the same as host tabular emulsion D except for the following changes.
Prepared. Contains 20 g of normal alkali-treated gelatin
Instead of adding the aqueous solution G-1,
An aqueous solution containing 30 g of hatched gelatin was added.
The average equivalent circle diameter of the obtained particles was 3.43 μm, flat
The average grain thickness was 0.098 μm (host tabular emulsion)
The same applies to H and I). (Host tabular emulsion H) Host tabular emulsion
In G, nucleation was changed as follows, and aging conditions were changed
Adjust (Final grain shape matched to host tabular emulsion G)
Except for the above, it was prepared in the same manner as the host tabular emulsion G. (1st
Liquid preparation), KBr 1.0g was changed to 0.3g
And an alkali-treated gelatin having an average molecular weight of 100,000
Change it to 5,000 alkali-treated gelatin and replace it with 35 ℃
Instead, it was kept at 30 ° C. (Host tabular emulsion I) Host tabular emulsion
In G, nucleation was changed as follows, and aging conditions were changed
Adjust (Final grain shape matched to host tabular emulsion G)
Except for the above, it was prepared in the same manner as the host tabular emulsion G. (1st
Liquid preparation), KBr 1.0g was changed to 0.3g
And an alkali-treated gelatin having an average molecular weight of 100,000
5,000 oxidized gelatin (acidified methionine with hydrogen peroxide
To gelatin with an average molecular weight of 15,000)
The temperature was kept at 30 ° C instead of 35 ° C. (Host tabular emulsion J) Host tabular emulsion
G is the same as the host tabular emulsion G except for the following changes.
Prepared. In (Addition 3), an Ag-3 aqueous solution and X
-3 Instead of adding an aqueous solution by the double jet method,
g-3 'aqueous solution (AgNO in 100 mL)_ThreeContains 16g
1066 mL and X-3 'aqueous solution (in 100 mL)
11.5 g of KBr and methionine oxidized with hydrogen peroxide
Contains 20 g of gelatin having an average molecular weight of 15,000
1015 mL of magnetism described in JP-A-10-43570
A main body reaction vessel having a gas coupling induction stirrer;
Are mixed in a separate chamber and the ultra-fine silver bromide particles are mixed together.
Prepared and added continuously to the reaction vessel of the main body. this
When adding silver iodobromide ultrafine particles, the bulk of the reaction vessel
Keep silver potential of emulsion solution at 0 mV (saturated calomel electrode)
Went so. The average equivalent circle equivalent diameter of the obtained particles is
3.67 μm, average particle thickness was 0.085 μm
(The same was true for host tabular emulsions K and L). (Host tabular emulsion K) Host tabular emulsion
In J, nucleation was changed as follows, and aging conditions were changed
Adjust (final grain shape matched to host tabular emulsion J)
Except for the above, it was prepared in the same manner as the host tabular emulsion J. (1st
Liquid preparation), KBr 1.0g was changed to 0.3g
And an alkali-treated gelatin having an average molecular weight of 100,000
Change it to 5,000 alkali-treated gelatin and replace it with 35 ℃
Instead, it was kept at 30 ° C. (Host tabular emulsion L) Host tabular emulsion
In J, nucleation was changed as follows, and aging conditions were changed
Adjust (final grain shape matched to host tabular emulsion J)
Except for the above, it was prepared in the same manner as the host tabular emulsion J. (1st
Liquid preparation), KBr 1.0g was changed to 0.3g
And an alkali-treated gelatin having an average molecular weight of 100,000
5,000 oxidized gelatin (acidified methionine with hydrogen peroxide
To gelatin with an average molecular weight of 15,000)
The temperature was kept at 30 ° C instead of 35 ° C. (Epitaxial Sensitized Emulsion 1-A)
1000 g of strike plate emulsion A was dissolved at 50 ° C.
In this way, an epitaxial junction was formed. First, fe
Noxyethanol to host tabular grains 5.0 × 10^-2
mol / molAg (The same applies to the silver mole of the host tabular grain.
Added), then KI is 1.0 × 10^-3
Add an aqueous solution containing mol / molAg, and
Sensitizing dye 1, 2, 3 (gelatin dispersion)
An amount corresponding to 90% of the saturated adsorption amount was added. More
1.5 kg of potassium hexacyanoruthenium (II)
× 10^-Five An aqueous solution containing mol / mol Ag was added. Then Na
Cl 1.2 × 10^-2 After adding an aqueous solution containing mol / mol Ag, Ag
NO_Three4.8 × 10^-3 An aqueous solution containing mol / mol Ag was added. The
In addition, AgNO_Three3.2 × 10^-3 Aqueous solution containing mol / mol Ag and K
An aqueous solution containing Br and KI at a molar ratio of 52:48
Added in a wet bed. At this time, the silver potential of the emulsion solution is 80 m.
V (saturated calomel electrode). Finally shown in chemical formula 4 below
6.3 × 10^-Five Only mol / mol Ag was added. [0171] [Chemical 1] [0172] [Chemical 2] [0173] [Chemical Formula 3] [0174] [Formula 4] At 50 ° C., the silver potential was changed to saturated calomel
It adjusted to 80 mV with respect to the pole. Then thiocyanic acid
Potassium, chloroauric acid, sodium thiosulfate and N, N
-Dimethylselenourea is added sequentially for optimal chemical sensitization.
Then, add the water-soluble mercapto compound shown in Chemical Formula 5 below
This terminated the chemical sensitization. Optimal chemical sensitization
Means that the sensitivity is highest at 1/100 second exposure.
The [0176] [Chemical formula 5] (Epitaxial sensitized emulsion 1-B)
Except for the following changes in Pitaxial Sensitized Emulsion 1-A
Prepared in the same manner as Emulsion 1-A. D limited to the particle apex
KI is set to 1.0 × 10 for multi-point formation of the pitch junction.
^-3 2.0 × 10 instead of mol / molAg^-3 Water solution containing mol / mol Ag
As the liquid is added, the sensitizing dye
Instead of 90%, add in an amount corresponding to 80%, and
NaCl 1.2 × 10^-2 6.2 × 10 instead of mol / molAg^-2
 Add an aqueous solution containing mol / molAg, and then the first Ag
NO_Three  4.8 × 10^-3 2.4 × 10 instead of mol / molAg^-2 mol /
Add aqueous solution containing molAg and add AgNO for the second time_Three  3.2
× 10^-3 1.6 × 10 instead of mol / molAg^-2 Contains mol / mol Ag
Aqueous solution was added. (Epitaxial sensitized emulsion 1-C)
In addition to the following changes in Pitax Sensitized Emulsion 1-B
Was prepared in the same manner as Emulsion 1-B. Epitaxial junction
Epitaxial formation and chemical sensitization to prevent dissolution
Instead of at 50 ° C, it was at 40 ° C. Epita
In order to prevent dissolution of the axial joint, the compound shown in Chemical formula 4
6.3 × 10^{- Five} Instead of adding only mol / mol Ag,
1.0 × 10^-Four Only mol / mol Ag was added. (Epitaxial Sensitized Emulsion 1-D)
Except for the following changes in Pitaxial Sensitized Emulsion 1-C
Prepared in the same manner as Emulsion 1-C. Host tabular emulsion A
To tabular emulsion B. (Epitaxial sensitized emulsion 1-E)
Except for the following changes in Pitaxial Sensitized Emulsion 1-C
Prepared in the same manner as Emulsion 1-C. Host tabular emulsion A
To tabular emulsion C. (Epitaxial sensitized emulsion 1-F)
Except for the following changes in Pitaxial Sensitized Emulsion 1-A
Prepared in the same manner as Emulsion 1-A. Host tabular emulsion A
To tabular emulsion D. (Epitaxial Sensitized Emulsion 1-G)
Except for the following changes, in Pitaxial sensitized emulsion 1-B
Prepared in the same manner as Emulsion 1-B. Host tabular emulsion A
To tabular emulsion D. (Epitaxial sensitized emulsion 1-H)
Except for the following changes in Pitaxial Sensitized Emulsion 1-C
Prepared in the same manner as Emulsion 1-C. Host tabular emulsion A
To tabular emulsion D. (Epitaxial Sensitized Emulsion 1-I)
Except for the following changes in Pitaxial Sensitized Emulsion 1-D
Prepared in the same manner as Emulsion 1-D. Host tabular emulsion B
To tabular emulsion E. (Epitaxial sensitized emulsion 1-J)
Except for the following changes in Pitaxial Sensitized Emulsion 1-E
Prepared in the same manner as Emulsion 1-E. Host tabular emulsion C
To tabular emulsion F. (Epitaxial sensitized emulsion 1-K)
Except for the following changes in Pitaxial Sensitized Emulsion 1-H
Prepared in the same manner as Emulsion 1-H. Host tabular emulsion D
To tabular emulsion G. (Epitaxial sensitized emulsion 1-L)
Except for the following changes in Pitaxial Sensitized Emulsion 1-K
Prepared in the same manner as Emulsion 1-K. Of epitaxial junctions
Repair the apex of the dissolved host tabular grain before formation
Therefore, before adding phenoxyethanol, AgNO
_ThreeAqueous solution and KBr of 2.0 × 10^-2 An aqueous solution containing mol / mol Ag
Added with double jet. (Epitaxial sensitized emulsion 1-M)
Except for the following changes, in Pitaxial sensitized emulsion 1-L
Prepared in the same manner as Emulsion 1-L. Host tabular emulsion G
To tabular emulsion H. (Epitaxial sensitized emulsion 1-N)
Except for the following changes, in Pitaxial sensitized emulsion 1-L
Prepared in the same manner as Emulsion 1-L. Host tabular emulsion G
To tabular emulsion I. (Epitaxial Sensitized Emulsion 1-O)
Except for the following changes, in Pitaxial sensitized emulsion 1-L
Prepared in the same manner as Emulsion 1-L. Host tabular emulsion G
To tabular emulsion J. (Epitaxial sensitized emulsion 1-P)
Except for the following changes in PITAXIAL SENSITIZED EMULSION 1-O
Prepared in the same manner as Emulsion 1-O. Of epitaxial junctions
Host tabular grain and epitaxial junction itself during formation
Add phenoxyethanol to prevent dissolution
The compound shown in Chemical Formula 6 was converted to 8.0 × 10^-Five Add only mol / molAg
did. [0192] [Chemical 6] (Epitaxial Sensitized Emulsion 1-Q)
Except for the following changes in PITAXIAL sensitized emulsion 1-O
Prepared in the same manner as Emulsion 1-O. Host tabular emulsion J
To tabular emulsion K. (Epitaxial Sensitized Emulsion 1-R)
Except for the following changes in PITAXIAL SENSITIZED EMULSION 1-O
Prepared in the same manner as Emulsion 1-O. Host tabular emulsion J
To tabular emulsion L. Regarding the above emulsions 1-A to 1-R, grains
Shape data, silver halide elements at the top of the host tabular grain
There is at least one pitch junction per particle
Or the ratio of the number of tabular grains to 6 to the total grains (number
Ratio), each of the silver halide epitaxial junctions
However, when viewed from a direction perpendicular to the (111) main plane,
60% or more of the projected area is outside the host tabular grain
The proportion of tabular grains, which are projection-like joints, in the total grains
(Number ratio) less at each epitaxial junction
The proportion of tabular grains having one dislocation line in all grains
(Number ratio), the distance between two parallel twin planes is 0.01
Tabular grains of 2 or 0.008 μm or less occupy all grains
Table 1 below summarizes the ratio (number ratio)
The value of the value is also determined by observing with the method described in the text using an electron microscope.
) [0196] [Table 1](Preparation of coated sample and its evaluation)
Table 2 below shows the cellulose triacetate film support provided.
Under the coating conditions as shown in FIG.
R was applied. [0198] [Table 2] These samples 101 to 118 were mixed at 40 ° C.
The film was cured for 14 hours under the condition of 70% humidity. So
After FUJIFILM Corporation gelatin filter SC-
50 (Long wavelength light transmission with a cutoff wavelength of 500 nm
Filter) and continuous wedge for 1/100 second exposure
The green filter
Measure sensitivity and gradation by measuring density with
went. Negative processor manufactured by Fuji Photo Film Co., Ltd.
Using FP-350, the method described below (cumulative solution compensation)
Process until the charge is 3 times the mother liquor tank capacity)
It was. [0201]   (Processing method)     Process Processing time Processing temperature Replenishment amount   Color development 2 minutes 15 seconds 38 ° C 45 mL   White drift 1 minute 00 seconds 38 ℃ 20mL                                             Bleach solution overflow                                             Full flow into bleach-fixing tank   Bleach fixing 3 minutes 15 seconds 38 ° C 30mL   Flushing (1) 40 seconds From 35 ℃ (2) to (1)                                                 Counterflow piping system   Washing with water (2) 1 min 00 sec 35 ° C 30 mL   Stable 40 seconds 38 ° C 20 mL   Drying 1 min 15 sec 55 ° C     * Replenishment amount is 35mm width per 1.1m length (equivalent to 24Ex.1) Next, the composition of the treatment liquid will be described.   (Color developer) Tank solution (g) Replenisher (g)   Diethylenetriaminepentaacetic acid 1.0 1.1   1-hydroxyethylidene-1,1-diphosphonic acid                                              2.0 2.0   Sodium sulfite 4.0 4.4   Potassium carbonate 30.0 37.0   Potassium bromide 1.4 0.7   Potassium iodide 1.5mg −   Hydroxylamine sulfate 2.4 2.8   4- [N-ethyl-N- (β-hydroxyethyl) amino]     -2-Methylaniline sulfate 4.5 5.5   Add water 1.0L 1.0L   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.10 [0203]   (Bleaching solution) Common for tank solution and replenisher solution (Unit: g)   Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0   Ethylenediaminetetraacetic acid disodium salt 10.0   Ammonium bromide 100.0   Ammonium nitrate 10.0   Bleach accelerator 0.005 mol    (CH_Three)₂N-CH₂-CH₂-S-S-CH₂-CH₂-N (CH_Three)₂・ 2HCl   Ammonia water (27%) 15.0mL   1.0L with water   pH (adjusted with ammonia water and nitric acid) 6.3 [0204]   (Bleaching fixer) Tank solution (g) Replenisher (g)   Ethylenediaminetetraacetic acid ferric ammonium ammonium dihydrate                                             50.0 −   Ethylenediaminetetraacetic acid disodium salt 5.0 2.0   Sodium sulfite 12.0 20.0   Ammonium thiosulfate aqueous solution (700 g / L)                                             240.0 mL 400.0 mL   Ammonia water (27%) 6.0 mL −   Add water 1.0L 1.0L   pH (adjusted with aqueous ammonia and acetic acid) 7.2 7.3 (Washing liquid) Common for tank liquid and replenisher Tap water is converted into an H-type strongly acidic cation exchange resin (Rohm and Ha
Amberlite IR-120B manufactured by Seuss Corporation and OH type
Filled with Nion exchange resin (Amberlite IR-400)
Calcium and Magnesium by passing water through a packed bed column
Treatment of um ion concentration to 3 mg / L or less, followed by dichloride
Sodium isocyanurate 20mg / L and sodium sulfate
0.15 g / L was added. The pH of this solution is 6.5-
It was in the range of 7.5. [0206]   (Stabilizer) Tank fluid and replenisher common (Unit: g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether     (Average polymerization degree 10) 0.2   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazole-1-     Ilmethyl) Piperazine 0.75   Add water and add 1.0 L   pH 8.5 The results of photographic sensitivity and gradation are shown in Table 3 below.
Show. Sensitivity is the fog density of the obtained characteristic curve plus 0.
Relative value of reciprocal of exposure necessary to reach density of 15
(The sensitivity of the sample 101 is 100). [0208] [Table 3] Comparative samples (101 to 107, 111,
115) and the sample of the present invention (108 to 110, 112 to 1)
14, 116-118), the emulsion of the present invention is used.
The sample was highly sensitive and reduced in fog
I understand that. (Example 2) (Preparation of emulsion) (Em-A) 0.96 g of low molecular weight gelatin, KBr,
Keep 1192 mL of an aqueous solution containing 0.9 g at 40 ° C.
Stir vigorously. AgNO_Three, 1.49g containing aqueous solution 3
7.5 mL and 37.5 mL of aqueous solution containing 1.5 g of KBr
Was added over 30 seconds by the double jet method. KBr
After adding 1.2 g, the mixture was heated to 75 ° C. and aged. sufficient
After aging, the amino group was chemically modified with trimellitic acid
30g of trimellitated gelatin with a molecular weight of 100,000
Was added to adjust the pH to 7. Thiourea dioxide 6mg
Was added. AgNO_Three, 29 g of aqueous solution containing 29 g
The final flow rate of L and KBr aqueous solution is initial by double jet method.
The flow rate was accelerated so that the flow rate would be 3 times the flow rate. this
At this time, the silver potential is kept at -20 mV to the saturated calomel electrode.
It was. AgNO_Three, 110.2 g of aqueous solution 440.
Final flow rate of 6mL and KBr aqueous solution by double jet method
Accelerate the flow rate to 5.1 times the initial flow rate for 30 minutes
Was added over time. At the same time, the particle size is 0.037.
A silver iodide content of 1 μm with a silver fine grain emulsion of μm
At the same time, the flow rate is accelerated so that it becomes ol%
The potential was kept at 0 mV with respect to the saturated calomel electrode. Ag
NO_Three, 24.1g in aqueous solution 96.5mL and KBr
The aqueous solution was added over 3 minutes by the double jet method. This
At that time, the silver potential was kept at 0 mV. Ethylthiosulfonic acid
After adding 26 mg of sodium, the temperature was lowered to 55 ° C.
An aqueous KBr solution was added to adjust the silver potential to -90 mV.
Add 8.5g of the above-mentioned AgI fine grain emulsion in terms of KI mass.
Added. Immediately after the addition, AgNO_Three57g included
228 mL of aqueous solution was added over 5 minutes. At this time
KBr aqueous solution so that the potential at the end of heating is +20 mV
Adjusted. After washing with water, add gelatin and p at 40 ° C.
Adjusted to H, 5.8, pAg, 8.7. Compound 1 and
Then, the temperature was raised to 60 ° C. Sensitizing dye 4 and
5 and after addition, potassium thiocyanate, gold chloride
Acid, sodium thiosulfate, N, N-dimethylselenoure
A was added for optimal chemical sensitization. Compound at the end of chemical sensitization
Product 3 and compound 4 were added. Here, optimal chemical increase
Sensitizing dye and silver halide
10 per mole^-1To 10^-8Select from the range of molar addition amount
Means that [0211] [Chemical 7] [0212] [Chemical 8] [0213] [Chemical 9] [0214] Embedded image [0215] Embedded image [0216] Embedded image (Em-B) 35 μmol of meg / g
Thionine-containing phthalation rate of 100,000 and a molecular weight of 9
7% phthalated gelatin 1.02g, KBr 0.97g
Keeping 1192 mL of aqueous solution containing 35 ° C and stirring vigorously
did. AgNO_ThreeSolution containing 4.47 g, 42 mL
And an aqueous solution containing 3.16 g of KBr, 42 mL
It was added over 9 seconds by the jet method. Add 2.6g of KBr
After the addition, the temperature was raised to 66 ° C. and fully aged. Matured
After that, the molecular weight of 100,000 used in the preparation of Em-A
Remeritized gelatin 41.2g and NaCl, 18.5
g was added. After adjusting the pH to 7.2, dimethyl alcohol
Minborane, 8 mg was added. AgNO_Three26g
Double jet of 203mL aqueous solution and KBr aqueous solution
Add so that the final flow rate is 3.8 times the initial flow rate.
It was. At this time, the silver potential is -30 with respect to the saturated calomel electrode.
It was kept at mV. AgNO_ThreeAn aqueous solution containing 110.2 g
440.6 mL and KBr aqueous solution
Accelerate the flow rate so that the final flow rate is 5.1 times the initial flow rate.
Added over 24 minutes. At this time, it is used for the preparation of Em-A.
The AgI fine grain emulsion used had a silver iodide content of 2.3 mo.
At the same time, the flow rate is accelerated so that it becomes 1%.
The position was kept at -20 mV to a saturated calomel electrode. 1
Add 10.7 mL of N potassium thiocyanate aqueous solution
After that, AgNO_Three, 24.1g in aqueous solution 153.5
mL and KBr aqueous solution for 2 minutes 30 seconds by double jet method
Was added over time. At this time, the silver potential was kept at 10 mV.
Adjust the silver potential to -70 mV by adding KBr aqueous solution.
It was. The above AgI fine grain emulsion was converted to 6.4 in terms of KI mass.
g was added. Immediately after the addition, AgNO_Three57g
An aqueous solution containing 404 mL was added over 45 minutes. this
KBr so that the potential at the end of the addition is -30 mV
Prepared with aqueous solution. Wash with water in the same way as Em-A
Sensitized. (Em-C) Nuclear form in the preparation of Em-B
AgNO at the time of growth_ThreeThe addition amount was changed to 2.0 times. So
The final AgNO_Three, 57 g of aqueous solution containing 57 g
KBr water so that the potential at the end of the addition of +90 mV
Changed to adjust with solution. Otherwise, with Em-B
Prepared in substantially the same manner. (Em-D) Phthalization with a phthalation rate of 97%
31.7 g of low molecular weight gelatin having a molecular weight of 15000,
Keep 42.2L of aqueous solution containing 31.7g of KBr at 35 ° C.
And stirred vigorously. AgNO_ThreeWater containing 316.7 g
1583 mL of solution and KBr, 221.5 g, molecular weight 15
Aqueous solution 15 containing 52.7 g of 000 low molecular weight gelatin
83 mL was added over 1 minute by the double jet method.
Immediately after the addition, 52.8 g of KBr is added and AgN is added.
O_Three, 398.2 g of aqueous solution 2485 mL and KB
r, 2581 mL of an aqueous solution containing 291.1 g
It was added over 2 minutes by the wet method. Immediately after the addition
KBr, 47.8 g was added. Then, heat up to 40 ° C
And matured enough. After aging, the phthalation rate is 97%.
923 g of gelatinized molecular weight of 100,000 and K
Br, 79.2 g was added and AgNO_Three, 5103g
Double solution containing 15947 mL of aqueous solution and KBr aqueous solution
So that the final flow rate is 1.4 times the initial flow rate.
The amount was accelerated and added over 12 minutes. At this time, the silver potential
It was kept at -60 mV to a saturated calomel electrode. Washing with water
After adding gelatin, pH, 5.7, pAg, 8.8,
131.8 g of silver equivalent per 1 kg of emulsion, gelatin
The seed weight was adjusted to 64.1 g. Phthalization rate
Contains 46g of 97% phthalated gelatin and 1.7g of KBr
1211 mL of the aqueous solution was kept at 75 ° C. and stirred vigorously.
After adding 9.9 g of the above-mentioned seed emulsion, the modified silicon oy
Le (Nihon Unicar Co., Ltd. product, L7602) 0.3
g was added. H₂SO_FourTo adjust the pH to 5.5
After, AgNO_Three, 7.0 g of aqueous solution containing 7.0 g
And KBr aqueous solution with double jet method, final flow is initial flow
Accelerate the flow rate so that it is 5.1 times the amount and add for 6 minutes.
Added. At this time, the silver potential is
It was kept at 20 mV. Sodium benzenethiosulfonate
2 mg and 2 mg of thiourea dioxide are added, then Ag
NO_Three, Aqueous solution containing 144.5 g, 410 mL and KI
A mixed aqueous solution of KBr and KI containing 7 mol%
So that the final flow rate is 3.7 times the initial flow rate
The flow rate was accelerated and added over 56 minutes. At this time, the silver potential
Was kept at -30 mV to a saturated calomel electrode. Ag
NO_Three, 41.3 g containing 121.3 mL aqueous solution
Add the aqueous solution over 22 minutes by the double jet method.
It was. At this time, the silver potential is +20 with respect to the saturated calomel electrode.
It was kept at mV. Increase the temperature to 82 ° C, add KBr and add silver
After adjusting the position to −80 mV, a 0.037 μm particle support
6.33g of AgI fine grain emulsion added in terms of KI weight
Added. Immediately after the addition, AgNO_Three, 66.4g
Add 206.2 mL of aqueous solution over 16 minutes.
It was. The silver potential is -80 with aqueous KBr solution for the first 5 minutes of addition.
It was kept at mV. After washing with water, add gelatin and
The pH was adjusted to 5.8, pAg, 8.7. Same as Em-A
Like, chemical sensitization. (Em-E) Low molecular weight molecular weight 15000
Gelatin, 0.71 g, KBr, 0.92 g, Em-D
Containing 0.2 g of modified silicone oil used in the preparation of
Maintain 1200 mL of solution at 39 ° C and adjust pH to 1.8
And stirred vigorously. AgNO_Three, 0.45g in water
Solution and KBr aqueous solution containing 1.5 mol% KI
It was added over 17 seconds by the jet method. At this time, KBr
The excess concentration of was kept constant. The temperature was raised to 56 ° C and aging was performed.
After sufficient aging, 35 μmol methionine per gram
Containing 97% of phthalate with a molecular weight of 100,000
Talted gelatin 20g was added. Adjust pH to 5.9
After that, KBr, 2.9 g was added. AgNO_Three, 2
Duplicate 288mL of aqueous solution containing 8.8g and KBr aqueous solution
Added over 53 minutes by Ludgett method. At this time, Em
-AgI fine grain emulsion used in the preparation of A contains silver iodide
At the same time so that the rate is 4.1 mol%, and silver
The potential was kept at -60 mV to a saturated calomel electrode.
After adding KBr, 2.5 g, AgNO_Three, 87.7
The aqueous solution containing g and the aqueous KBr solution
Accelerate the flow rate so that the final flow rate is 1.2 times the initial flow rate.
Added over 63 minutes. At this time, the above-mentioned AgI fine particles
Emulsion so that the silver iodide content is 10.5 mol%
At the same time, the flow rate is accelerated and added, and the silver potential is -70 mV.
Kept. After adding 1 mg of thiourea dioxide, AgN
O_Three, 41.8 g of aqueous solution 132 mL and KBr aqueous solution
The liquid was added over 25 minutes by the double jet method. Addition
Of the aqueous KBr solution so that the potential at the end is +20 mV.
The addition was adjusted. Sodium benzenethiosulfonate,
After adding 2 mg, the pH was adjusted to 7.3. KBr
After adjusting the silver potential to -70 mV, A
5.73 g of gI fine grain emulsion was added in terms of KI mass.
Immediately after the addition, AgNO_Three, 66.4g water-soluble
609 mL of solution was added over 10 minutes. 6 at the beginning of addition
The silver potential was kept at -70 mV with an aqueous KBr solution for a minute. water
After washing, gelatin is added, pH 6.5 at 40 ° C., pA
g, adjusted to 8.2. Add compounds 1 and 2 above
Then, the temperature was raised to 56 ° C. The above-mentioned AgI fine grain emulsion
After adding 0.0004 mol to 1 mol of silver,
Sensitizing dyes 6 and 7 were added. Potassium thiocyanate
Chloroauric acid, sodium thiosulfate, N, N-dimethyl
Selenourea was added for optimal chemical sensitization. End of chemical sensitization
Upon completion, compounds 3 and 4 described above were added. [0221] Embedded image [0222] Embedded image(Em-F) Nuclear form in the preparation of Em-E
AgNO at the time of growth_ThreeE except that the addition amount was changed to 3.1 times
Prepared in substantially the same manner as m-E. However, Em-E sensitization
The dye was changed to sensitizing dyes 8, 9 and 10. [0224] Embedded image [0225] Embedded image [0226] Embedded image (Em-G) Low molecular weight molecular weight 15000
Gelatin 0.70g, KBr, 0.9g, KI, 0.1
75g, modified silicone oil (Nihon Unicar Co., Ltd
Product L7602) 1200 mL of aqueous solution containing 0.2 g
While maintaining at 33 ° C, the pH was adjusted to 1.8 and stirred vigorously.
AgNO_Three, 1.8g aqueous solution and 3.2mol%
KBr aqueous solution containing KI in 9 seconds by double jet method
Added over. At this time, the excessive concentration of KBr is kept constant.
It was. The temperature was raised to 69 ° C. and aging was performed. Per gram after ripening
Molecular weight 10,000 containing 35 μmol methionine
Trimelli chemical modification of 0 amino group with trimellitic acid
27.8 g of gelatinized gelatin was added. pH to 6.3
After preparation, 2.9 g of KBr was added. AgN
O_Three, 270 mL of aqueous solution containing 27.58 g and KBr water
The solution was added over 37 minutes by the double jet method. This
A low molecular weight gelatin aqueous solution having a molecular weight of 15000 and A
gNO_ThreeAn aqueous solution and an aqueous KI solution are disclosed in JP-A-10-43570.
Another having a magnetic coupling induction stirrer
Particle size prepared by mixing immediately before addition in the chamber
A silver iodide content of 0.008 μm AgI fine grain emulsion
4.1 mol% at the same time and silver potential
Was kept at -60 mV to a saturated calomel electrode. KB
After adding r, 2.6 g, AgNO_Three, 87.7g
Final flow of aqueous solution containing KBr and aqueous solution of KBr
49 Accelerate the flow rate so that the amount is 3.1 times the initial flow rate.
Added over a minute. At this time, mix immediately before the above addition.
The AgI fine grain emulsion prepared in this manner has a silver iodide content of 7.9.
At the same time, the flow rate is accelerated to reach mol%, and the silver potential is
-70 mV was maintained. Add 1mg of thiourea dioxide
After that, AgNO_Three, 41.8 g of aqueous solution 132mL
And KBr aqueous solution for 20 minutes by double jet method
Added. K so that the potential at the end of addition is +20 mV
Addition of Br aqueous solution was adjusted. Raise the temperature to 78 ° C and adjust the pH
After adjusting to 9.1, KBr is added and the potential is −60 m.
V. AgI fine grain emulsion used in the preparation of Em-A
Was added in an amount of 5.73 g in terms of KI mass. Immediately after addition
AgNO_Three, 321 mL of an aqueous solution containing 66.4 g
Added over 4 minutes. KBr water for 2 minutes at the beginning of the addition
The silver potential was kept at −60 mV with the solution. Same as Em-F
Washed with water and chemically sensitized. (Em-H) Ion exchanged molecular weight 100
000 gelatin 17.8 g, KBr, 6.2 g, K
I, Keeping aqueous solution containing 0.46g at 45 ° C, stirring vigorously
did. AgNO_ThreeAn aqueous solution containing 11.85 g and KBr
An aqueous solution containing 3.8 g in 47 seconds by the double jet method
Added over. Ion-exchanged molecular weight after heating to 63 ° C
Add 24.1g of 100000 gelatin and ripen
It was. After fully aging, AgNO_Three, Including 133.4g
Final flow rate of aqueous solution and KBr aqueous solution by double jet method
Add over 20 minutes to 2.6 times the initial flow rate
did. At this time, the silver potential is +4 with respect to the saturated calomel electrode.
It was kept at 0 mV. 10 minutes after the start of addition₂IrCl₆
0.1 mg of was added. After adding 7 g of NaCl, A
gNO_ThreeAn aqueous solution containing 45.6 g and KBr aqueous solution
It was added over 12 minutes by the Luget method. At this time, silver
The potential was kept at +90 mV. Also 6 minutes after the start of addition
Add 100 mL of an aqueous solution containing 29 mg of yellow blood salt
It was. After the addition of 14.4 g of KBr, in the preparation of Em-A
Add 6.3 g of the used AgI fine grain emulsion in terms of KI mass
Added. Immediately after the addition, AgNO_Three, 42.7g
11 minutes by double jet method with aqueous solution containing KBr and aqueous solution
Added in between. At this time, the silver potential is kept at +90 mV.
It was. It was washed with water in the same manner as Em-F and chemically sensitized. (Em-I) Nuclear form in the preparation of Em-H
The temperature was adjusted in the same way except that the temperature during the formation was changed to 38 ° C.
Made. (Em-J) Low molecular weight with a molecular weight of 15000
Aqueous solution 12 containing 4.9 g of gelatin and 5.3 g of KBr
00 mL was kept at 60 ° C. and stirred vigorously. AgNO_Three,
27 mL of aqueous solution containing 8.75 g and KBr, 6.45 g
Double-jet method with 36 mL of aqueous solution containing
Added at. After heating to 77 ° C, AgNO_Three6.9
21 mL of an aqueous solution containing g was added over 2.5 minutes.
NH_FourNO_Three, 26g, 1N, NaOH, 56mL
Next, after adding, it was aged. After completion of aging, the pH is adjusted to 4.8
Prepared. AgNO_Three, 141 g of aqueous solution containing 141 g
Dub 458mL of aqueous solution containing 102.6g of L and KBr
The final flow rate is 4 times the initial flow rate by the Lujet method.
Added. After dropping to 55 ° C, AgNO_Three7.1g
Aqueous solution containing 240 mL and 6.46 g of KI
Was added over 5 minutes by the double jet method. KBr
After adding 7.1 g, sodium benzenethiosulfonate
4mg and K₂IrCl₆, 0.05 mg was added. A
gNO_Three, 177 mL of aqueous solution containing 57.2 g and KB
r, A solution containing 40.2g, 223mL passed over 8 minutes
It was added by the double jet method. After washing with water, gelatin
And adjusted to pH 6.5, pAg, 8.2 at 40 ° C.
did. After adding compounds 1 and 2 above, to 61 ° C
The temperature rose. Add sensitizing dyes 11, 12, 13 and 14
K then₂IrCl₆, Potassium thiocyanate, gold chloride
Acid, sodium thiosulfate, N, N-dimethylselenoure
A was added for optimal chemical sensitization. At the end of chemical sensitization
Compounds 3 and 4 were added. [0231] Embedded image [0232] Embedded image [0233] Embedded image [0234] Embedded image (Em-K) Nucleation in Em-J preparation
Except that the hour temperature was changed to 42 ° C, the adjustment was performed in the same manner.
Made. (Em-L, M, N) Em-G, H or
Prepared in substantially the same manner as Em-I. However, chemical sensitization is E
It carried out by the method substantially the same as mJ. (Em-O) Molecular weight 1 with 97% phthalation rate
00000 phthalated gelatin, 0.38 g, KBr,
Keep 1200 mL of an aqueous solution containing 0.99 g at 60 ° C.,
The pH was adjusted to 2 and stirred vigorously. AgNO_Three1.9
An aqueous solution containing 6 g and KBr, 1.97 g, KI, 0.1
72 g of aqueous solution containing 72 g was transferred for 30 seconds by the double jet method.
Added. After ripening, 35 μmol of meg / g
Thionine-containing amino group having a molecular weight of 100,000
Trimellited gelatin chemically modified with Limellitic acid 1
2.8 g was added. After adjusting the pH to 5.9, KB
r, 2.99 g, NaCl 6.2 g were added. AgN
O_Three, 27.3g containing aqueous solution 60.7mL and KBr water
The solution was added over 35 minutes by the double jet method. This
At -50 mV with respect to the saturated calomel electrode
Kept. AgNO_Three, 65.6 g of aqueous solution and KBr
1. The final flow rate of the aqueous solution by the double jet method is the initial flow rate.
Accelerate the flow rate to 1x and add over 37 minutes
It was. At this time, the AgI fine particle milk used in the preparation of Em-A
At the same time so that the silver iodide content is 6.5 mol%.
Accelerate the flow rate and add the silver potential to -50mV
It was. After adding 1.5 mg of thiourea dioxide, AgN
O_Three, 41.8 g of aqueous solution 132 mL and KBr aqueous solution
The liquid was added over 13 minutes by the double jet method. Addition
KBr aqueous solution so that the silver potential at the end is +40 mV
The addition of was adjusted. Sodium benzenethiosulfonate
After adding 2 mg, KBr is added to reduce the silver potential.
Adjusted to 100 mV. The above AgI fine grain emulsion is changed to KI.
6.2 g was added in terms of mass. Immediately after the addition, Ag
NO_Three, 88.5g of aqueous solution 300mL in 8 minutes
Added over. The potential at the end of the addition will be + 60mV
It adjusted by addition of KBr aqueous solution. For Em-J
Change the sensitizing dyes to 1, 2 and 3 to optimize chemical sensitization.
Proceed appropriately to obtain Em-O. The silver halide emulsion thus obtained
The characteristics of Em-A to Em-O are shown in (Table 4). [0239] [Table 4] 1) Support The support used in this example was prepared by the following method.
It was. Polyethylene-2,6-naphthalate polymer 10
0 parts by weight and Tinuvin P.I. 3
26 (Ciba-Geigy Ciba-Geigy) 2 quality
After drying the part and melting at 300 ° C,
Extrude, 3.3 times longitudinal stretch at 140 ° C,
The film is stretched 3.3 times at 130 ° C, and then 250 ° C
PEN (polyethylene with a thickness of 90 μm was fixed by heat for 6 seconds.
Nnaphthalate) film was obtained. This PEN fi
Lum has blue, magenta and yellow dyes
(Public technique: I-1, described in public technical number 94-6023,
I-4, I-6, I-24, I-26, I-27, II-
An appropriate amount of 5) was added. Furthermore, stainless steel with a diameter of 20 cm
Wrapped around a loess core and heat history at 110 ° C for 48 hours
To provide a support that is difficult to curl. 2) Application of undercoat layer The above support has corona discharge treatment and UV discharge treatment on both sides.
Then, after further glow discharge treatment,
Latin 0.1g / m²Sodium α-sulfodi-2-
Ethylhexyl succinate 0.01g / m², Salici
Luric acid 0.04 g / m², P-chlorophenol 0.2g
/ M², (CH₂= CHSO₂CH₂CH₂NHCO)₂CH
₂ 0.012 g / m², Polyamide-epichlorohydride
Polycondensate 0.02 g / m²Apply a primer solution (10
mL / m², Using bar coater)
Provided on the surface side. Drying was performed at 115 ° C. for 6 minutes (dry drying
All rollers and conveyors in the machine are at 115 ° C
) 3) Coating of back layer The following set as a back layer on one side of the support after undercoating
An antistatic layer, a magnetic recording layer, and a sliding layer were coated. 3-1) Coating of antistatic layer Tin oxide-antimony oxide composite with an average particle size of 0.005 μm
The specific resistance of the compound is a dispersion of fine powder of 5 Ω · cm (secondary
Aggregated particle diameter of about 0.08 μm) is 0.2 g / m², Gelatin
0.05 g / m², (CH₂= CHSO₂CH₂CH₂N
HCO)₂CH₂0.02 g / m², Poly (degree of polymerization 10)
Oxyethylene-p-nonylphenol 0.005 g /
m²And coated with resorcin. 3-2) Coating of magnetic recording layer 3-poly (degree of polymerization 15) oxyethylene-propyloxy
Coated with citrimethoxysilane (15% by mass)
Cobalt-γ-iron oxide (specific surface area 43m²/ G, long axis
0.14 μm, uniaxial 0.03 μm, saturation magnetization 89 Am²
/ Kg, Fe⁺²/ Fe⁺³= 6/94, surface is aluminum oxide
Treated with 2% by mass of iron oxide with silicon oxide) 0.0
6g / m²Diacetylcellulose 1.2 g / m²(Oxidation
Dispersion of iron is carried out with an open kneader and a sand mill.
C) as a curing agent₂H_FiveC (CH₂OCONH-C₆H
_Three(CH_Three) NCO)_Three 0.3 g / m²As a solvent
Using seton, methyl ethyl ketone, and cyclohexanone
Apply with a bar coater and have a thickness of 1.2μm
Got. Silica particles (0.3 μm) and 3 as a matting agent
-Poly (degree of polymerization 15) oxyethylene-propyloxy
A coating coated with trimethoxysilane (15% by mass)
10 mg each of aluminum oxide (0.15 μm) as a polishing agent
/ M²It added so that it might become. Drying at 115 ° C for 6 minutes
(All the rollers and conveyors in the drying zone are 11
5 ° C). Magnetic recording with X-light (blue filter)
Layer D^BThe increase in color density is about 0.1, and the magnetic recording layer
The saturation magnetization moment is 4.2 Am²/ Kg, coercive force 7.
3 × 10^FourA / m, the squareness ratio was 65%. 3-3) Preparation of sliding layer Diacetylcellulose (25mg / m²), C₆H₁₃CH
(OH) C_TenH₂₀COOC₄₀H₈₁(Compound a, 6 mg /
m²) / C₅₀H₁₀₁O (CH₂CH₂O)₁₆H (compound b,
9 mg / m²) The mixture was applied. This mixture
Xylene / propylene monomethyl ether (1 /
1) Propylene monomethyl melted at 105 ° C in room temperature
After pouring and dispersing in ruether (10 times amount),
After making dispersion (average particle size 0.01μm) in Seton
Added. Silica particles (0.3 μm) as a matting agent
Abrasive 3-poly (degree of polymerization 15) oxyethylene propylene
Coated with ruoxytrimethoxysilane (15% by mass)
15 mg / m each of aluminum oxide (0.15 μm)
²It added so that it might become. Drying was performed at 115 ° C. for 6 minutes.
(All the rollers and conveyors in the drying zone are 115
° C). The sliding layer has a dynamic friction coefficient of 0.06 (5 mmφ step).
Nres hard ball, load 100g, speed 6cm / min), static
Coefficient of friction 0.07 (clip method), emulsion surface described later
The coefficient of dynamic friction of the sliding layer was also excellent at 0.12.
It was. 4) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, the following composition
Sample 2 which is a color negative photosensitive material
01-207 were created. (Composition of photosensitive layer) Main materials used for each layer
Are classified as follows:     ExC: Cyan coupler UV: UV absorber     ExM: Magenta coupler HBS: High boiling point organic solvent     ExY: Yellow coupler H: Gelatin hardener (Specific compounds are described below.
The chemical formula is listed behind) The number corresponding to each component is g / m²Application amount expressed in units
For silver halide, the coating amount in terms of silver is shown.
The [0248]   (Sample 201)   First layer (first antihalation layer)     Black colloidal silver Silver 0.155     0.07 μm surface fogging AgBrI (2) Silver 0.01     Gelatin 0.87     ExC-1 0.002     ExC-3 0.002     Cpd-2 0.001     HBS-1 0.004     S-37 0.002 [0249]   Second layer (second antihalation layer)     Black colloidal silver Silver 0.066     Gelatin 0.407     ExM-1 0.050     ExF-1 2.0 × 10^-3     HBS-1 0.074     Solid disperse dye ExF-2 0.015     Solid disperse dye ExF-3 0.020 [0250]   Third layer (intermediate layer)     0.07 μm AgBrI (2) 0.020     ExC-2 0.022     Polyethyl acrylate latex 0.085     Gelatin 0.294 [0251]   4th layer (low sensitivity red sensitive emulsion layer)     Silver iodobromide emulsion Em-L Silver 0.065     Silver iodobromide emulsion Em-M Silver 0.100     Silver iodobromide emulsion Em-N Silver 0.158     ExC-1 0.109     ExC-3 0.044     ExC-4 0.072     ExC-5 0.011     ExC-6 0.003     Cpd-2 0.025     Cpd-4 0.025     HBS-1 0.17     Gelatin 0.80 [0252]   5th layer (medium sensitivity red emulsion layer)     Silver iodobromide emulsion Em-J Silver 0.21     Silver iodobromide emulsion Em-K Silver 0.62     ExC-1 0.14     ExC-2 0.026     ExC-3 0.020     ExC-4 0.12     ExC-5 0.016     ExC-6 0.007     Cpd-2 0.036     Cpd-4 0.028     HBS-1 0.16     Gelatin 1.18 [0253]   6th layer (high-sensitivity red-sensitive emulsion layer)   Emulsion 1-A, F, J, K, N, O, R of Example 1 Silver 1.67     ExC-1 0.18     ExC-3 0.07     ExC-6 0.047     Cpd-2 0.046     Cpd-4 0.077     HBS-1 0.37     Gelatin 2.12 [0254]   7th layer (intermediate layer)     Cpd-1 0.089     Solid disperse dye ExF-4 0.030     HBS-1 0.050     Polyethyl acrylate latex 0.83     Gelatin 0.84 [0255]   Eighth layer (Multilayer effect donor layer (layer that gives a multilayer effect to the red-sensitive layer))     Silver iodobromide emulsion Em-E Silver 0.560     Cpd-4 0.030     ExM-2 0.096     ExM-3 0.028     ExY-1 0.031     ExG-1 0.006     HBS-1 0.085     HBS-3 0.003     Gelatin 0.58 [0256]   9th layer (low sensitivity green emulsion layer)     Silver iodobromide emulsion Em-G Silver 0.39     Silver iodobromide emulsion Em-H Silver 0.28     Silver iodobromide emulsion Em-I Silver 0.35     ExM-2 0.36     ExM-3 0.045     ExG-1 0.005     HBS-1 0.28     HBS-2 0.01     S-2 0.27     Gelatin 1.39 [0257]   10th layer (medium sensitive green sensitive emulsion layer)     Silver iodobromide emulsion Em-F Silver 0.20     Silver iodobromide emulsion Em-G Silver 0.25     ExC-6 0.009     ExM-2 0.031     ExM-3 0.029     ExY-1 0.006     ExM-4 0.028     ExG-1 0.005     HBS-1 0.064     HBS-2 2.1 × 10^-3     Gelatin 0.44 [0258]   11th layer (high sensitivity green emulsion layer)     Silver iodobromide emulsion Em-O Silver 1.200     ExC-6 0.004     ExM-1 0.016     ExM-3 0.036     ExM-4 0.020     ExM-5 0.004     ExY-5 0.008     ExM-2 0.013     Cpd-4 0.007     HBS-1 0.18     Polyethyl acrylate latex 0.099     Gelatin 1.11 [0259]   12th layer (yellow filter layer)     Yellow colloidal silver Silver 0.047     Cpd-1 0.16     ExF-5 0.010     Solid disperse dye ExF-6 0.010     HBS-1 0.082     Gelatin 1.057 [0260]   13th layer (low sensitivity blue-sensitive emulsion layer)     Silver iodobromide emulsion Em-A Silver 0.18     Silver iodobromide emulsion Em-B Silver 0.20     Silver iodobromide emulsion Em-C Silver 0.07     ExC-1 0.041     ExC-8 0.012     ExY-1 0.035     ExY-2 0.71     ExY-3 0.10     ExY-4 0.005     Cpd-2 0.10     Cpd-3 4.0 × 10^-3     HBS-1 0.24     Gelatin 1.41 [0261]   Fourth layer (high-sensitivity blue-sensitive emulsion layer)     Silver iodobromide emulsion Em-D Silver 0.75     ExC-1 0.013     ExY-2 0.31     ExY-3 0.05     ExY-6 0.062     Cpd-2 0.075     Cpd-3 1.0 × 10^-3     HBS-1 0.10     Gelatin 0.91 [0262]   15th layer (first protective layer)     0.07 μm AgBrI (2) Silver 0.30     UV-1 0.21     UV-2 0.13     UV-3 0.20     UV-4 0.025     F-11 0.009     F-18 0.005     F-19 0.005     HBS-1 0.12     S-2 5.0 × 10^-2     Gelatin 2.3 [0263]   16th layer (second protective layer)     H-1 0.40     B-1 (diameter 1.7 μm) 5.0 × 10^-2     B-2 (diameter 1.7 μm) 0.15     B-3 0.05     S-1 0.20     Gelatin 0.75 Furthermore, preservability, processability, and pressure are appropriately applied to each layer.
Resistance, antifungal and antibacterial, B-4 to B-6, no F-1
F-18 and iron salt, lead salt, gold salt, platinum salt, parajiu
Contains salt, iridium, ruthenium and rhodium salts
Has been. In addition, the silver halide 1 mol
8.5 x 10 per ru^-3Gram, 7.9 x 1 in the 11th layer
0^-3Add gram of calcium with aqueous calcium nitrate solution
A sample was prepared. To further improve antistatic properties
Contains at least one of W-1, W-6, W-7, W-8
In order to improve coatability, less W-2 and W-5
Contains at least one. Preparation of dispersion of organic solid disperse dye The following ExF-3 was dispersed by the following method. That is, water 2
1.7 mL and 5% aqueous p-octylphenoxye
Toxiethoxyethane sulfonic acid soda 3 mL and 5
P-Octylphenoxypolyoxyethylene in 1% aqueous solution
Add 700g of ether (polymerization degree 10) 0.5g.
Put in tomill, 5.0g of dye ExF-3 and zirco oxide
Add 500mL of Ni beads (diameter 1mm)
The product was dispersed for 2 hours. The BO type manufactured by Chuo Koki is used for this dispersion.
A vibrating ball mill was used. After dispersion, take out the contents,
Add to 8 g of 12.5% gelatin solution and filter the beads
A gelatin dispersion of the dye was obtained. Of dye fine particles
The average particle size was 0.44 μm. Similarly, a solid dispersion of ExF-4 was obtained.
It was. The average particle size of the dye fine particles was 0.45 μm. E
xF-2 is European Patent Application Publication (EP) No. 549,489.
Microprecipitation described in Example 1 of the A specification (Microp
dispersion).
The average particle size was 0.06 μm. The solid dispersion of ExF-6 was separated by the following method.
Scattered. ExF-6 wet cake 2 containing 18% water
To 800 g, 37 g of 4000 g of water and 3% solution of W-2
Add 6g, stir, and slurry of ExF-6 32%
It was. Next, Ultra Visco Mill manufactured by Imex Co., Ltd.
(UVM-2) zirconia beads having an average particle size of 0.5 mm
1700 mL of slurry is filled and the peripheral speed is about 10 through the slurry.
crush for 8 hours at m / sec, discharge rate 0.5L / min
It was. The compounds used for forming the above layers are as follows.
It is shown. [0269] Embedded image [0270] Embedded image[0271] Embedded image[0272] Embedded image[0273] Embedded image[0274] Embedded image[0275] Embedded image[0276] Embedded image[0277] Embedded image[0278] Embedded image [0279] Embedded image[0280] Embedded image[0281] Embedded image[0282] Embedded image[0283] Embedded image [0284] Embedded image The evaluation method of the sample is as follows. FUJIFILM
Gelatin filter SC-39 (cut-off wave)
Long wavelength light transmission filter with a length of 390 nm) and continuous
1/100 second exposure through the wedge. Development is Fuji Photo
Using an automatic processor FP-360B manufactured by Film Co., Ltd.
More went. The overflow solution from the bleaching bath is allowed to flow to the back bath.
Instead, it was modified so that everything was discharged into the waste liquid tank. This
FP-360B is the Japan Society of Invention Disclosure Technique 94-4992
Is mounted. The processing steps and the processing liquid composition are shown below.   (Processing process)     Process Processing time Processing temperature Replenishment amount * Tank capacity   Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5 L   Whitening 50 seconds 38.0 ℃ 5 mL 5L   Fixing (1) 50 seconds 38.0 ℃ -5L   Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L   Washing with water 30 seconds 38.0 ℃ 17 mL 3L   Stable (1) 20 seconds 38.0 ℃ -3L   Stable (2) 20 seconds 38.0 ℃ 15 mL 3L   Dry 1 min 30 sec 60.0 ° C   * Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex.1) The stabilizing solution and the fixing solution are changed from (2) to (1).
This is a counter-current system, and all overflow water in the washing water is fixed.
Introduced into bath (2). Bring the developer into the bleaching process
Amount of bleaching solution, amount of bleaching solution brought into the fixing process, and amount of fixing solution
The amount brought into the washing process is 35 mm photosensitive material, 1.1 m wide
Per 2.5 mL, 2.0 mL, and 2.0 mL, respectively
there were. The crossover time is 6 seconds.
Yes, this time is included in the processing time of the previous step. The opening area of the processor is 10 with a color developer.
0cm²120cm with bleach solution²About 1 other processing solution
00cm²Met. The composition of the treatment liquid is shown below.   (Color developer) Tank solution (g) Replenisher (g)   Diethylenetriaminepentaacetic acid 3.0 3.0   Catechol-3,5-disulfonic acid     Disodium 0.3 0.3   Sodium sulfite 3.9 5.3   Potassium carbonate 39.0 39.0   Disodium-N, N-bis (2-sulfur     Honatoethyl) hydroxylamine 1.5 2.0   Potassium bromide 1.3 0.3   Potassium iodide 1.3mg −   4-hydroxy-6-methyl-1,3     3a, 7-tetrazaindene 0.05-   Hydroxylamine sulfate 2.4 3.3   2-Methyl-4- [N-ethyl-N-     (Β-hydroxyethyl) amino]     Aniline sulfate 4.5 6.5   Add water 1.0L 1.0L   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18 [0290]   (Bleaching solution) Tank solution (g) Replenisher solution (g)   1,3-diaminopropanetetraacetic acid second     Iron ammonium monohydrate 113 170   Ammonium bromide 70 105   Ammonium nitrate 14 21   Succinic acid 34 51   Maleic acid 28 42   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia] 4.6 4.0 (Fixing (1) Tank liquid) The above bleach tank liquid
And 5 to 95 (volume ratio) of the following fixing tank solution (pH)
6.8). [0292]   (Fixing (2)) Tank liquid (g) Replenisher (g)   Ammonium thiosulfate aqueous solution 240 mL 720 mL   (750g / L)   Imidazole 7 21   Ammonium methanethiosulfonate 5 15   Ammonium methanesulfinate 10 30   Ethylenediaminetetraacetic acid 13 39   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45 (Washing water) Tap water is exchanged with H-type strongly acidic cation.
Replacement resin (Rum & Haas Amberlite IR-
120B) and OH type strongly basic anion exchange resin (same as above)
To a mixed bed column packed with mberlite IR-400)
Pass water and adjust calcium and magnesium ion concentration to 3m
g / L or less, followed by isocyanuric dichloride
Thorium 20mg / L and sodium sulfate 150mg / L
Was added. The pH of this solution is in the range of 6.5 to 7.5.
It was. [0294]   (Stabilizer) Tank fluid and replenisher common (Unit: g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether 0.2     (Average polymerization degree 10)   1,2-Benzisothiazoline-3-one sodium 0.10   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazole-1-     Ilmethyl) piperazine 0.75   Add water and add 1.0L   pH 8.5 The samples 201 to 207 were subjected to the above treatment.
did. Measure the concentration of the processed sample with a red filter.
The photographic performance was evaluated by the above. Photo sensitivity and fog
The results are shown in Table 5 below. Sensitivity is the characteristic curve obtained.
Dew required to reach fog density plus 0.1
The relative value of the reciprocal of the amount of light is displayed (the sensitivity of the sample 201 is 1
00). [0296] [Table 5] Comparative samples (201, 202, 204,
206) and the samples of the present invention (203, 205, 207)
From a comparison, a sample using the emulsion of the present invention has high sensitivity and a high sensitivity.
It can be seen that yellowtail has been reduced.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view of a tabular grain in which an epitaxial junction protrudes in the side surface direction of a host tabular grain, as viewed from a direction perpendicular to the main plane.

Claims (1)

1. A silver halide photographic emulsion characterized in that tabular grains satisfying the following (i) to (iv) occupy 70% or more (number ratio) of all grains. (I) Silver iodochlorobromide grains having a (111) plane as a main plane and two parallel twin planes. (Ii) The equivalent circle equivalent diameter is 2.5 μm or more and the particle thickness is 0.15 μm or less. (Iii) A silver halide epitaxial junction is selectively provided at the apex of the host tabular grain, at least one per grain.
Have one. (Iv) The silver halide epitaxial junction is
When viewed from a direction perpendicular to the (111) main plane, 60% or more of the projected area of each joint is a protrusion-like joint existing outside the host tabular grain.