JP2001194741A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic emulsion having improved sensitivity and fog, improved preservability before exposure, improved latent image retentivity after exposure and improved characteristics to pressure by the application of an organic hole trapping dopant and a silver halide photographic sensitive material containing the silver halide photographic emulsion. SOLUTION: In the silver halide photographic emulsion, flat platy silver halide grains having an aspect ratio of >=5 occupy >=50% of the total projected area of all the silver halide grains, the coefficient of variation of the particle size distribution of all the silver halide grains is <=25% and an organic hole trapping dopant is contained in the flat platy silver halide grains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic emulsion having improved sensitivity, fog, preservability before exposure, preservation of latent image after exposure, and anti-pressure characteristics, and the silver halide photographic emulsion. The present invention relates to a silver halide photographic material.

[0002]

2. Description of the Related Art In recent years, demands for higher sensitivity and higher image quality of silver halide photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) have been more and more increased. In addition, in recent years, there has been an increasing demand for improved reliability of photosensitive materials, such as fluctuations in photographic characteristics under various storage conditions before exposure and storage stability of images after exposure.

[0003] In terms of increasing the sensitivity, various analyzes and technical developments have been made. There are various inefficiency factors related to the sensitivity of a silver halide photographic emulsion (hereinafter, also simply referred to as a silver halide emulsion), but from the viewpoint of preventing recombination of free electrons and holes, which is one factor. It has been known for a long time that reduction sensitization is effective. U.S. Pat. Nos. 2,487,850 and 2,5
12,925 and British Patent 789,823 disclose reduction sensitization techniques.

[0004] However, for example, Journal of Imaging Science (Journal of Imaging Science)
ging Science) 29, 233 (198
As reported in 5), the effect of reduction sensitization on increasing the sensitivity is lower than that of hydrogen sensitization in which a photosensitive material is processed in a hydrogen atmosphere. Hydrogen sensitization is a technology that prevents recombination, similar to reduction sensitization, but it has been applied to practical photographic photosensitive materials, such as handling of photosensitive materials in a hydrogen atmosphere and preservation of the sensitizing effect. The technology to be applied has various points to be improved.

In other words, it has been suggested that the application of the technique for preventing recombination can achieve higher sensitivity than reduction sensitization, and that recombination prevention more suitable for practical photosensitive materials than hydrogen sensitization. Technology is waiting.

As a recent attempt to prevent the recombination to increase the sensitivity of the photosensitive material, a technique which has achieved great results is disclosed in Japanese Patent Application Laid-Open No. Hei 11-237710, which uses an organic hole trapping dopant. It is.

[0007]

SUMMARY OF THE INVENTION The inventors of the present invention have focused on the above-mentioned technology and have conducted studies. By applying an organic hole-trapping dopant to a specific silver halide emulsion, not only the sensitizing effect but also the sensitizing effect can be obtained. It has been found that it is possible to dramatically improve the characteristics of the photosensitive material such as fog, storage stability, latent image storage stability, and pressure resistance.

Accordingly, an object of the present invention is to provide a silver halide photographic emulsion having improved sensitivity, fog, pre-exposure preservation, post-exposure latent image preservation and anti-pressure characteristics by applying an organic hole trapping dopant. And a silver halide photographic material containing the silver halide photographic emulsion.

[0009]

The object of the present invention has been attained by the following constitutions.

[0010] 1. Tabular silver halide grains having an aspect ratio of 5 or more occupy 50% or more of the projected area of all silver halide grains, and the coefficient of variation of the particle size distribution of all silver halide grains is 2%.
A silver halide photographic emulsion containing 5% or less, and wherein the tabular silver halide grains contain an organic hole trapping dopant.

2. It contains tabular silver halide grains having an aspect ratio of 2 or more, the tabular silver halide grains have dislocation lines in a central region and a peripheral region of a main plane, and have an organic positive electrode in the tabular silver halide grains. A silver halide photographic emulsion containing a hole trapping dopant.

3. A halogen characterized in that tabular silver halide grains having an aspect ratio of 8 or more occupy 50% or more of the projected area of all silver halide grains, and the tabular silver halide grains contain an organic hole-trapping dopant. Silver halide photographic emulsion.

4. It contains tabular silver halide grains having an aspect ratio of 2 or more, and 50% of the tabular silver halide grains are contained.
The above (number) satisfies the following formula 1, and the tabular silver halide grains contain an organic hole trapping dopant.

Formula 1: Average outermost layer silver iodide content in main plane portion> Average surface average silver iodide content in side surface portion A silver halide photographic emulsion containing silver halide grains formed by the inter-grain distance control method and containing an organic hole trapping dopant in the silver halide grains.

6. 1. A silver halide photographic emulsion comprising normal crystal silver halide grains having 10 or more dislocation lines and an organic hole trapping dopant in the normal crystal silver halide grains.

[7] Aspect ratio 2 or more and {100}
A silver halide photographic emulsion containing tabular silver halide grains having a main plane, and further comprising an organic hole-trapping dopant in the tabular silver halide grains.

8. 8. The silver halide photographic emulsion according to any one of the above items 1 to 7, wherein the organic hole trapping dopant is a compound represented by the following general formula (I).

In the formula (I), R is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aromatic group. M represents a hydrogen atom or a metal atom or an organic group capable of forming a salt.

9. 9. The silver halide photographic emulsion according to the above item 8, wherein in the general formula (I), R is a hydrogen atom.

[10] 8. The silver halide photographic emulsion according to any one of the above items 1 to 7, wherein the organic hole trapping dopant is a compound represented by the following general formula (II).

[0021]

Embedded image

In the formula, X and Y represent O, S or Se;
m is 1; n is 1 or 2; R ₁ and R _{2 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted group; Represents a substituted aromatic heterocyclic residue, wherein R ₁ and R ₂ may be the same or different, and may form a ring; E is a group linked to a carbon atom by a heteroatom having at least one free electron pair, and M ⁺ is a proton, organic or inorganic cation.

11. A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to any one of the above 1 to 10.

The mechanism by which the effects of the present invention are exhibited is not clear, but as a result of investigation, it was found that an organic hole trapping dopant was applied to an emulsion in which the characteristics of silver halide grains themselves were improved as shown below. By doing so, photographic characteristics such as sensitivity, fog, storage stability, latent image storage stability and pressure resistance can be improved more synergistically than expected. Tabular emulsion with high monodispersity Tabular emulsion with dislocation lines at specific locations High aspect ratio tabular emulsion Tabular emulsion with controlled average silver iodide content in main plane and side plane Emulsions Performed Normal crystal emulsion having dislocation lines Tabular emulsion having {100} major planes Each invention of the present application will be described in detail below.

The silver halide emulsion of the present invention contains silver halide grains containing an organic hole trapping dopant. In the present invention, the organic hole trapping dopant is an organic compound which is added to a reactant solution during the formation of silver halide grains and can be contained in a silver halide crystal lattice, and is a silver halide grain or a sensitized organic compound. An organic compound that reacts with holes formed during the absorption process of dye photons and emits one or more electrons.

Examples of compounds that function as organic hole trapping dopants are shown below. Compound examples shown below, as described in JP-A-11-237710, by defragmentation of a part of the molecule,
It can emit electrons.

The compound represented by the above formula (I) is preferable as the organic hole trapping dopant of the present invention.

In the general formula (I), R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aromatic heterocyclic residue; M is a hydrogen atom, a metal atom capable of forming a salt, or an organic group.

More preferred examples of the compound represented by the general formula (I) are an inorganic salt or an organic salt of formic acid in which R is a hydrogen atom, and a formic acid in which M is an alkali metal atom or an alkaline earth metal atom. Salts are more preferred. Particularly preferred compounds as organic hole trapping dopants of the present invention are sodium formate and potassium formate.

As another example of a compound which is preferable as an organic hole trapping dopant, the compound represented by the general formula (I)
Compounds represented by I) can be mentioned.

In the general formula (II), X and Y are O, S
Or Se, m is 1, n is 1 or 2,
R ₁ and R ₂ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted, an aralkyl group or a substituted unsubstituted, an unsubstituted aromatic heterocyclic residue, R ₁ and R ₂ may be the same or different, and may form a ring. E is a group linked to a carbon atom by a heteroatom having at least one free electron pair, and M ⁺ is a proton, organic or inorganic cation.

Among the compounds represented by the general formula (II), a more preferred compound is described in JP-A-11-23771.
No. 0, page 5, compound II. 1 to II. 11 is given.

In the present invention, the organic hole trapping dopant needs to be added during the formation of silver halide grains.

In general, the grain forming step of a silver halide emulsion is roughly divided into a nucleus forming step (consisting of a nucleus forming step and a nucleus ripening step) and a subsequent nucleus growing step. Also,
It is also possible to separately grow a previously prepared nuclear emulsion (or seed emulsion). The growing step includes a first growing step,
It may include several steps such as a second growth step. In the present invention, the organic hole trapping dopant is preferably added in the step of growing silver halide grains.

In the present invention, any method can be employed for adding an organic hole trapping dopant (hereinafter, also referred to as a dopant) to a reaction solution of a silver halide emulsion. As a preferable addition method, a method of adding the solution of the dopant alone, a method of mixing and adding the dopant to another additive solution such as a halide solution, and preparing a silver halide fine grain emulsion containing the dopant in advance In this case, a method of adding the silver halide fine grain emulsion can be mentioned.

In the present invention, the pAg at the time of adding the organic hole trapping dopant is preferably set to 2 to 9, more preferably 3 to 8. Further, the pH is preferably from 1 to 10, more preferably from 2 to 9.

The amount of the organic hole trapping dopant preferably used in the present invention is from 10 ^-8 to 10 ^-2 mol, more preferably from 5 × 10 ^-8 to 1 mol per mol of silver halide.
5 × 10 ⁻³ mol, most preferably 10 ^{−7 to} 5 × 10 ⁻³ mol
mol.

The silver halide emulsions defined in claims 1 to 4 and 7 of the present invention contain tabular silver halide grains (hereinafter, also simply referred to as tabular grains or tabular grains). There are roughly two types of tabular grains.
It is classified into 11-type tabular grains and {100} -type tabular grains. The tabular grains defined in claims 1 to 4 of the present invention have a size of $ 1.
It may be a 00-type tabular grain, but is preferably a {111} -type tabular grain.

The {111} type tabular grains have a {111} crystal plane as an opposite main plane, and are crystallographically classified as twins.

Twins are silver halide crystals having one or more twin planes in one grain, and the twin morphology is classified according to the report by Klein and Moiser in Photographic correspondence.
(Korrespondenz) Vol. 99, p100, and Vol. 100, p57.

In the present invention, {111} type tabular grains are
It has two or more twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide photographic emulsion is coated on a support so that the contained tabular grains are substantially parallel to the main plane, thereby preparing a sample. This is cut using a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

The distance between the twin planes of the {111} type tabular grains was determined by observing the section using a transmission electron microscope as described above. It can be obtained by arbitrarily selecting 1000 or more, obtaining the distance between the two twin planes having the shortest distance among the even twin planes parallel to the main plane for each particle, and averaging them.

In the present invention, the average distance between twin planes is preferably 0.01 μm to 0.05 μm, more preferably 0.013 μm to 0.025 μm.

In the present invention, the distance between twin planes is a factor affecting the supersaturation state during nucleation, for example, gelatin concentration, gelatin type, temperature, iodine ion concentration, pBr, pBr.
It can be controlled by appropriately selecting a combination of various factors such as H, ion supply speed, and stirring rotation speed. In general, the more the nucleation is performed in a supersaturated state, the narrower the distance between twin planes can be.

For details regarding the supersaturation factor, see, for example, JP-A-63-92924 or JP-A-1-21363.
The description of No. 7, etc. can be referred to.

Next, $ 10 defined in claim 7 of the present invention.
Tabular grains having a 0 major plane (hereinafter abbreviated as {100} tabular grains) will be described. The {100} type tabular grains are tabular grains having two opposing {100} planes as main planes, and the shape of the main plane is a right-angled parallelogram or a right-angled parallelogram with one to four corners missing. It is a shape. Each side of the main plane may be curved as a convex curve.

The {100} tabular grains can be produced by referring to a known method. Preferably, the following (1) to
It can be manufactured with reference to the manufacturing method of (5).

(1) Method for forming silver bromide {100} tabular grains in which monodisperse seed grains are aged in the presence of ammonia, as described in JP-A-51-88017. (2) JP-A-58-95337. A method for forming silver bromide {100} tabular grains in which the seed grains are aged without the presence of a silver ion complexing agent other than a halide as described in (3) JP-A-6-308648, EP 670,
515A2, JP-A-7-234470, JP-A-8-
{100} tabular grains formed by forming one or more halogen composition gap planes at the time of forming seed grains or seed grains and introducing crystal defects that promote anisotropic growth described in JP-A-122950 and JP-A-8-122954. (4) The method described in EP 0,534,395 A1
^- in the dispersion medium solution in the presence of ions, to form a high AgCl content nucleus forming method of {100} tabular grains forming the crystal defects (5) JP-A-8-339044, JP-A 11-202
No. 437, etc., a method for forming {100} tabular particles by forming particles in the presence of a compound selected from adsorbents that promote the formation of {100} planes. Is particularly preferred.

In the emulsion defined in claim 7 of the present invention, the ratio of {100} tabular grains to the projected area of all silver halide grains is preferably at least 50%, more preferably at least 70%. It is more preferably 90% or more.

The thickness of the silver halide grains of the present invention is determined by observing the thickness of the shadow on an electron micrograph by performing metal vapor deposition from an oblique direction of the grains together with a reference latex, taking an electron micrograph, It is determined by referring to the shadow length of the latex.

According to the invention, the average thickness d of the particles is
Defined as the thickness di when the product ni × di ³ of the frequency ni and di ³ of the particles having i is maximum (three significant figures,
The smallest digit is rounded off to the nearest 5). However, the number of measured particles is indiscriminately 600 or more.

In the present invention, the average thickness d of the tabular grains is preferably from 0.05 μm to 1.5 μm, more preferably from 0.07 μm to 0.50 μm.

In the silver halide emulsion of the present invention, 50% or more of the total projected area of all silver halide grains are preferably grains having an aspect ratio (particle size / grain thickness) of 5 or more,
More preferably, 50% or more of the total projected area is a particle having an aspect ratio of 8 or more.

In the emulsion as defined in claim 1, 50% or more of the total projected area of all silver halide grains must be grains having an aspect ratio of 5 or more. It is necessary that 50% or more of the total projected area be particles having an aspect ratio of 8 or more, and 50% of the total projected area.
The above is preferably an aspect ratio of 10 or more.

The grain size of the silver halide grains in the present invention is represented by the equivalent circle diameter of the projected area of the silver halide grains (the diameter of a circle having the same projected area as the silver halide grains). Can be obtained by actually measuring the projected area of each particle on an electron micrograph.

[0056] In the present invention, the average particle diameter r is the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is defined as the particle size ri when the maximum (three significant figures, The smallest digit is rounded off to the nearest 5). However, the number of measured particles is indiscriminately 600 or more. The average grain size of the grains of the silver halide emulsion of the present invention is preferably from 0.1 to 5.0 μm, more preferably from 0.2 to 2.5 μm.

The silver halide emulsion of the present invention has a particle size of ri.
Standard deviation / average particle size r) × 100 = 25% when the width of the particle size distribution is defined by the variation coefficient [%] of the particle size distribution
The following are preferred. In particular, in the emulsion defined in claim 1, the width of the particle size distribution must be 25% or less. The width of the particle size distribution is more preferably 20% or less, and still more preferably 16% or less.

In the present invention, a monodispersed silver halide emulsion means that the variation coefficient of the particle size distribution of the silver halide emulsion is 25% or less.

Similarly, in the emulsion of the present invention, the width of the distribution of the grain thickness is determined by (standard deviation of the grain thickness di / average particle diameter d) × 100 = coefficient of variation [%] of the grain thickness distribution. Is preferably 35% or less, more preferably 25% or less, and still more preferably 20% or less.

The silver halide emulsion of the present invention as defined in claim 2 is a tabular grain having dislocation lines in the central region and the peripheral region of the main plane of the tabular grain (hereinafter referred to as "main plane / fringe dislocation line tabular grain"). ).

Dislocation lines possessed by silver halide grains are described, for example, in J. Am. F. Hamilton, Photo. Sci. E
ng. 11 (1967) 57; Shiozawa,
J. Soc. Photo. Sci. Japan 35 (19
72) It can be observed by a direct method using a transmission electron microscope at low temperature as described in 213 and the like.

That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for an electron microscope, and damage (print-out, etc.) by an electron beam is caused. Observation is performed by a transmission method in a state where the sample is cooled so as to prevent it. At this time, the thicker the particle, the more difficult it is for an electron beam to pass through, so that a method using a high-pressure electron microscope can observe more clearly. From the grain photograph obtained by such a method, the position and number of dislocation lines in each grain can be determined.

In the present invention, the central region of the main plane of the tabular grain has a radius of 80% of the radius of a circle having the same area as the main plane of the tabular grain, and shares the center with the main plane of the tabular grain. This is a region corresponding to a circular portion and having a thickness of tabular grains. On the other hand, the peripheral region of a tabular grain refers to a region having an area corresponding to an annular region outside the central region, existing around the tabular grain, and having a thickness of the tabular grain.

In the case of tabular grains, the number of dislocation lines present in one grain is measured as follows. A series of particle photographs with different inclination angles with respect to the incident electrons are taken for each particle to confirm the existence of dislocation lines. At this time, if the number of dislocation lines can be counted, the number of dislocation lines is counted. When it is not possible to count the number of dislocation lines per particle, such as when the dislocation lines exist densely or when the dislocation lines intersect each other, it is counted that there are many dislocation lines.

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

On the other hand, dislocation lines present in the outer peripheral region of the main plane / fringe dislocation line tabular grains of the present invention are observed as lines extending radially from the center of the grains toward the sides, but meandering. There is also.

In the silver halide emulsion of the present invention, 30% or more of the number ratio of the tabular grains contained therein has dislocation lines in both the central region and the peripheral region of the main plane and 1% in the peripheral region.
It is preferable that the tabular grains have 20 or more dislocation lines per grain, and 50% or more (number ratio) of tabular grains have dislocation lines in both the central region and the outer peripheral region of the main plane and have the outer peripheral region. More preferably, the grains have 30 or more dislocation lines per grain, and 70% or more (number ratio) of tabular grains have dislocation lines in both the central region and the peripheral region of the main plane, and have the outer periphery. More preferably, the region has 50 or more dislocation lines per particle.

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

The iodine ion releasing agent is, for example, a compound represented by the following general formula (III).

Formula (III) RI The compound represented by the formula (III) is a compound that releases iodide ions by reaction with a base or a nucleophile.

In the general formula (III), R represents a monovalent organic group. R represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group, a carbamoyl group, an alkyloxycarbonyl group,
Aryloxycarbonyl group, alkylsulfonyl group,
It is preferably an arylsulfonyl group or a sulfamoyl group. R is preferably an organic group having 30 or less carbon atoms, more preferably 20 or less, and even more preferably 10 or less.

It is preferable that R has a substituent, and the substituent may be further substituted with another substituent.

Preferred substituents include a halide, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Aralkyl group, heterocyclic group, acyl group, acyloxy group,
Carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, urethane group, sulfonylamino group, sulfinyl group, Examples include a phosphoric amide group, an alkylthio group, an arylthio group, a cyano group, a sulfo group, a carboxyl group, a hydroxy group, and a nitro group.

Specific examples of the iodine ion releasing agent RI are preferably iodoalkanes, iodoalcohol, iodocarboxylic acid, iodoamide and derivatives thereof, more preferably iodoamide, iodoalcohol and derivatives thereof, and a heterocyclic group Are more preferred, and the most preferred example is (iodoacetamido) benzenesulfonate.

Compounds (1) to (13) described on page 7 of JP-A-11-190885 are also specific examples of the iodine ion releasing agent which can be preferably used. Specific examples of (iodoacetamido) benzenesulfonate, which is the most preferable example, are compounds (10) to (13) described on page 7 of JP-A-11-190885.

When an iodide ion releasing agent is reacted with a nucleophile to release iodide ions, hydroxide ions, sulfite ions, thiosulfate ions, sulfinates, carboxylates, ammonia, Amines, alcohols, ureas, thioureas, phenols, hydrazines, sulfides, hydroxamic acids, and the like can be used, and hydroxide ions, sulfite ions, thiosulfate ions, sulfinates, carboxylate salts can be used. ,ammonia,
Amines are preferred, and hydroxide ions and sulfite ions are more preferred.

Preferred reaction conditions for introducing dislocation lines into the silver halide emulsion of the present invention with an iodine ion releasing agent are shown below.

The reaction temperature is preferably from 70 ° C. to 30 ° C., more preferably from 65 ° C. to 35 ° C. p
Br is preferably at most 1.50, more preferably at most 1.30, even more preferably at most 1.10.

The amount of the iodine ion releasing agent to be added is 0.5 to 3 mol based on the total amount of silver halide after completion of grain growth.
It is preferably 1%.

In the case where hydroxide ions are used as nucleophiles during the iodine ion releasing reaction, that is, when the iodide ion releasing agent is reacted by adjusting the pH, the reaction is carried out at a pH of 9.0 to 12.0. It is preferable to perform
More preferably, the pH is 10.0 to 11.0.

When a nucleophile other than hydroxide ion is used, the amount of the nucleophile is preferably 0.25 to 2.0 times the amount of the iodide ion releasing agent,
It is more preferably 0 to 1.5 times, and more preferably 0.80 to 1.2 times. PH at the time of iodine ion release reaction when the nucleophile is other than hydroxide ion
Is preferably from 5.0 to 11.0, and more preferably from 6.0 to 11.0.
More preferably, it is 10.0.

Preferred reaction conditions when dislocation lines are introduced into the silver halide emulsion of the present invention by a fine grain emulsion containing silver iodide are shown below.

The temperature at which the fine grain emulsion containing silver iodide is added is preferably from 70 ° C. to 30 ° C.,
C. is more preferable.

PBr is preferably 1.50 or less, more preferably 1.30 or less, and 1.10 or less.
It is more preferred that:

The amount of the fine grain emulsion containing silver iodide to be added is
The amount of silver iodide is preferably 0.5 to 3 mol% with respect to the total amount of silver halide after completion of grain growth.

Next, the normal crystal grains having dislocation lines defined in claim 6 of the present invention will be described.

In the case of normal crystal grains, similarly to tabular grains,
It can be observed by a method using a transmission electron microscope at a low temperature. However, in the case of normal crystal grains, transmission observation of an electron beam is often difficult due to the grain thickness. In such a case, the silver halide grains are cut into 0.25 μm or thinner in parallel with the (100) plane while paying careful attention so as not to apply enough pressure to generate dislocations. , The presence or absence of dislocation lines can be confirmed.

The number of dislocation lines per grain of the normal crystal grains of the present invention is 10 or more, preferably 20 or more.
30 or more are more preferable. The number of dislocation lines per normal crystal grain referred to herein means that a flake having a thickness of 0.2 ± 0.05 μm including one (100) surface per cubic particle is cut out as described above. Is defined as the number of dislocation lines when observed from the (100) direction.

In the present invention, when dislocation lines are introduced into normal crystal grains, the pAg is preferably less than 7.8.

The start of the introduction of dislocation lines is preferably 30 to 90%, more preferably 40 to 70% in terms of the amount of silver consumed for grain growth before the introduction of dislocation lines. .

The average silver iodide content of the outermost layer in the main plane portion and the side surface portion of the silver halide grain defined in claim 4 of the present invention will be described.

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

A specific method for measuring the average silver iodide content of the outermost layer in the main plane portion and the side surface portion is as follows.

The tabular silver halide grains in the silver halide photographic emulsion are decomposed by gelatin using a proteolytic enzyme, taken out, embedded in methacrylic resin, and continuously cut into pieces having a thickness of about 500 mm with a diamond cutter. Of these sections, those having a tomographic plane perpendicular to the two parallel principal planes of the tabular silver halide grains, including a principal plane surface on the tomographic planes of the tabular silver halide grains. The silver halide phase from the surface parallel to the main plane surface to a depth of 50 ° is referred to as a main plane portion, and the outermost layer of the silver halide crystal, other than the main plane portion, is referred to as a side surface portion.

The main plane portion and the side surface portion are made to have a spot diameter of 50 ° or less by using the EPMA method well known in the art.
Preferably, the silver iodide content is measured by point analysis narrowed to 20 ° or less.

Five or more measurements are made at equal intervals, including both ends of the main plane portion and the side surface portion, and the number average of the measured values is defined as the average silver iodide content of the outermost layer.

[0097] Emulsions as defined in claim 4 of the present invention, I ₁ the average silver iodide content outermost layer of the silver halide grains in the main flat portion, when the I ₂ in a side section, I _1> It is characterized in that tabular silver halide grains of I ₂ account for 50% or more (number). The relationship between I ₁ and I ₂ is preferably I ₁ / I ₂ > 1.3, more preferably I ₁ / I ₂ > 2.0, and I ₁ / I ₂ > 2.5. Is most preferred. In the present invention, I ₁ is preferably less than 30 mol% and 0.5 mol% or more, more preferably less than 20 mol% and 1 mol% or more.

A particularly preferred method for producing the emulsion defined in claim 4 of the present invention is as follows: (1) First, a high iodide silver halide phase is preferentially grown in the main plane direction, and (2) Conversely, a low iodide silver halide phase is preferentially grown in the lateral direction, and then a high iodine halide is grown in the main plane direction. There are two types of manufacturing methods for growing a silver halide phase.

The preferred pBr for growing tabular grains preferentially in the lateral direction is 1.0 to 2.5, and the gelatin concentration is 0.5 to 2.0%. In order to form high aspect ratio tabular silver halide grains not to be formed, the pH is preferably set to 2.0 to 5.0. On the other hand, the preferred pBr for growing preferentially in the main plane direction is 2.5 to 4.5.

In order to suppress the growth of tabular grains in the main plane direction or the side direction, it is also preferable to use additives called silver halide growth control agents, crystal habit control agents or inhibitors in the art.

For example, for tabular silver halide grains,
First, after growing a low silver iodide-containing surface phase in the lateral direction, U.S. Patent Nos. 5,147,771 and 5,14
7,772 and 5,147,773,
By adding a polyalkylene oxide-related compound described in, for example, Japanese Patent No. 308644, growth in the lateral direction can be suppressed, and as a result, it can be preferentially grown in the main plane direction. A sensitizing dye having surface-selective adsorptivity can also be used to suppress the growth in the main plane direction or side direction.

In addition to the above methods (1) and (2), preferred methods for producing the emulsion defined in claim 4 of the present invention include a conversion method by adding a halide solution alone, and a method described in JP-A-58-108526. No., 59-1335
No. 40, No. 59-162540, etc. can also be used.

The operations for producing the silver halide phases having different halogen compositions in the various lateral directions / principal plane directions are performed from the start of silver halide grain formation to the crystal growth of silver halide grains, physical ripening, and desalting. The color sensitization and the chemical sensitization can be carried out in any one or more steps, as necessary, until the coating liquid preparation step is completed. 9 in silver
It is preferably performed in a step after completion of 0% or more, and preferably performed before completion of color sensitization and chemical sensitization.

The emulsion defined in claim 5 of the present invention is characterized in that it contains silver halide grains formed by using a grain-to-grain distance control method.

In the present invention, the method of controlling the distance between grains means that in the step of forming silver halide grains, a reactant solution for forming grains is concentrated to reduce the volume of the reactant solution or to reduce the volume of the reactant solution. By concentrating the volume increase due to the addition liquid of (1) and keeping the volume increase, or by suppressing the volume increase, the average interparticle distance = [volume of reactant solution /
Number of growing grains in reactant solution] × 1/3, and controls the average intergranular distance between silver halide grains in the reactant solution.

More specifically, the intergranular distance control method uses a device in which a concentrating mechanism such as an ultrafiltration device is connected to a reaction vessel for forming silver halide grains. This is achieved by removing only water or an aqueous solution containing a soluble substance from the reaction solution.

The concentrating mechanism is connected to the reaction vessel by a pipe or the like, and the reactant solution can be circulated at an arbitrary flow rate between the reaction vessel and the concentrating mechanism by a circulating mechanism for the reactant solution such as a pump, and stopped arbitrarily. It is a facility that has a device capable of detecting the volume of an aqueous solution containing a salt extracted from a reaction solution by the concentration mechanism, and a mechanism capable of arbitrarily controlling the amount. . Further, other functions can be provided as necessary.

Further, an apparatus such as an ultrafiltration apparatus to which a concentrating mechanism is connected is preferably an apparatus having a mechanism for increasing the average interparticle distance by adding water at a set temperature to a reaction vessel.

As means for achieving the intergranular distance control method in the present invention, the production equipment and production method for silver halide emulsions described in JP-A-10-339923 can be particularly preferably used.

In the present invention, the method of controlling the distance between grains during grain formation means that (1) the volume of the reaction solution is reduced by using the above-mentioned concentration mechanism in the step of forming silver halide grains.

(2) In the step of forming silver halide grains, an aqueous solution containing water or a soluble substance in the same amount as the amount of the added liquid for forming silver halide is removed from the reaction solution using the above-mentioned concentration mechanism. Keep the volume of the reactant solution constant.

(3) In the step of forming silver halide grains, an aqueous solution containing water or a soluble substance is removed from the reaction solution simultaneously with the addition of an additive for silver halide formation by using the above-mentioned concentration mechanism. In addition, the increase in the volume of the reactant solution is suppressed.

The above operations (1) to (3) or combinations thereof are meant. In (3), the volume of the reactant solution may increase or decrease as a result of suppressing the volume increase.

In the present invention, the above (1) to (1)
The following operation (4) is preferably used in combination with (3).

(4) Water or an aqueous solution containing a soluble substance is added to increase the volume of the reaction solution.

In the present invention, when the emulsion is not circulated between the concentration mechanism such as an ultrafiltration device and the reaction vessel to remove water or an aqueous solution containing a soluble substance, the interparticle distance control method is applied. Does not prescribe.

In the present invention, the method for controlling the distance between particles does not necessarily need to be applied over the entire step of forming particles.
Rather, it is preferable to use it in the step of forming particles.

As described above, the grain formation step of the silver halide emulsion is roughly classified into a nucleation step (consisting of a nucleation step and a nucleation step) and a growth step. The control method is preferably applied to a step of growing silver halide grains.

The silver halide emulsion of the present invention may contain a polyvalent metal compound as a metal dopant. In particular, it is preferable that at least one or more polyvalent metal compounds are contained in the outer periphery of the tabular grains contained in the silver halide emulsion of the present invention.

The metal dopant is a polyvalent metal compound to be contained in, or doped with, the crystal lattice of silver halide grains, and is different from an organic hole trapping dopant.

In the present invention, as a metal dopant,
Mg, Al, Ca, Sc, Ti, V, Cr, Mn, F
e, Co, Cu, Zn, Ga, Ge, Sr, Y, Zr,
Nb, Mo, Tc, Ru, Rh, Pd, Cd, Sn, B
a, Ce, Eu, W, Re, Os, Ir, Pt, Hg,
Metal compounds such as Tl, Pb, Bi, and In can be preferably used.

The metal dopant is preferably selected from a single salt or a metal complex. When selecting from metal complexes, 6-coordinate, 5-coordinate, 4-coordinate and 2-coordinate complexes are preferred, and octahedral 6-coordinate and planar 4-coordinate complexes are more preferred. The complex may be a mononuclear complex or a polynuclear complex.

The ligands constituting the complex include C
N ⁻ , CO, NO ₂ ⁻ , 1,10-phenanthroline,
2,2′-bipyridine, SO ₃ ⁻ , ethylenediamine, N
H ₃ , pyridine, H ₂ O, NCS ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , O
_{^{H -, N 3 -, S}} 2 -, F -, Cl -, Br -, I - or the like can be used. Particularly preferred metal dopants are K ₄ Fe (CN) ₆ , K ₃ Fe (CN) ₆ , Pb (NO
₃ ) ₂ , K ₂ IrCl ₆ , K ₃ IrCl ₆ , K ₂ IrBr ₆ , I
nCl ₃ .

The above-mentioned metal dopant can be added during the grain formation step of the silver halide emulsion of the present invention or in any step after the formation step, but is preferably added during the grain growth step. The metal dopant can be added as its own solution,
It can also be mixed and added to another additive liquid for forming particles, such as a halide liquid. It is also possible to add it in a state of being doped in the silver halide fine grain emulsion in advance.

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

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

When gelatin is used as the protective colloid in the grain formation step of the silver halide emulsion of the present invention, the gelatin may be either lime-treated or acid-treated. The details of the method for producing gelatin are described in Arthur Guice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

Japanese Patent Application Laid-Open Nos. 5-72658 and 9-72
Chemically modified gelatin in which the amino group of gelatin is substituted as described in 197595 and JP-A-9-251193 can be preferably used as a protective colloid during grain formation.

When a chemically modified gelatin is used in the particle forming step, it is preferable that 10% by mass or more of the total dispersion medium used for the particle formation is the chemically modified gelatin, more preferably 30% by mass or more.
More preferably, it is 50% by mass or more.
The substitution ratio of the amino group is preferably 30% or more, more preferably 50% or more, and further preferably 80% or more.

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

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

As a means for forming the silver halide emulsion of the present invention, various methods well known in the art can be used. That is, a single jet method, a controlled double jet method, a controlled triple jet method, or the like can be used in any combination. In determining the addition rate, refer to JP-A-54-4
No. 8521 and the technology described in JP-A-58-49938 can be referred to.

In the production of the silver halide emulsion of the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like may be present, or a silver halide solvent may not be used. The pH / temperature of the aging step is preferably 7.0 to 11.0 / 40 ° C to 80 ° C,
8.5-10.0 / 50 degreeC-70 degreeC is more preferable.

The silver halide emulsion of the present invention may be one obtained by removing unnecessary soluble salts after completion of the growth of silver halide grains, or may be one which contains unnecessary soluble salts. It is preferable that they have been removed. When the salts are removed, Research Disclosure may be used.
e, hereinafter abbreviated as RD) can be carried out based on the method described in 17643 No. II.

More specifically, in order to remove the soluble salt from the emulsion after the formation of the precipitate or after the physical ripening, a Nudel washing method, which is performed by gelling gelatin, may be used. A precipitation method (flocculation) using an activator, an anionic polymer (eg, polystyrene sulfonic acid), or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used. A method using a chemically modified gelatin obtained by substituting an amino group of gelatin described in JP-A-5-72658 can be preferably used.
In particular, the use of chemically modified gelatin in which the amino group of gelatin is phenylcarbamoylated is preferred. When chemically modified gelatin is used for removing salts, the substitution ratio of amino groups is 30.
% Or more, more preferably 50% or more, and 80% or more.
The above is more preferred.

The silver halide emulsion of the present invention may be used alone in the emulsion layer, provided that the effects of the present invention are not impaired.
It can be used by mixing with other silver halide emulsions.

It is preferable to use a mixture of two or more emulsions of the present invention or to use them separately in different layers of the same light-sensitive material.

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

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

The silver halide emulsion of the present invention may contain an antifoggant, a stabilizer and the like.

As the binder, it is advantageous to use gelatin. The emulsion layer and other hydrophilic colloid layers
It can be hardened and can contain a plasticizer, a dispersion (latex) of a water-insoluble or soluble synthetic polymer.

The silver halide photographic emulsion of the present invention can be used for light-sensitive materials, and can be preferably used for color light-sensitive materials such as color films for general use and motion pictures, color paper, color reversal films and color reversal papers. .

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

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

To the light-sensitive material, a matting agent, a lubricant, an image stabilizer, a formalin scavenger, an ultraviolet absorber, a fluorescent brightener, a surfactant, a development accelerator and a development retarder can be added.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

[0147]

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

Example 1 (Preparation of Em-10) A tabular emulsion containing no organic hole-trapping dopant was prepared as follows.

[Nucleation Step] The following gelatin solution B-101 in a reaction vessel was kept at 30 ° C.
Stirring speed of 40 using a mixing stirrer described in JP-A-28
While stirring at 0 revolutions / minute, the pH was adjusted to 1.96 with 1 mol / L sulfuric acid. Thereafter, the S-101 solution and the X-101 solution were added to the B-101 solution for one minute by a double jet method at a constant flow rate to form nuclei.

(B-101) 32.4 g of alkali-treated inert gelatin (average molecular weight 100,000), potassium bromide 9.
An aqueous solution containing 92 g and 12938 ml of water (S-101) 237.5 m of a 1.25 M silver nitrate aqueous solution
l (X-101) 1.25 M aqueous potassium bromide solution 23
7.5 ml [Aging step] After the above addition was completed, add G-101 solution and add
The temperature was raised to 60 ° C. over a period of 0 minutes. After the temperature was raised, the pH was adjusted to 5.0 using an aqueous potassium hydroxide solution, and
Hold for minutes. During this time, the pAg was controlled at 8.6 using a 1 M aqueous potassium bromide solution while measuring the silver potential of the solution (using a saturated silver-silver chloride electrode as a reference electrode and using a silver ion selective electrode).

(G-101) 139.1 g of alkali-treated inert gelatin (average molecular weight 100,000), 4.64 ml of a 10% by mass methanol solution of the following [Compound A], water 32
Aqueous solution containing 66 ml [Compound A] HO (CH ₂ CH ₂ O) m [CH (CH ₃ )
CH ₂ O] _19.8 (CH ₂ CH ₂ O) nH (m + n = 9.7
7) [Grain growth step-1] After the ripening, the flow rates of the S-102 solution and the X-102 solution are accelerated using the double jet method (the ratio of the addition flow rate at the end to the start is about 12). Times)
It was added to the solution. After completion of the addition, the solution G-102 was added, and the stirring speed was adjusted to 550 rpm, followed by S
The -103 solution and the X-103 solution were added to the solution while accelerating the flow rates (the ratio of the addition flow rates at the end and at the start was about twice). During this time, the pAg of the solution was controlled at 8.9.

(S-102) 1.25 M aqueous solution of silver nitrate 3013 ml (X-102) 1.25 M aqueous solution of potassium bromide 301
Aqueous solution (S-103) containing 3M (G-102) 203.4 g of alkali-treated inert gelatin (average molecular weight: 100,000), 6.2 ml of a 10% by mass methanol solution of [Compound A], and 1867 ml of water (S-103) 2069 ml of aqueous silver nitrate solution (X-103) 3.43 M potassium bromide and 0.07 M
2069 ml of an aqueous solution containing potassium iodide [Grain growth step-2] After completion of the above addition, the pAg was adjusted to 7.6 using a 1M aqueous solution of silver nitrate, and then the S-104 solution and the X-104 solution were obtained by using a double jet method. Was added to the solution while accelerating the flow rate (the ratio of the addition flow rate at the end to the start was 1.2 times).

(S-104) 3.5 M aqueous silver nitrate solution 8
07ml (X-104) 3.47M potassium bromide and 0.03M
807 ml of an aqueous solution containing potassium iodide after the completion of the growth, subjected to a desalting / washing treatment in accordance with a conventional method, adding gelatin, dispersing well, and adjusting the pH to 5.8 at 40 ° C.
The pAg was adjusted to 8.1. The emulsion thus obtained was
m-10. Em-10 was an emulsion in which tabular grains having an aspect ratio of 5 or more accounted for 44% of the projected area of all silver halide grains, and the coefficient of variation of the grain size was 27%.

(Preparation of Em-11) Except for the following steps, Em
In the same manner as in -10, a tabular emulsion Em-11 containing an organic hole trapping dopant was prepared. Em-1
1 is that tabular grains having an aspect ratio of 5 or more occupy 44% of the projected area of all silver halide grains, and the coefficient of variation of the grain size is 2%.
7% of the emulsion had dislocation lines in the central region and the peripheral region of the main plane of the tabular grains.

[Grain Growth Step-2] After the addition of the particle growth step-1, 200 ml of an aqueous solution containing 2.0 g of sodium p-toluenethiosulfonate was added, and the pAg was adjusted to 7.6 using a 1M aqueous silver nitrate solution. S-
Solution 114, solution X-114 and solution D-114 were added to the solution by the triple jet method while accelerating the flow rate (the ratio of the addition flow rate at the end to the addition at the start was 1.2 times). Then, S-1
Solution 15 and X-115 were added to the solution at a constant flow rate using the double jet method.

(S-114) 3.5 M silver nitrate aqueous solution 5
65 ml (X-114) 3.47 M potassium bromide and 0.03 M
565 ml of an aqueous solution containing potassium iodide (D-114) 565 ml of an aqueous solution containing 94 mg of sodium formate (S-115) 242 ml of a 3.5 M silver nitrate aqueous solution (X-115) 3.47 M of potassium bromide and 0.03 M
242 ml of an aqueous solution containing potassium iodide (Preparation of Em-12) A tabular emulsion Em-12 containing no organic hole-trapping dopant was prepared in the same manner as Em-10 except for the following steps. Em-12 was an emulsion in which tabular grains having an aspect ratio of 5 or more occupied 95% of the projected area of all silver halide grains and had a variation coefficient of grain size of 14%.

[Nucleation Step] The following gelatin solution B-301 in a reaction vessel was kept at 30 ° C.
Stirring speed of 40 using a mixing stirrer described in JP 28
While stirring at 0 revolutions / minute, the pH was adjusted to 1.96 with 1 mol / L sulfuric acid. Thereafter, the S-101 solution and the X-101 solution were added to the B-121 solution in one minute by a double jet method at a constant flow rate to form nuclei.

(B-121) Oxidized low molecular weight gelatin (average molecular weight: 20,000, methionine content: 10 [μmole]
/ Gelatin [g] or less) 32.4 g, potassium bromide 9.
Aqueous solution containing 92 g and 12938 ml of water [Maturation step]
The temperature was raised to 60 ° C. over a period of 0 minutes. During this time, pAg was controlled at 8.9 using a 1 M aqueous solution of potassium bromide. After the temperature was raised, 90.0 ml of a 28% ammonia aqueous solution was added, and the pH was adjusted to 9.3 with an aqueous potassium hydroxide solution to adjust the pH to 9.3.
Hold for 0 minutes, and then use 1 mol / L sulfuric acid
H was adjusted to 5.0.

(Preparation of Em-13) The steps from [nucleation step] to [particle growth step-1] were carried out in the same manner as Em-12, and [particle growth step-2] was carried out in the same manner as Em-11. Thus, a tabular emulsion Em-13 containing an organic hole trapping dopant was prepared. Em-13 was an emulsion in which tabular grains having an aspect ratio of 5 or more occupied 95% of the projected area of all silver halide grains and had a variation coefficient of grain size of 14%.

(Preparation of Em-14)
In the same manner as in -10, tabular emulsion Em-14 containing no organic hole-trapping dopant was prepared. Em-
No. 14, tabular grains having an aspect ratio of 2 or more occupy 98% of the projected area of all silver halide grains, the coefficient of variation of the grain size is 16%, and dislocation lines are formed in the central region and the peripheral region of the main plane of the tabular grains. Emulsion.

[Grain Growth Step-2] After the completion of the grain growth step-1, 0.283 mol equivalent of silver iodide fine grain emulsion (average grain size: 0.04 μm) was added. Subsequently, the pAg was adjusted to 7.6 using a 1M aqueous solution of silver nitrate, and the flow rates of the S-144 solution and the X-144 solution were continuously accelerated using the double jet method (the addition flow rate at the end and at the start). The ratio was 1.2 times).

(S-144) 3.5 M silver nitrate aqueous solution 7
27 ml (X-144) 3.47 M potassium bromide and 0.03 M
727 ml of an aqueous solution containing potassium iodide (Preparation of Em-15) A tabular emulsion Em-15 containing an organic hole trapping dopant was prepared in the same manner as Em-14 except for the following steps. In Em-15, tabular grains having an aspect ratio of 2 or more occupy 98% of the projected area of all silver halide grains, have a variation coefficient of grain size of 16%, and have dislocations in the central region and the peripheral region of the main plane of the tabular grains. It was an emulsion with lines.

[Grain Growth Step-2] After the completion of the grain growth step-1, 200 ml of an aqueous solution containing 2.0 g of sodium p-toluenethiosulfonate and 0.283 mol of silver iodide fine grain emulsion (average grain size) 0.04 μm) was added. Subsequently, pAg7.6 using a 1M aqueous solution of silver nitrate was used.
, And then S-154 solution, X-154 solution and D
The -154 liquid was added to the liquid by a triple jet method while accelerating the flow rate (the ratio of the flow rate at the end to the flow at the start was 1.2 times). Thereafter, the S-115 solution and the X-115 solution were added in the liquid at a constant flow rate using a double jet method.

(S-154) 3.5 M silver nitrate aqueous solution 4
84 ml (X-154) 3.47M potassium bromide and 0.03M
484 ml of an aqueous solution containing potassium iodide (D-154) 484 ml of an aqueous solution containing 94 mg of sodium formate (preparation of Em-16) A flat plate containing no organic hole-trapping dopant in the same manner as Em-12 except for the following steps. A solid emulsion Em-16 was prepared. In Em-16, tabular grains having an aspect ratio of 8 or more occupy 86% of the projected area of all silver halide grains, have a variation coefficient of grain size of 22%, and have dislocations in the central region and the peripheral region of the main plane of the tabular grains. It was an emulsion with lines.

[Maturation Step] After the addition of the nucleation step, G-
Solution 161 was added, and the temperature was raised to 60 ° C. over 30 minutes.
During this time, the pAg was controlled at 9.2 using a 1 M aqueous potassium bromide solution. After raising the temperature, 28% aqueous ammonia 4
Add 5.0 ml and adjust the pH using an aqueous solution of potassium hydroxide.
Was adjusted to 9.3 and maintained for 15 minutes. Then, 13 L of water at 60 ° C. was added, and the pH was adjusted to 5.0 using 1 mol / L sulfuric acid.

(G-161) Oxidized low molecular weight gelatin (average molecular weight 50,000, methionine content 10 [μmole]
/ Gelatin [g] or less) 139.1 g, water 3266 ml
[Grain-growing step-2] 0.2 after completion of the particle-growing step-1
83 mole equivalent silver iodide fine grain emulsion (average grain size 0.04μ)
m) was added. Subsequently, the pAg was adjusted to 7.9 using a 1M aqueous solution of silver nitrate, and then the S-144 solution and the X-144 solution were accelerated using the double jet method while increasing the flow rates (the addition flow rates at the end and at the start). The ratio was 1.2 times).

(Preparation of Em-17)
In the same manner as in -16, a tabular emulsion Em-17 containing an organic hole-trapping dopant was prepared. Em-1
In No. 7, tabular grains having an aspect ratio of 8 or more occupy 86% of the projected area of all silver halide grains, and the variation coefficient of the grain size is 2
2%, an emulsion having dislocation lines in the central region and the peripheral region of the main plane of the tabular grains.

[Grain Growth Step-2] After the completion of the grain growth step-1, 200 ml of an aqueous solution containing 3.0 g of sodium p-toluenethiosulfonate and a silver iodide fine grain emulsion equivalent to 0.283 mol (average grain size) 0.04 μm) was added. The pAg was adjusted to 7.9 with a 1M aqueous silver nitrate solution, and then the S-154 solution, X-154 and D-174 were adjusted.
The liquid was added to the liquid by a triple jet method while accelerating the flow rate (the ratio of the addition flow rate at the end to the start was 1.2 times). Thereafter, the S-115 solution and the X-115 solution were added in the liquid at a constant flow rate using a double jet method.

(D-174) Sodium formate 1
726 ml of an aqueous solution containing 41 mg (Preparation of Em-18) A tabular emulsion Em-18 containing no organic hole-trapping dopant was prepared in the same manner as Em-12 except for the following steps. In Em-18, tabular grains having an aspect ratio of 5 or more occupy 90% of the projected area of all silver halide grains, have a variation coefficient of grain size of 16%, and have dislocations in the central region and the peripheral region of the main plane of the tabular grains. It was an emulsion with lines. Further, the analysis method described in Japanese Patent Application No. Hei 10-314669, the outermost layer average silver iodide content I ₁ of the main plane of the tabular grain, the outermost layer average silver iodide content I ₂ of the side surface portion is, It was confirmed that I ₁ > I ₂ .

[Grain Growth Step-2] After the completion of the grain growth step-1, 0.283 mol equivalent of silver iodide fine grain emulsion (average grain size 0.04 μm) was added, and pAg 7.6 was added using a 1M silver nitrate aqueous solution. Then, the S-184 solution and the X-184 solution were added to the solution using the double jet method while accelerating the flow rates (the ratio of the addition flow rate at the end to the addition at the start was 1.1 times). PA using 3.5 M aqueous potassium bromide solution
g10.3, and then the S-185 solution and the X-185 solution were added to the solution at a constant flow rate using the double jet method.

(S-184) 3.5 M silver nitrate aqueous solution 4
84 ml (X-184) 3.22 M potassium bromide and 0.28 M
Aqueous solution containing potassium iodide 484 ml (S-185) 1.0 M aqueous silver nitrate solution 848 ml (X-185) 1.0 M aqueous potassium bromide solution 848 m
l (Preparation of Em-19) A tabular emulsion Em-19 containing an organic hole trapping dopant was prepared in the same manner as Em-18 except for the following steps. In Em-19, tabular grains having an aspect ratio of 5 or more occupy 90% of the projected area of all silver halide grains, have a variation coefficient of grain size of 16%, and have dislocations in the central region and the peripheral region of the main plane of the tabular grains. It was an emulsion with lines. Further, the analysis method described in Japanese Patent Application No. Hei 10-314669, the outermost layer average silver iodide content I ₁ of the main plane of the tabular grain, the outermost layer average silver iodide content I ₂ of the side surface portion is, It was confirmed that I ₁ > I ₂ .

[Particle Growth Step-2] After the completion of the particle growth step-1, sodium p-toluenethiosulfonate 2.0
g of an aqueous solution containing 200 g and a silver iodide fine grain emulsion (average particle size: 0.04 μm) equivalent to 0.283 mol were added. 1M
Then, the pAg was adjusted to 7.6 using an aqueous silver nitrate solution, and then the S-184 solution, the X-184 solution, and the D-194 solution were accelerated while increasing the flow rates (the ratio of the addition flow rate at the end to the start was 1. (1x) Added in liquid by triple jet method.
PAg 10.3 using 3.5 M aqueous potassium bromide solution
And then S-18 using the double jet method
Liquid 5 and liquid X-185 were added at a constant flow rate in the liquid.

(D-194) Sodium formate 9
484 ml of an aqueous solution containing 4 mg (Preparation of Em-20) Em-1 up to the particle growth step-1
6 and the subsequent steps from grain growth step-2
A tabular emulsion Em-20 containing no organic hole-trapping dopant was prepared by a method for controlling the distance between grains using a silver halide emulsion production facility having the same configuration as that shown in FIG. 1 of JP-A-339923. In Em-20, tabular grains having an aspect ratio of 8 or more occupy 91% of the projected area of all silver halide grains, have a variation coefficient of grain size of 18%, and have dislocations in the central region and the peripheral region of the main plane of the tabular grains. It was an emulsion with lines. Further, the analysis method described in Japanese Patent Application No. Hei 10-314669, the outermost layer average silver iodide content I ₁ of the main plane of the tabular grain, the outermost layer average silver iodide content I ₂ of the side surface portion is, I
_1> it was confirmed that the relationship of I _2.

[Particle Growth Step-2] After the completion of the particle growth step-1, the reactant solution in the reaction vessel is circulated to the ultrafiltration unit to concentrate the reactant solution to 1/5 (the distance between the particles is (Reduced to 58% at the end of step-1). afterwards,
0.283 mole equivalent silver iodide fine grain emulsion
04 μm) and pAg using a 1 M aqueous solution of silver nitrate.
Adjusted to 7.6 and then S using the double jet method
The -184 liquid and the X-184 liquid were added to the liquid while accelerating the flow rates (the ratio of the addition flow rate at the end to the start was 1.1 times).
PAg 10.3 using 3.5 M aqueous potassium bromide solution
And then S-18 using the double jet method
Liquid 5 and liquid X-185 were added at a constant flow rate in the liquid. The circulation of the reactant solution to the ultrafiltration unit was continued throughout the entire area of the particle growth step-2, and was maintained at 58% of the value at the end of the particle growth step-1.

(Preparation of Em-21) The steps up to the grain growth step-1 are carried out in the same manner as in the case of Em-20, and the steps following the grain growth step-2 are the same as those in FIG. 1 of JP-A-10-339923. A tabular emulsion Em-21 containing an organic hole trapping dopant was prepared by a silver halide emulsion production facility by a method of controlling the distance between grains. Em-21 is
Tabular grains having an aspect ratio of 8 or more occupy 91% of the projected area of all silver halide grains, have a grain size variation coefficient of 18%,
The emulsion had dislocation lines in the central region and the peripheral region of the main plane of the tabular grains. Further, the analysis method described in Japanese Patent Application No. Hei 10-314669, the outermost layer average silver iodide content I ₁ of the main plane of the tabular grain, the outermost layer average silver iodide content I ₂ of the side surface portion is, It was confirmed that I ₁ > I ₂ .

[Particle Growth Step-2] After the completion of the particle growth step-1, the reactant solution in the reaction vessel is circulated to the ultrafiltration unit to concentrate the reactant solution to 1/5 (the distance between the particles is (Reduced to 58% at the end of step-1). afterwards,
0.283 mole equivalent silver iodide fine grain emulsion
04 μm) and pA was added using a 1M aqueous solution of silver nitrate.
g to 7.6, and then increasing the flow rates of the S-184 solution, X-184 solution, and D-194 solution using the double jet method (the ratio of the addition flow rate at the end to the start was 1. 1
Fold) was added in the liquid by the triple jet method. 3.5M
The solution was adjusted to pAg 10.3 using an aqueous potassium bromide solution, and then the S-185 solution and the X-185 solution were added to the solution at a constant flow rate by a double jet method. In addition, the circulation of the reaction solution to the ultrafiltration unit was continued over the entire area of the particle growth step-2.
It was kept at 8%.

[Photosensitive material sample No. 10-A-No. 1
Preparation of 5-B] Each of the emulsions Em-10 to Em-21 was added to 5
While maintaining the temperature at 2 ° C., the sensitizing dyes SSD-1, SSD-2, and S-2 shown on page 17 of JP-A-10-339923 are described.
SD-3 was added. After aging for 20 minutes, chloroauric acid and potassium thiocyanate were added, and sodium thiosulfate and trifurylphosphine selenide were further added. After ripening so as to obtain an optimum sensitivity-fog relationship for each emulsion, 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1,3,3a, 7-
Stabilization was achieved by adding tetraazaindene. The amount of sensitizing dye, sensitizer and stabilizer added to each emulsion and the ripening time were 1
/ 200 sec. Exposure was set so that the sensitivity-fog relationship was optimized.

Em-10 to Em-21 after sensitization
In each emulsion of the above, MCP-1 shown in page 17 of JP-A-10-339923 was dissolved in ethyl acetate and tricresyl phosphate and emulsified and dispersed in an aqueous solution containing gelatin, a spreading agent, and a hardener. A coating solution was prepared by adding a general photographic additive such as a coating agent, and was coated on an undercoated cellulose triacetate film support according to a conventional method and dried.
Color photosensitive material sample No. 10-A-No. Fifteen
-B was produced.

[0179]

[Table 1]

Immediately after preparing these samples,
Wedge exposure was performed through a Toshiba glass filter (Y-48) using a light source with a color temperature of 5400 ° K, and development was performed according to the following processing steps.

Further, in order to confirm the effects of the present invention, storage stability, pressure resistance and latent image stability were also evaluated.

In order to evaluate the storage stability, the target sample was subjected to a forced deterioration test (preserved at 40 ° C. and a relative humidity of 80% for 7 days), and then subjected to the same treatment.

In order to evaluate the pressure resistance, the target sample was
After holding for 24 hours in an atmosphere of 3 ° C. and a relative humidity of 55%, a 5 g load was applied to a needle having a tip having a curvature radius of 0.025 mm using a scratch strength tester (manufactured by Shinto Kagaku) under the same conditions. And the same process was performed by scanning the sample surface at a constant speed.

To evaluate the stability of the latent image, a forced deterioration test (40 ° C., 80% relative humidity) was performed on the target sample after exposure.
) For 4 days, followed by the same treatment.

(Processing Step) Processing Time Processing Time Processing Temperature Replenishment Color Development 2 min 50 sec 38 ± 0.3 ° C. 780 ml Bleaching 45 sec 38 ± 2.0 ° C. 150 ml Fixing 1 min 30 sec 38 ± 2.0 ° C. 830 ml stable 1 minute 38 ± 5.0 ° C. 830 ml dry 1 minute 55 ± 5.0 ℃ - ※ replenishing amount is a value per photosensitive material 1 m ^2.

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

Color developer Water 800 cc Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino- 3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and add potassium hydroxide or 20
The pH is adjusted to 10.06 with% sulfuric acid.

Replenisher for color development Water 800 cc Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyl Ethyl) aniline sulfate 6.3 g potassium hydroxide 2 g diethylenetriaminepentaacetic acid 3.0 g water was added to make 1 liter, and potassium hydroxide or 20
Adjust to pH 10.18 with%.

Bleaching solution Water 700 cc Ammonium iron (III) 1,3-diaminopropanetetraacetate 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Add water to make 1 liter, and use ammonia water or glacial acetic acid. And adjust to pH 4.4.

Bleach replenisher Water 700 cc 1,3-Diaminopropanetetraacetate iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting to pH 4.4 using aqueous ammonia or glacial acetic acid Add water to make 1 liter.

Fixing solution Water 800 cc Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher Water 800 cc Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizing Solution and Stabilizing Replenisher Water 900 cc paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 cc Add water to make 1 liter, then add ammonia water or 5
Adjust to pH 8.5 with 0% sulfuric acid.

The sensitivity and fog of the obtained color photographic material sample were measured using green light. At the same time, storage stability, pressure resistance, and latent image storage stability were also evaluated. The evaluation method is described below.

The relative fog was measured by measuring the density (= Dmin) of the unexposed portion of each sample and calculating the Dmin of each reference sample.
The values are shown as relative values with the value being 100. The smaller the value of the relative fog, the lower the fog. Relative sensitivity was calculated as the minimum concentration (Dmin) +0.2 in each sample.
The reciprocal of the exposure amount giving the density of was determined, and the relative value was expressed assuming that the sensitivity of each reference sample was 100. The higher the relative sensitivity value, the higher the sensitivity, which is preferable.

The storage stability was evaluated by the relative sensitivity fluctuation width and the relative fog fluctuation width. Relative fog fluctuation width was obtained by calculating the absolute value (Δfog) of the difference between the Dmin value immediately after sample preparation and the Dmin value after the forced deterioration test in each sample, and calculating the Δf in each reference sample.
The values are shown as relative values with fog being 100. The smaller the value of the relative fog fluctuation width, the better the storage stability.

Similarly, the relative sensitivity fluctuation width is determined by measuring the density Dmi of the unexposed portion immediately after sample preparation and after the forced deterioration test in each sample.
The absolute value (Δ sensitivity) of the difference between the values of the reciprocal of the exposure amount giving a density of n + 0.2 was determined, and the Δ sensitivity
The relative value is set to 0. The smaller the value of the relative sensitivity variation width, the better the storage stability.

The pressure resistance was evaluated by the relative fog increase due to the pressure. The relative fog increase width was obtained by measuring the amount of increase in the density of the unexposed portion of the portion to which the load was applied, and expressed as a relative value (ΔDp1) with the amount of increase in the density of each reference sample being 100. The smaller the value, the smaller the fog increase due to the pressure being applied, and the more excellent the pressure resistance.

The latent image stability was evaluated by the relative sensitivity fluctuation width. The relative sensitivity variation width is obtained by calculating the absolute value (Δ sensitivity) of the difference between the reciprocal of the exposure value that gives a density of Dmin + 0.2 immediately after sample preparation and after the forced degradation test in each sample, and calculating the sensitivity variation from each reference sample. It is shown as a relative value with the width being 100. The smaller the value of the relative sensitivity variation width, the better the latent image stability.

Table 2 shows the obtained results.

[0201]

[Table 2]

From the results shown in Table 2, the following (1) to
(5) is understood. From the behavioral behavior of Samples 10-B and 11-B with respect to each reference sample, (1) the silver halide photographic emulsion of Claim 1 of the present invention was used while maintaining the sensitizing effect of the organic hole trapping dopant. It can improve fog increase and deterioration of storage stability of a silver halide photographic emulsion.

From the performance behavior of Samples 10-B and 12-B with respect to each reference sample, (2) the sensitizing effect of the organic hole trapping dopant was maintained by the silver halide photographic emulsion of Claim 2 of the present invention. As it is, deterioration of the pressure resistance of the silver halide photographic emulsion can be improved.

From the performance behavior of Samples 10-B and 13-B with respect to each reference sample, (3) the silver halide photographic emulsion of claim 3 of the present invention makes the effect of sensitizing organic hole trapping dopants more remarkable. Can be obtained.

From the performance behavior of Samples 10-B and 14-B with respect to each reference sample, (4) the silver halide photographic emulsion of claim 4 of the present invention further improves the sensitizing effect of the organic hole trapping dopant. And the deterioration of the storage stability of the latent image of the silver halide photographic emulsion can be improved.

Comparison of the performance behavior of Samples 10-B and 15-B shows that (5) the silver halide photographic emulsion according to claim 5 of the present invention can further improve sensitivity, storage stability and latent image stability. It can be seen that the effect of improving the properties can be obtained. Further, by combining the respective constitutions of the silver halide photographic emulsion of the present invention, the effects of the present invention can be obtained independently or as higher effects.

In the above examples, the organic hole-trapping dopant (sodium formate) used in the preparation of the emulsion was replaced with a Rongalit compound (JP-A-11-233771).
No. 0, page 5, compound II. When evaluation was performed in place of 1), the effect of the present invention could be similarly confirmed.

Example 2 (Preparation of Seed Emulsion N-1) 500% aqueous solution of 2.0% alkali-treated inert gelatin (average molecular weight 100,000) at a temperature of 40 ° C.
250 ml of a 4M silver nitrate aqueous solution and 25 ml of an aqueous solution containing 3.92 M potassium bromide and 0.08 M potassium iodide in accordance with the method described in JP-A-50-45437.
0 ml is pA by the controlled double jet method.
g was controlled at 9.0 and the pH was controlled at 2.0 over 35 minutes. After completion of the addition, the mixture was subjected to a desalting and washing treatment by a coagulation sedimentation method, and an aqueous gelatin solution was added thereto to redisperse the seed emulsion to prepare a seed emulsion (total amount: 435 ml). This seed emulsion is designated as N-1. As a result of observation by an electron microscope, it was found that the emulsion was a monodispersed normal crystal emulsion having an average particle size of 0.093 μm.

(Preparation of silver iodide fine grain emulsion N-2) 9.9
6.0 m% aqueous alkali-treated inert gelatin (average molecular weight 100,000) aqueous solution containing 6 g of potassium iodide 5000 m
While maintaining the temperature at 40 ° C., a 3.53 M aqueous solution of silver nitrate and a 3.53 M aqueous solution of potassium iodide were each 2,000 m 2.
was added over 10 minutes. During the addition, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate, and the mass was adjusted to 12.53 kg. As a result of observation with an electron microscope, the average particle size of the silver iodide fine particles was about 0.05 μm.

(Preparation of silver iodobromide fine grain emulsion N-3)
2000 ml of a 3.53 M silver nitrate aqueous solution while maintaining 5000 ml of a 6.0 mass% aqueous solution of low molecular gelatin (average molecular weight: 20,000) containing 14 g of potassium bromide at 30 ° C.
And 2000 ml of an aqueous solution containing 3.46 M potassium bromide, 0.07 M potassium iodide and 4.4 × 10 ⁻³ mol of K ₂ IrCl ₆ were added over 10 minutes. P during addition
H was controlled at 2.0 using nitric acid, and the temperature was controlled at 30 ° C.
After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate, and the mass was adjusted to 12.53 kg. As a result of observation with an electron microscope, the average particle size of the silver iodobromide fine particles was about 0.0
It was 3 μm.

(Preparation of silver bromide fine grain emulsion N-4) 7.1
While maintaining 5000 ° C. of a 6.0% by mass aqueous solution of low molecular gelatin (average molecular weight: 20,000) containing 4 g of potassium bromide at 30 ° C., 2,000 ml of a 3.53 M aqueous silver nitrate solution and 2000 ml of a 3.53 M aqueous potassium bromide solution were added. Added over 10 minutes. The pH during the addition was adjusted to 2.0 using nitric acid,
The temperature was controlled at 30 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate, and the mass was adjusted to 12.
The weight was 53 kg. As a result of observation with an electron microscope, the average particle size of the silver iodobromide fine particles was about 0.03 μm.

(Preparation of Emulsion Em-1) Emulsion Em-1 was prepared by the following method.

To Gr-10 stirred at 70 ° C., 4230 ml of S-10 and X-10 were added by a controlled double jet method. During this time, 1.75M
The pAg was maintained at 7.7 with an aqueous potassium bromide solution, and the pH was maintained at 4.0 with an aqueous acetic acid solution. Next, 300 ml of an aqueous solution containing 3.5 g of sodium p-toluenethiosulfonate was added, and the pAg was adjusted to 5.5 in S-10.
10 and X-11 were added by the controlled double jet method. The pAg was maintained at 5.5 and the pH at 4.0 until the addition of S-10 was completed. The above S-10, X-1
The addition rates of 0 and X-11 were optimally set so that no new small particles were generated. After the addition of S-10,
A 3.5 M aqueous potassium bromide solution was added to adjust the pAg to 9.1.
And then stirred for 2 minutes.

(Gr-10) Alkali-treated inert gelatin (average molecular weight: 100,000), 161.1 g, a 10% by mass methanol solution of the compound A in 3.0 ml, a seed emulsion (N-
1) Aqueous solution containing 97.7 ml and water 3980 ml (S-10) 3.5M silver nitrate aqueous solution 5983 ml (X-10) aqueous solution containing 3.43 M potassium bromide and 0.07 M potassium iodide 4230 ml (X- 11) 1753 ml of an aqueous solution containing 3.36 M potassium bromide and 0.14 M potassium iodide, followed by desalting according to the method described in JP-A-5-72658, adding gelatin and dispersing, followed by iodine odor After adding 736 g of a silver halide fine grain emulsion (N-3) solution and dispersing and ripening until the fine grains were dissolved, the pH was adjusted to 5.8 and the pAg to 8.1 at 40 ° C. The emulsion thus obtained is designated as Em-1. The silver halide grains contained in Em-1 had an average side length of one cube of 0.42 μm,
The cubic normal crystal grains had a variation coefficient of side length of 13%.

(Preparation of Emulsion Em-2) Emulsion Em-2 was prepared by the following method.

To Gr-10 stirred at 70 ° C., 4230 ml of S-10 and X-10 were added by a controlled double jet method. During this time, 1.75
The pAg was maintained at 7.7 with an aqueous potassium bromide solution of M, and the pH was maintained at 4.0 with an aqueous acetic acid solution. Next, 300 ml of an aqueous solution containing 3.5 g of sodium p-toluenethiosulfonate
Was added and the pAg was adjusted to 5.5 with S-10.
-10, X-11 and D-10 were added by a controlled triple jet method. The pAg was maintained at 5.5 and the pH at 4.0 until the addition of S-10 was completed. The above S
The addition rates of -10, X-10 and X-11 were optimally set so that no new small particles were generated. After the addition of S-10 was completed, a 3.5 M aqueous potassium bromide solution was added and p
After adjusting the Ag to 9.1, the mixture was stirred for 2 minutes.

(D-10) Sodium formate 14
1753 ml of an aqueous solution containing 1 mg, followed by desalting according to the method described in JP-A-5-72658, and adding and dispersing gelatin, and then adding 736 g of a silver iodobromide fine grain emulsion (N-3) solution to add fine grains. After dispersing and aging until was dissolved, the pH was adjusted to 5.8 and the pAg to 8.1 at 40 ° C. The emulsion thus obtained is referred to as Em-2. The silver halide grains contained in Em-2 had an average side length of one cube of 0.42 μm,
Cubic normal crystal grains having a side length variation coefficient of 15% were obtained.

(Preparation of Emulsion Em-3) Emulsion Em-3 was prepared by the following method.

4230 ml of S-20 and X-20 were added to Gr-10 stirred at 70 ° C. by a controlled double jet method. During this time, 1.75
The pAg was maintained at 7.7 with an aqueous potassium bromide solution of M, and the pH was maintained at 4.0 with an aqueous acetic acid solution. Next, 300 ml of an aqueous solution containing 3.5 g of sodium p-toluenethiosulfonate
Was added and B-10 was added at a constant rate over 2 minutes. Thereafter, pAg was adjusted to 5.5 with a 1.75 M aqueous silver nitrate solution, and S-20 and X-21 were added by a controlled double jet method. The pAg was maintained at 5.5 and the pH at 4.0 until the addition of S-20 was completed. The above S-
The addition rates of 20, X-20 and X-21 were optimally set so that no new small particles were generated. After the addition of S-20, a 3.5 M aqueous solution of potassium bromide was added to add pA
After adjusting g to 9.1, the mixture was stirred for 2 minutes.

(S-20) 3.5 M aqueous silver nitrate solution 58
67 ml (X-20) 4230 ml of an aqueous solution containing 3.43 M potassium bromide and 0.07 M potassium iodide (X-21) 1632 ml of an aqueous solution containing 3.36 M potassium bromide and 0.14 M potassium iodide ( B-10) Silver iodide fine grain emulsion (N-2) solution 752.
1 g Then, desalting treatment is performed according to the method described in JP-A-5-72658, gelatin is added and dispersed, and then 736 g of a silver iodobromide fine grain emulsion (N-3) solution is added until the fine grains are dissolved. After dispersion and aging, the pH was adjusted to 5.8 and the pAg to 8.1 at 40 ° C. The emulsion thus obtained is named Em-3. The silver halide grains contained in Em-3 had an average length of one side of the cube of 0.42 μm,
The cubic normal crystal grains had a variation coefficient of side length of 13%. In addition, according to the method described in Japanese Patent Application No. 11-231057, it was confirmed that the particles had 10 or more dislocation lines.

(Preparation of Emulsion Em-4) Emulsion Em-4 was prepared by the following method.

Into Gr-10 stirred at 70 ° C., 4230 ml of S-20 and X-20 were added by a controlled double jet method. During this time, 1.75
The pAg was maintained at 7.7 with an aqueous potassium bromide solution of M, and the pH was maintained at 4.0 with an aqueous acetic acid solution. Next, 300 ml of an aqueous solution containing 3.5 g of sodium p-toluenethiosulfonate
Was added and B-10 was added at a constant rate over 2 minutes. Thereafter, the pAg was adjusted to 5.5 with a 1.75 M silver nitrate aqueous solution, and S-20, X-21 and D-20 were added by a controlled triple jet method. The pAg was maintained at 5.5 and the pH at 4.0 until the addition of S-20 was completed. The addition rates of S-20, X-20 and X-21 were optimally set so that no new small particles were generated. After the addition of S-20 was completed, a 3.5 M aqueous solution of potassium bromide was added to adjust the pAg to 9.1, and the mixture was stirred for 2 minutes.

(D-20) Sodium formate 14
1632 ml of an aqueous solution containing 1 mg, followed by desalting according to the method described in JP-A-5-72658, adding and dispersing gelatin, and then adding 736 g of a silver iodobromide fine grain emulsion (N-3) solution to add fine grains. After dispersing and aging until was dissolved, the pH was adjusted to 5.8 and the pAg to 8.1 at 40 ° C. The emulsion thus obtained is named Em-4. The silver halide grains contained in Em-4 had an average length of one side of the cube of 0.42 μm,
Cubic normal crystal grains having a side length variation coefficient of 15% were obtained. In addition, according to the method described in Japanese Patent Application No. 11-231507, it was confirmed that the particles had 10 or more dislocation lines.

(Preparation of Emulsion Em-5) Emulsion Em-5 was prepared by the following method.

The pH of Gr-50 maintained at 40 ° C. was adjusted to 3.00 with nitric acid while stirring in a reaction vessel.
In 20 seconds, S-50 and X-50 were added. After the addition was completed, the pAg was adjusted to 6.6 with an aqueous silver nitrate solution and the pH was adjusted to 6.0 with an aqueous sodium hydroxide solution, and the temperature was raised to 75 ° C. Immediately after the temperature was raised, the pAg was adjusted to 5.5 and physical ripening was performed for 90 minutes. Next, 2.3 ml of an aqueous solution containing 26.4 mg of sodium p-toluenethiosulfonate was added, and 101 g of a silver bromide fine grain emulsion (N-4) solution was further added at a constant rate by a single jet method for another 60 minutes. Physical ripening was performed. S-5 in 34 minutes
1 and X-51 were added by a controlled double jet method while maintaining the pAg at 5.6.

(Gr-50) Aqueous solution containing 200 g of alkali-treated inert gelatin (average molecular weight 100,000) and 10,000 ml of water (S-50) 156 ml of 1.0 M silver nitrate aqueous solution (X-50) 1.0 M potassium bromide 156 ml of an aqueous solution (S-51) 373 ml of an aqueous solution of 0.01 M silver nitrate (X-51) 373 ml of an aqueous solution of 0.01 M silver nitrate The obtained emulsion was subjected to desalting / washing treatment by ultrafiltration, and additional gelatin was added. In addition, it was redispersed. Thereafter, 5.5 g of a silver iodobromide fine grain emulsion (N-3) solution was added and dispersed and ripened until the fine grains were dissolved. Then, the pH was adjusted to 5.8 and the pAg to 8.1 at 40 ° C. . The emulsion thus obtained is named Em-5. In Em-5, two parallel main planes are (100) planes, and tabular silver halide grains having an aspect ratio of 2 or more have a total projected area of 8 of the silver halide grains.
Occupies 3%, and the average value of one side length in cube is 0.42 μm
Silver halide emulsion.

(Preparation of Emulsion Em-6) Emulsion Em-6 was prepared by the following method.

The pH of Gr-50 kept at 40 ° C. was adjusted to 3.00 with nitric acid while stirring in a reaction vessel.
In 20 seconds, S-50 and X-50 were added. After the addition was completed, the pAg was adjusted to 6.6 with an aqueous silver nitrate solution and the pH was adjusted to 6.0 with an aqueous sodium hydroxide solution, and the temperature was raised to 75 ° C. Immediately after the temperature was raised, the pAg was adjusted to 5.5 and physical ripening was performed for 90 minutes. Next, after adding 2.3 ml of an aqueous solution containing 26.4 mg of sodium p-toluenethiosulfonate, 101 g of a silver bromide fine particle emulsion (N-4) solution and D-50 were added at a constant rate by a double jet method. Physical ripening was further performed for 60 minutes. Continue 34
In a minute, S-51 and X-51 were added by a controlled double jet method while maintaining the pAg at 5.6.

(D-50) Sodium formate
12.3 ml of an aqueous solution containing 0 mg The obtained emulsion was subjected to a desalting and washing treatment using an ultrafiltration method, and additional gelatin was added to redisperse the emulsion. Thereafter, 5.5 g of a silver iodobromide fine grain emulsion (N-3) solution was added and dispersed and ripened until the fine grains were dissolved. Then, the pH was adjusted to 5.8 and the pAg to 8.1 at 40 ° C. . The emulsion thus obtained is named Em-6. In Em-6, two parallel main planes are (100) planes, and tabular silver halide grains having an aspect ratio of 2 or more have a total projected area of 8 of the silver halide grains.
Occupies 3%, and the average value of one side length in cube is 0.42 μm
Silver halide emulsion.

[Photosensitive material sample No. 1-A to No. 3-
Preparation of B] While keeping each of the emulsions Em-1 to Em-6 at 52 ° C., sensitizing dyes SSD-1, SSD-2, and SSD-3 shown on page 17 of JP-A-10-339923.
Was added. After aging for 20 minutes, chloroauric acid and potassium thiocyanate were added, and sodium thiosulfate and trifurylphosphine selenide were further added. After ripening each emulsion so as to obtain the optimum sensitivity-fog relationship, A1-phenyl-5-mercaptotetrazole and
-Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added for stabilization. The amount of sensitizing dye, sensitizer and stabilizer added to each emulsion and the ripening time were 1/20.
The sensitivity-fog relation at the time of 0 second exposure was set to be optimal.

To each of the emulsions Em-1 to Em-6 which had been subjected to the sensitization treatment, MCP-1 shown in page 17 of JP-A-10-339923 was dissolved in ethyl acetate and tricresyl phosphate to prepare gelatin. A coating solution is prepared by adding a general photographic additive such as a dispersion, a spreading agent and a hardening agent, which is emulsified and dispersed in an aqueous solution containing the solution, and coated on an undercoated cellulose triacetate film support according to a conventional method. After drying, the color photographic material sample No. 1-A to No. 3-B was produced.

[0232]

[Table 3]

Immediately after the preparation of these samples, the evaluation of relative fog and relative sensitivity was performed in the same manner as in Example 1. Further, in order to confirm the effects of the present invention, evaluations of storage stability and pressure resistance were also performed.

The pressure resistance was evaluated based on the relative fog increase due to pressure and the decrease in relative sensitivity.

The relative fog increase width is determined by measuring the amount of increase in the density of the unexposed portion where a load is applied in the same manner as in Example 1, and calculating the relative value (Δ
Dp1). The smaller the value, the smaller the fog increase due to the pressure being applied, and the more excellent the pressure resistance.

The range of decrease in the relative sensitivity is the intermediate density D (= [maximum density−minimum density]) in the portion where no load is applied.
/ 2) and the ΔD (= D−D ′) of the density D ′ of the portion where the load was applied at the same exposure amount was measured, and the relative value (ΔDp2) with the density increase amount of each reference sample as 100 was obtained. Indicated. The smaller this value is, the smaller the decrease in sensitivity due to the pressure being applied and the better the pressure resistance.

Table 4 shows the obtained results.

[0238]

[Table 4]

From the results shown in Table 4, claim 6 of the present invention was obtained.
It can be seen that the silver halide photographic emulsion described above can further improve the sensitizing effect of the organic hole trapping dopant, and can also improve the deterioration of fog, storage stability and pressure resistance.

Further, it can be seen that the silver halide photographic emulsion according to claim 7 of the present invention can improve fog, storage stability and deterioration of pressure resistance, and can obtain a more remarkable sensitizing effect.

In the above examples, the organic hole-trapping dopant (sodium formate) used in the preparation of the emulsion was replaced with a Rongalit compound (JP-A-11-237771).
No. 0, page 5, compound II. When evaluation was performed in place of 1), the effect of the present invention could be similarly confirmed.

[0242]

The silver halide photographic emulsion according to the present invention and the silver halide photographic light-sensitive material containing the silver halide photographic emulsion can be prepared by applying an organic hole-trapping dopant to obtain sensitivity, fog, storage stability before exposure, It has an excellent effect of improving the latent image preservability and pressure resistance after exposure.

Claims (11)

[Claims] 1. A tabular silver halide grain having an aspect ratio of 5 or more occupies 50% or more of the projected area of all silver halide grains, and the coefficient of variation of the grain size distribution of all silver halide grains is 25%.
% Or less, wherein the tabular silver halide grains contain an organic hole trapping dopant. 2. Tabular silver halide grains having an aspect ratio of 2 or more, wherein said tabular silver halide grains have dislocation lines in a central region and a peripheral region of a main plane, and A silver halide photographic emulsion comprising an organic hole-trapping dopant in grains. 3. The tabular silver halide grains having an aspect ratio of 8 or more occupy 50% or more of the projected area of all silver halide grains, and the tabular silver halide grains contain an organic hole trapping dopant. A silver halide photographic emulsion comprising: 4. The tabular silver halide grains containing tabular silver halide grains having an aspect ratio of 2 or more, wherein 50% or more (number) of the tabular silver halide grains satisfy the following formula 1, and A silver halide photographic emulsion comprising an organic hole trapping dopant therein. Formula 1 Average outermost layer silver iodide content in main plane portion> Average outermost layer silver iodide content in side surface portion 5. A silver halide photograph containing silver halide grains formed by the intergranular distance control method and containing an organic hole-trapping dopant in the silver halide grains. emulsion. 6. A silver halide photographic emulsion comprising normal-crystal silver halide grains having 10 or more dislocation lines and containing an organic hole-trapping dopant in the normal-crystal silver halide grains. . 7. Tabular silver halide grains having an aspect ratio of 2 or more and having a {100} principal plane, and an organic hole-trapping dopant is contained in the tabular silver halide grains. Silver halide photographic emulsion. 8. The silver halide photographic emulsion according to claim 1, wherein the organic hole trapping dopant is a compound represented by the following general formula (I). Formula (I) R-COOM (wherein, R is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aromatic heterocyclic ring Represents a residue, and M is a hydrogen atom or a metal atom or an organic group capable of forming a salt). 9. The silver halide photographic emulsion according to claim 8, wherein in the general formula (I), R is a hydrogen atom. 10. The silver halide photographic emulsion according to claim 1, wherein the organic hole trapping dopant is a compound represented by the following general formula (II). Embedded image (Wherein, X and Y represent O, S or Se, m is 1, n is 1 or 2, R ₁ and R ₂ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted A substituted aryl group,
Represents a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aromatic heterocyclic residue, wherein R ₁ and R ₂ may be the same or different, and may form a ring; E is a group linked to a carbon atom by a heteroatom having at least one free electron pair, and M ⁺ is a proton, organic or inorganic cation. ) 11. A silver halide photographic material comprising the silver halide photographic emulsion according to claim 1. Description: