JP2003222967A - Silver halide emulsion and silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide emulsion having high sensitivity, excellent pressure resistance and improved processing stability and to provide a silver halide photographic sensitive material using the emulsion. <P>SOLUTION: In the silver halide emulsion, 70-100% of the total projected area of all silver halide grains is occupied by tabular silver halide grains, the average aspect ratio of the tabular silver halide grains is 8-500, the tabular silver halide grains have ≥30 dislocation lines per grain in the periphery, and when the density of dislocation lines near the vertexes is represented by D<SB>1</SB>and that in the fringes by D<SB>2</SB>, the ratio of tabular silver halide grains satisfying D<SB>1</SB>/D<SB>2</SB>=1.3-1,000 is 50-100% by number. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion and a silver halide photographic light-sensitive material using the same, and more specifically, a silver halide emulsion having high sensitivity, excellent pressure resistance and processing stability, and a silver halide emulsion containing the same. The present invention relates to the silver halide photographic light-sensitive material used (hereinafter, also simply referred to as light-sensitive material).

[0002]

2. Description of the Related Art In recent years, compact cameras and autofocus 1
Due to the increasing popularity of eye reflex cameras, and the widespread use of cameras with lenses, etc., it has been strongly demanded that silver halide photographic light-sensitive materials be highly functional and inexpensive. Therefore, it is necessary to develop a photographic silver halide emulsion having improved manufacturing costs as well as improved performance such as sensitivity, graininess and sharpness.

Further, the silver halide light-sensitive material is subjected to various pressures during its production and use. For example, a negative film for general photography is subjected to great pressure during cutting and perforation in the manufacturing process, and is also bent or rubbed when conveyed in a camera. As described above, it is known that photographic performance changes when various pressures are applied to the silver halide light-sensitive material, and a technique for improving resistance to these pressures is desired.

As a method of increasing the sensitivity of a silver halide emulsion, a technique of introducing a transition line into tabular silver halide grains is disclosed in US Pat. No. 4,956,269. It is generally known that when pressure is applied to silver halide grains, fogging or desensitization occurs, but grains introduced with dislocation lines have a problem of being significantly desensitized when pressure is applied. Was.

Further, a technique for improving the sensitivity / size ratio per silver halide grain is being researched in order to further improve the sensitivity and the image quality, and one of them is a tabular halogenation. A technique using silver particles is disclosed in JP-A-58-1.
No. 11935, No. 58-111936, No. 58-11
No. 1937, No. 58-113927, No. 59-994.
No. 33, etc. Comparing these tabular silver halide grains with so-called normal crystal silver halide grains such as hexahedral, octahedral, and dodecahedral grains, the surface area per unit volume of silver halide grains is large, so that the surface area of the grains increases. The spectral sensitizing dye can be adsorbed, and high sensitivity including improvement of color sensitization efficiency can be expected.

Further, JP-A-63-220238 and JP-A-1-201649 disclose tabular silver halide grains in which dislocation lines are intentionally introduced. The tabular silver halide grains having dislocation lines introduced are superior to tabular silver halide grains having no dislocation lines in photographic characteristics such as sensitivity and reciprocity law, and when they are used in a light-sensitive material, they are sharp and granular. It has been shown to be excellent in sex. In order to further increase the sensitivity of silver halide grains, it is necessary to introduce dislocation lines uniformly and at high density within individual grains and between grains, and to limit the dislocation line balance within each grain. Homogeneity,
It is considered preferable in terms of efficient chemical sensitization and efficiency of the latent image forming site.

JP-A-1-329231 discloses that a tabular silver halide grain having 10 or more dislocation lines per grain in the fringe portion of the grain is highly sensitive and has improved graininess, gradation and fog. It has been shown that a silver emulsion is obtained.

Further, JP-A-3-175440 discloses a method for producing an emulsion in which dislocations are concentrated near the apexes of tabular silver halide grains. This is because after bonding silver iodide or silver halide having a high silver iodide content to the apex of tabular silver halide grains directly or through halogen conversion by iodide ions to form a joined silver halide. , Followed by the growth of tabular silver halide grains.

However, in the conventional dislocation line introduction as shown in these patents, the sensitivity and pressure resistance are contradictory, the photographic performance is insufficient, and further improvement is required.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a silver halide emulsion having high sensitivity, excellent pressure resistance, and improved processing stability. And further to provide a silver halide photographic light-sensitive material using the emulsion.

[0011]

The above objects of the present invention have been achieved by the following constitutions.

1. 70 of the projected area of all silver halide grains
To 100% are tabular silver halide grains, the tabular silver halide grains have an average aspect ratio of 8 to 500, and each tabular silver halide grain has 30 or more dislocations in the outer peripheral portion. has a line, when the density of the dislocation line near the apex and D _1, the density of the dislocation lines of the fringe portion and D ₂ D ₁ /
A silver halide emulsion characterized in that the ratio of tabular silver halide grains having a D ₂ value of 1.3 or more and 1000 or less is 50 to 100% by number.

2. 70 of the projected area of all silver halide grains
To 100% are tabular silver halide grains, the tabular silver halide grains have an average aspect ratio of 8 to 500, and each tabular silver halide grain has 30 or more dislocations in the outer peripheral portion. The average length of dislocation lines near the apex is S ₁ , and the average length of dislocation lines in the fringe portion is S ₂
, The ratio of tabular silver halide grains having an S ₁ / S ₂ value of 1.5 or more and 100 or less is 50 to 100% by number, and a silver halide emulsion is characterized.

3. 50 to 50 of the tabular silver halide grains
3. The silver halide emulsion as described in 1 or 2 above, wherein 100% by number has dislocation lines in the main plane.

4. 70 of the projected area of all silver halide grains
˜100% are tabular silver halide grains, the tabular silver halide grains have an average aspect ratio of 8 to 500, and the tabular silver halide grains have a dislocation line localized near the apex in the outer peripheral portion. And the proportion of tabular silver halide grains having dislocation lines in the main plane is 50 to 100% by number, a silver halide emulsion.

5. 5. The silver halide emulsion according to any one of 1 to 4 above, wherein the tabular silver halide grains have a variation coefficient of grain size distribution of 30% or less.

6. 6. The silver halide emulsion as described in any one of 1 to 5 above, wherein the tabular silver halide grains have an average aspect ratio of 15 to 500.

7. Any one of the above items 1 to 6, characterized in that the tabular silver halide grains have an average value of projected area circle conversion grain sizes of 1.0 to 50 µm and an average thickness of 0.005 to 0.1 µm. Item 8. Silver halide emulsion according to the item 8. From an n-valent cation radical with an intramolecular cyclization reaction (n
+ M) at least one organic compound capable of forming a cation (provided that n and m each independently represent an integer of 1 or more and 100 or less), and any of 1 to 7 above The silver halide emulsion according to item 1.

9. 9. A silver halide photographic light-sensitive material comprising the silver halide emulsion described in any one of 1 to 8 above in at least one silver halide emulsion layer on a support.

The present invention will be described in detail below. The present invention provides a ratio of dislocation line density of each part of a tabular silver halide grain, a ratio of average length of dislocation lines, and
One of the characteristics is that it relates to the ratio of dislocation line existence positions, and optimizes the density of dislocation lines existing in the vicinity of vertices, fringes, and main planes, the average length, and the position of existence. As a result, they have found that the sensitivity is high, the pressure resistance is excellent, and the processing stability is improved.

In the present invention, the vicinity of the apexes of tabular silver halide grains (hereinafter, also simply referred to as tabular grains) means the center of the tabular grains, that is, the main plane, when it has a triangular or hexagonal outer surface. when the length of the line segment connecting the centroid and each vertex of which taken as a two-dimensional figure was L ₁ and refers to a region within a distance of 0.05 L ₁ from each vertex.

When the tabular grains are rounded, the vertices are ambiguous, but in this case as well, it is 6 with respect to the outer circumference.
Two tangents can be obtained, and the point where the straight line connecting the intersection of each tangent and the center of the tabular grain intersects the outer periphery of the tabular grain can be obtained as the apex. When the outer surface has a hexagonal shape, there are six vertices, and when the outer surface has a triangular shape, there are three vertices.

In the present invention, the outer peripheral portion of the tabular silver halide grain means the center of the tabular grain, that is, the main plane when the shape of the tabular silver halide grain is viewed as a two-dimensional figure from the direction perpendicular to the principal plane. when the length of the perpendicular line drawn from the center of gravity of which taken as a two-dimensional figure in each side was L _2, it refers to a region of the distance from the contain and each side of each side until 0.05 L ₂ inside.

The fringe portion as referred to in the present invention means a region which is included in the outer peripheral portion of the tabular silver halide grains and which is the remaining portion of the outer peripheral portion excluding the vicinity of the apex.

The dislocation lines possessed by the silver halide grains are described in, for example, J. F. Hamilton, Photo. Sci.
Eng. 11 (1967) 57 and T.I. Shiozawa
a, J. Soc. Photo. Sci. Japan, 3
5 (1972) 213 and can be observed by a direct method using a transmission electron microscope at low temperature described therein. That is, the silver halide grains taken out carefully so as not to apply a pressure to generate new dislocation lines from the emulsion, are placed on the mesh of the electron microscope to prevent damage (printout etc.) by the electron beam. The sample is observed by the transmission method in the cooled state. At this time, the thicker the silver halide grains, the more difficult it is for an electron beam to pass therethrough. Therefore, a high-voltage electron microscope can be used for clearer observation. The position, number, and density of dislocation lines in each silver halide grain can be determined from the grain photograph obtained by such a method.

In the present invention, the density of dislocation lines represents the number of dislocation lines existing per unit length of side. It is observed that the dislocation lines near the apex and in the fringe portion extend from the inside of the silver halide grain toward each side or apex when the tabular silver halide grain is viewed from the direction perpendicular to the main plane. For the density of dislocation lines of the tabular silver halide grains, a transmission electron micrograph of the tabular silver halide grains as seen from the direction perpendicular to the main plane is shown in Adobe P.
After uploading to image processing software such as photoshop, monochromatic processing is performed, and about 500 or more tabular silver halide grains are divided into the vicinity of the vertices and the fringe portion, and the number of dislocation lines is counted respectively, and the dislocation lines are counted in the vicinity of the vertices. It is determined by gradually dividing by the length of the side included in each fringe portion.

In the silver halide emulsion according to claim 1 of the present invention, 70 to 100% of the projected area of all silver halide grains are tabular silver halide grains, and the average aspect of the tabular silver halide grains is The ratio is 8 to 500, the tabular silver halide grains have 30 or more dislocation lines in the outer periphery per grain, the density of dislocation lines near the apex is D ₁ , and the density of dislocation lines in the fringe portion. the proportion of tabular silver halide grains values of D ₁ / D ₂ is 1.3 to 1,000 when the D ₂ is characterized in that 50 to 100% by number.

The value of D ₁ / D ₂ is 1.3 or more and 1000 or less, preferably 1.5 or more and 1000 or less,
More preferably 2 or more and 1000 or less, and D ₁
The ratio of tabular silver halide grains having a value of / D ₂ of 1.3 or more and 1000 or less is 50 to 100% by number, and 70
-100% by number is preferable, and 80-100% by number is more preferable.

If the value of D ₁ / D ₂ of the tabular silver halide grains is less than 1.3 or exceeds 1,000, pressure resistance and processing stability may be deteriorated. The ratio of tabular silver halide grains having a D ₁ / D ₂ value of 1.3 or more and 1000 or less is 5
If it is less than 0% by number, improvement in pressure resistance and processing stability may be insufficient. When the tabular silver halide grains are less than 70% of the projected area of all the silver halide grains, the sensitizing effect due to the increase of the light receiving area by using the tabular silver halide grains may not be fully enjoyed. If the aspect ratio of the tabular silver halide grains is less than 8, the sensitizing effect due to the increase in the light receiving area due to the use of the tabular silver halide grains may not be fully enjoyed. If it exceeds 500, it may be difficult to maintain the processing stability. If there are less than 30 dislocation lines in the outer peripheral portion of the tabular silver halide grains, the pressure resistance effect may be insufficient. Also, 1000
If the number of dislocation lines is exceeded, it may be difficult to measure the number of dislocation lines.

A silver halide emulsion according to claim 2 of the present invention
Is 70 to 100% of the projected area of all silver halide grains.
Tabular silver halide grains, said tabular silver halide
The average aspect ratio of the particles is 8 to 500,
The number of silver halide grains per grain is 30 or more
The average value of the length of dislocation lines near the top
S ₁, S is the average length of the dislocation lines in the fringe area.₂And
S₁/ S₂Of flat plate having a value of 1.5 or more and 100 or less
The ratio of silver rogenide grains is 50-100% by number.
Is characterized by.

The value of S ₁ / S ₂ is 1.5 or more and 100 or less, preferably 2.0 or more and 100 or less.
It is more preferably 0 or more and 100 or less, and S ₁ /
The ratio of tabular silver halide grains having an S ₂ value of 1.5 or more and 100 or less is 50 to 100% by number, and 70 to 1
00% by number is preferable, 80-100% by number
Is more preferable.

If the S ₁ / S ₂ value of the tabular silver halide grains is less than 1.5 or more than 1000, the processing stability may deteriorate. If the ratio of tabular silver halide grains having an S ₁ / S ₂ value of 1.5 or more and 100 or less is less than 50% by number, the pressure resistance and the processing stability may be insufficiently improved. When the tabular silver halide grains are less than 70% of the projected area of all the silver halide grains, the sensitizing effect due to the increase of the light receiving area by using the tabular silver halide grains may not be fully enjoyed. If the aspect ratio of the tabular silver halide grains is less than 8, the sensitizing effect due to the increase in the light receiving area due to the use of the tabular silver halide grains may not be fully enjoyed. If it exceeds 500, it may be difficult to maintain the processing stability. If there are less than 30 dislocation lines in the outer peripheral portion of the tabular silver halide grains, the pressure resistance effect may be insufficient. Further, if the number exceeds 1000, it may be difficult to measure the number of dislocation lines.

Average value S ₁ of the lengths of dislocation lines near the apex
And the average S ₂ of the lengths of the dislocation lines in the fringe portion is a transmission electron micrograph of the tabular silver halide grains used for the calculation of the dislocation line density as seen from the direction perpendicular to the main plane,
The lengths of the dislocation lines in the vicinity of the apex and in the fringe portion are measured, and the arithmetic mean of the dislocation lines is calculated. At this time, if the dislocation line extends from the vicinity of the apex and the inside of the fringe portion toward each side or apex, the length from the starting point of the dislocation line is measured.

In the silver halide emulsions according to claims 1 and 2 of the present invention, 50 to 1 of tabular silver halide grains are used.
00 number% preferably has dislocation lines in the main plane,
It is more preferable that 70 to 100% by number have dislocation lines in the main plane.

In the silver halide emulsion according to claim 4 of the present invention, 70 to 100% of the projected area of all silver halide grains are tabular silver halide grains, and the average aspect of the tabular silver halide grains is The ratio of the tabular silver halide grains is 8 to 500, the dislocation lines are localized near the apex of the tabular silver halide grains in the outer peripheral portion, and the proportion of the tabular silver halide grains having the dislocation lines in the main plane is 50 to 100. %.

In the above description, "dislocation lines are localized near the apex in the outer peripheral portion" means that 1/3 or more and all or less of the dislocation lines existing in the outer peripheral portion are present in the vicinity of the apex. If it is less than 1/3, the effect of improving the processing stability may not be sufficiently exhibited. The proportion of tabular silver halide grains having dislocation lines in the main plane is 50 to 100% by number.
And is preferably 70 to 100% by number. 5
If it is less than 0% by number, the pressure resistance improving effect may be insufficient. When the tabular silver halide grains are less than 70% by number of the projected area of all the silver halide grains, the sensitizing effect due to the increase in the light receiving area by using the tabular silver halide grains may not be fully enjoyed. If the aspect ratio of the tabular silver halide grains is less than 8, the sensitizing effect due to the increase in the light receiving area due to the use of the tabular silver halide grains may not be fully enjoyed. If it exceeds 500, it may be difficult to maintain the processing stability.

As a method of introducing dislocation lines into silver halide grains, for example, a method of adding an aqueous solution containing an iodine ion such as potassium iodide and a water-soluble silver salt solution by a double jet, or fine silver iodide grains are used. Method of adding, method of adding only solution containing iodide ion, JP-A-6-11781
A known method such as a method using an iodide ion-releasing agent as described in US Pat. Among these methods, a method of adding an aqueous solution containing iodide ions and a water-soluble silver salt solution by a double jet, a method of adding fine silver iodide grains, and a method of using an iodine ion releasing agent are preferable.

The technique of introducing dislocation lines into the fringe portion of silver halide grains in the present invention is described in JP-A-3-1.
No. 89642, No. 8-334850 and the like. The characteristic feature of the silver halide grains of the present invention is that dislocation lines are densely formed in the fringe portion, that is, 1 or more with respect to the grains corresponding to 80% or more of the projected area of the silver halide grains.
This is a tabular silver halide grain in which 30 or more dislocation lines are introduced per grain so that the number of dislocation lines per grain is uniform.

Regarding the technique of introducing a dislocation line in the vicinity of the apex in the present invention, Japanese Patent Laid-Open No. 3-175440 and 4-
No. 166926, No. 4-149541, No. 4-156.
No. 448, No. 4-195035, etc.
The feature of the silver halide grain of the present invention is that it is a tabular silver halide grain in which dislocation lines are introduced at high density near the apex of the tabular silver halide grain.

As a method of concentrating dislocation lines near the apex, for example, a silver halide having a halogen composition different from that of the tabular grain of the substrate is once bonded to the apex of the tabular grain of the substrate, and then the tabular grain is grown again. It is obtained by For example, when the tabular grains of the substrate are silver iodobromide, silver iodobromide or silver iodide having a higher degree of iodine, or silver chloride or silver chlorobromide may be bonded. Alternatively, JP-A-6-11781
There is a method using an iodide ion-releasing agent as described in No. It is particularly preferable to use sodium p-iodoacetamidobenzenesulfonate, 2-iodoethanol, 2-iodoacetamide and the following iodide ion-releasing agents.

The iodide ion-releasing agent in the present invention is a compound which releases iodine ion by reaction with a base represented by the following general formula (1) or a nucleophile.

General Formula (1) RI In the general formula (1), R represents a monovalent organic group.
R is, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group,
It is preferably a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, 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 further preferably 10 or less.

Further, R preferably has a substituent, and the substituent may be further substituted with another substituent. As the preferable substituent, a halide, an alkyl group,
Alkenyl group, alkynyl group, aryl group, aralkyl group, heterocyclic group, acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, alkoxy group, aryl Oxy group, amino group, acylamino group, ureido group, urethane group, sulfonylamino group, sulfinyl group, phosphoric acid amide group, alkylthio group, arylthio group, cyano group,
Examples thereof include a sulfo group, a carboxyl group, a hydroxy group and a nitro group.

As the iodine ion releasing agent represented by the general formula (1), iodoalkanes, iodoalcohols, iodocarboxylic acids, iodoamides and their derivatives are preferable, and iodoamides, iodoalcohols and their derivatives are more preferable. Iodoamides substituted with a heterocyclic group are more preferred, with the most preferred example being (iodoacetamido) benzenesulfonate.

Specific examples of the iodine ion releasing agent that can be preferably used in the present invention are shown below.

[0046]

[Chemical 1]

In the present invention, when the iodine ion-releasing agent and the nucleophilic reagent are reacted to release the iodine ion, examples of the nucleophilic reagent include hydroxide ion, sulfite ion,
Thiosulfate ion, sulfinate, carboxylate, ammonia, amines, alcohols, ureas, thioureas, phenols, hydrazines, sulfides, hydroxamic acids and the like can be used, hydroxide ion, Sulfite ion, thiosulfate ion, sulfinate,
Carboxylates, ammonia and amines are preferable, and hydroxide ion and sulfite ion are more preferable.

An example of preferable reaction conditions for introducing a dislocation line into the silver halide emulsion of the present invention with an iodine ion releasing agent is shown below.

The reaction temperature is preferably 80 ° C to 30 ° C, more preferably 70 ° C to 40 ° C. The pAg immediately before the introduction of the dislocation lines is preferably 7.0 or more and 10.0 or less, and more preferably 7.5 or more and 9.5 or less. The amount of iodine ion-releasing agent added is 1 to 5 mol% with respect to the total amount of silver halide after grain growth.
Is preferred. The pH during the iodine ion releasing reaction is preferably 7.0 or more and 11.0 or less, and more preferably 8.0 or more and 10.0 or less. When a compound other than hydroxide ion is used as the nucleophile, the amount of the nucleophile is 0.
It is preferably 25 times or more and 2.0 times or less, and 0.5
It is more preferable to be not less than 1.5 times and not more than 0.8 times.
It is preferably not less than 1.2 times and not more than 1.2 times.

An example of preferable reaction conditions when a dislocation line is introduced into the silver halide emulsion of the present invention by a fine grain emulsion containing silver iodide is shown below.

The temperature at which the fine grain emulsion containing silver iodide is added is preferably 80 ° C to 30 ° C, and 70 ° C to 4 ° C.
It is more preferably 0 ° C. The amount of the silver iodide-containing fine grain emulsion to be added is preferably 1 to 5 mol% in terms of silver iodide, based on the total amount of silver halide after grain growth.

The tabular silver halide grains according to the present invention are
Crystallographically classified as twins. Twins are "crystals having one or more twin planes in one grain", and the morphology of twins in silver halide grains is classified by Klein and Moiser in the article "Photographihe K.
Orrespondence, Vol. 99, p. 99, p. 100, p. 57. The tabular silver halide grain according to the present invention preferably has two or more twin planes parallel to each other in the grain. These twin planes are present substantially parallel to the plane having the largest area of the planes forming the surface of the tabular grains (referred to as main plane). A particularly preferred form in the present invention is a case having two twin planes parallel to the main plane. In the present invention, the number of silver halide grains having two twin planes parallel to the main plane is 70.
% Or more, preferably 80% or more, particularly preferably 90% or more. In the present invention, the average of the distances between two or more twin planes parallel to the principal plane is preferably 300 Å or less and 10 Å or more, 20
0 Å or less, 10 Å or more is more preferable, 120 Å or less 1
0 Å or more is particularly preferable. In the present invention, the inter-grain distribution of the twin plane distance is preferably 40% or less,
It is more preferably 30% or less.

The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a tabular silver halide grain to be contained is coated with a silver halide emulsion on a support so that the principal planes thereof are oriented in parallel to prepare a sample. This is cut with a diamond cutter to obtain a thin section having a thickness of about 0.1 μm.
The presence of twin planes can be confirmed by observing this section with a transmission electron microscope.

In the present invention, the average of the distances between two or more twin planes parallel to the main plane is the cross section cut substantially perpendicular to the main plane in the observation of the section using the transmission electron microscope. Tabular silver halide grains having
It is obtained by selecting 0 or more pieces, obtaining the distances between twin planes, and averaging them.

In the present invention, the distance between twin planes is a factor that influences the supersaturated state during nucleation, such as gelatin concentration, temperature, iodine ion concentration, pBr, ion supply rate,
It can be controlled by appropriately selecting the combination of various factors such as the stirring speed and the gelatin type. In general, the higher the supersaturation state of nucleation, the narrower the distance between twin planes. For details of the supersaturation factor, see, for example, JP-A-63-92942 or 1-213.
The description of No. 637 can be referred to.

In the silver halide emulsion of the present invention, 70 to 100% of the projected area of all silver halide grains are tabular silver halide grains, preferably 80 to 100%, and preferably 90 to 100%. It is more preferable that there is. 70
If it is less than a few percent, the sensitizing effect due to the increase in the light receiving area due to the use of tabular silver halide grains may not be fully enjoyed.

The average aspect ratio of the tabular silver halide grains according to the present invention is 8 to 500, preferably 12 to 500, more preferably 15 to 500, and more preferably 20 to 500. Is more preferable. 8
If it is less than the above range, the sensitizing effect due to the increase in the light receiving area due to the use of tabular silver halide grains may not be fully enjoyed. If it exceeds 500, it may be difficult to maintain the processing stability.

The aspect ratio of silver halide grains can be obtained by the following formula by determining the grain size and grain thickness of each silver halide grain by the following method.

Aspect ratio = grain size / grain thickness The tabular silver halide grain according to the present invention is a tabular silver halide grain having a (111) main plane having two twin planes parallel to the main plane. Preferably, the average particle size is 0.
3-50 micrometers is preferable, 1.0-50 micrometers is more preferable, 3.5-50 micrometers is the most preferable.

In the present invention, the average particle size means the particle size ri.
The arithmetic mean of However, 3 significant digits and the least significant digit are rounded off, and the number of measured particles is indiscriminately 1,000 or more. The grain size ri as used herein is a diameter when a projected image when viewed from a direction perpendicular to the main plane of the tabular silver halide grain is converted into a circular image having the same area.
The grain size ri is 1 for silver halide grains by an electron microscope.
This can be obtained by enlarging the image by 10,000 to 70,000 times and measuring the particle diameter on the print or the area at the time of projection.

The thickness of the tabular silver halide grains according to the present invention is preferably 0.25 μm or less, and 0.00
5 to 0.20 is more preferable, and 0.005 to
Particularly preferably, it is 0.10 μm.

In the present invention, the thickness distribution of tabular silver halide grains is preferably 40% or less, more preferably 30% or less, and most preferably 20% or less.

In the present invention, the projected area and thickness of individual grains for calculating the grain size and aspect ratio of silver halide grains can be determined by the following method. A sample was prepared by coating a latex ball with a known particle size as an internal standard on a support, and silver halide particles so that the main plane was oriented parallel to the substrate, and cast it onto the particle by carbon deposition from a certain angle. After that, a replica sample is prepared by a normal replica method. An electron micrograph of the same sample is taken, and the projected area and thickness of each particle are obtained using an image processing device or the like. In this case, the projected area of the particle can be calculated from the projected area of the internal standard, and the thickness of the particle can be calculated from the internal standard and the length of the shadow of the particle.

In the present invention, in addition to the tabular grains according to the present invention, arbitrary ones such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution can be used. When the particle size distribution (variation coefficient) is defined, the particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. If it exceeds 50%, the production stability and storage stability may deteriorate. Further, the smaller the lower limit is, the more preferable. However, if the lower limit is less than 3, production may be difficult, which may be disadvantageous in terms of cost.

Particle size distribution (%) = (standard deviation of particle size / average particle size) × 100 The average particle size and standard deviation are determined from the particle size ri defined above.

In the tabular silver halide grains in the present invention, 70% or more of the number of grains are preferably hexagonal tabular silver halide grains. In the present invention, a hexagonal tabular silver halide grain means a replica sample using a sample coated with silver halide grains such that the main plane is oriented parallel to the substrate, and the length of adjacent linear sides is The tabular silver halide grains have a thickness ratio of 0.1 to 10, and preferably 0.2 to 5.

In the present invention, the average silver iodide content of the tabular silver halide grains is preferably 0.1 to 40 mol%, more preferably 0.3 to 30 mol%, Most preferably, it is 0.5 to 20 mol%.

The silver iodide content of the silver halide grains is EP
MA method (Electron Probe Micro
(Analyzer method). Specifically, a sample was prepared in which silver halide grains were well dispersed so that they did not come into contact with each other, and the sample was irradiated with an electron beam while being cooled to -100 ° C. or lower with liquid nitrogen, and emitted from each silver halide grain. By determining the characteristic X-ray intensities of silver and iodine, the silver iodide content of each individual silver halide grain can be determined.

The silver iodide content of the silver halide grains determined for each silver halide grain by the above method was 10%.
The average silver iodide content is calculated by averaging zero or more silver halide grains.

In the present invention, the tabular silver halide grain preferably has a plurality of silver halide phases having different silver iodide contents inside the grain. A core-shell type silver halide grain in which the silver iodide content of the silver halide phase outside the grain is high or low relative to the silver iodide content in the grain is also preferable. The number of plural silver halide phases having different silver iodide contents in the grain is arbitrary, but is preferably 3 or more, more preferably 4 or more, and further preferably 5 or more. preferable.

In the present invention, Japanese Patent Application Laid-Open No. 11-1538.
The average silver iodide content outermost layer of the silver halide grains of No. 41 described in the main flat portion I ₁ (mol%), when the I ₂ (mol%) in a side portion, is I _1> I ₂ It is also preferable to use tabular silver halide grains, and JP-A-2000-30521
The silver halide grain described in No. 1 has at least a five-phase structure including a central phase, an internal phase, a first high iodine localized phase, an intermediate phase, a second high iodine localized phase, and a shell phase, and The ratio of the phases is 5% or more and 60% or less of the amount of silver grains, the average silver iodide content is 0 mol% or more and 10 mol% or less, and the ratios of the first and second high iodide localized phases are respectively. 0.5% to 5% of the amount of grain silver
In the following, the average silver iodide content is higher than 40 mol% and 100 mol% or less, the ratio of the intermediate phase is 10% or more and 70% or less of the amount of grain silver, and the average silver iodide content is 0% or less. A tabular silver halide having a mol ratio of 10 mol% or more, a shell phase ratio of 10% or more and 50% or less of the amount of silver grains, and an average silver iodide content of 0 mol% or more and 10 mol% or less. The grains and the silver halide grains described in JP-A-2000-321699 have at least a five-layer structure of a core, a first shell, a second shell, a third shell, and a fourth shell from the center, and the ratio of the core is 5% to 50% of total silver
And the average silver iodide content is 0 mol% or more and 3 or less.
Mol% or less, the ratio of the first shell is 5% or more and 30% or less with respect to the total silver amount, the average silver iodide content is 3 mol% or more and 10 mol% or less, and the second shell Is 10% or more and 30% or less with respect to the total silver amount, and the average silver iodide content is 0% or more and 3% or less,
The ratio of the third shell is 0.5% or more and 5% or less with respect to the total silver amount, and the average silver iodide content is 40 mol% or more and 1
A tabular halogen having a mol ratio of 00 mol% or less, a fourth shell ratio of 10% or more and 40% or less with respect to the total silver amount, and an average silver iodide content of 3 mol% or more and 10 mol% or less. It is also preferable to use silver halide grains. In addition, JP 2000
-258863, 2001-100346, 2
The tabular silver halide grains having a plurality of silver halide phases described in No. 001-242576 and the like can also be preferably used.

In the present invention, the average surface silver iodide content of the silver halide grains is preferably 0.5 mol% to 20 mol%, more preferably 1 mol% to 15 mol%. In the present invention, the surface silver iodide content of the silver halide grain means the silver iodide content in the silver halide phase including the surface of the silver halide grain and having a depth of 50Å from the surface of the silver halide grain.

The average silver iodide content I ₁ (mol%) of the outermost surface layer of silver halide grains is determined by the following method.

The surface silver iodide content of the above silver halide grains is determined by the XPS method (X-ray Photoelectron).
n Spectroscopy: X-ray photoelectron spectroscopy). That is, the sample is 1.3 × 10
Cool to -110 ° C or less in an ultrahigh vacuum of ^-6 Pa or less,
MgKα is used as the X-ray for the probe, the X-ray source voltage is 15 kV,
Irradiation with an X-ray source current of 40 mA, Ag3d5 / 2, Br3
d, measured for I3d3 / 2 electrons. The integrated intensity of the measured peak is determined by the sensitivity factor (Sensitivity).
Factor) and calculate the halide composition of the outermost layer from these intensity ratios.

The XPS method has heretofore been known as a method for obtaining the silver iodide content on the surface of silver halide grains as disclosed in JP-A-2-241.
No. 88, etc. However, when the measurement was performed at room temperature, the exact silver iodide content in the outermost layer could not be obtained because the sample was destroyed by the X-ray irradiation. We succeeded in accurately determining the silver iodide content of the outermost layer by cooling the sample to a temperature at which no destruction occurred. As a result, particularly for particles such as core / shell particles having a different composition between the surface and the interior or particles having a high iodine layer or a low iodine layer localized on the outermost surface, the measured value at room temperature is X-ray. It was revealed that the composition differs greatly from the true composition due to decomposition of silver halide by irradiation and diffusion of halide (particularly iodine).

The XPS method used here is specifically as follows. A 0.05 mass% aqueous solution of proteolytic enzyme (pronase) was added to the silver halide emulsion and stirred at 45 ° C. for 30 minutes to decompose gelatin. This is centrifuged to precipitate the emulsion particles and remove the supernatant. Next, distilled water is added to disperse the emulsion particles in distilled water, and the mixture is centrifuged to remove the supernatant. Redisperse the emulsion particles in water,
A thin sample is applied onto a mirror-polished silicon wafer to give a measurement sample. Using the sample prepared in this way, XP
The surface iodide is measured by S. In order to prevent the destruction of the sample due to X-ray irradiation, the sample is
Cool to 110-120 ° C.

As the probe X-ray, MgKα was irradiated with an X-ray source voltage of 15 kV and an X-ray source current of 40 mA to obtain Ag3d5.
/ 2, Br3d, I3d3 / 2 electrons were measured.
The integrated intensity of the measured peak is determined by the sensitivity factor (Sensit
(ivity Factor), and the halide composition of the outermost layer is determined from these intensity ratios.

The silver halide emulsion of the present invention preferably contains at least one kind of polyvalent metal atom ion, polyvalent metal atom complex or polyvalent metal atom complex ion inside or on the surface of the silver halide grain. .

Examples of the polyvalent metal atom ion, polyvalent metal atom complex or polyvalent metal atom complex ion include Fe and C.
o, Ni, Ru, Rh, Pd, Re, Os, Ir, P
t, Mg, Al, Ca, Sc, Ti, V, Cr, Mn,
Cu, Zn, Ga, Ge, As, Se, Sr, Y, M
o, Zr, Nb, Cd, In, Sn, Sb, Ba, L
a to W, Au, Hg, Tl, Pb, Bi, Ce and U etc. Periodic Table 3 to 7 periods (most commonly 4 to
At least one selected from metal atoms from 6 cycles), ions, complexes thereof, salts containing these (including complex salts), compounds containing these, and the like can be used.
It is preferably selected from simple salts or metal complexes.

When selected from metal complexes, hexacoordinated complexes,
A pentacoordinated complex, a tetracoordinated complex, and a two coordinated complex are preferable, and an octahedral hexacoordinated complex and a plane four coordinated complex are more preferable.

[0081] As a ligand which forms a complex, CN ^-,
CO, NO ^2- , 1,10-phenanthroline, 2,2 '
- bipyridine, SO ₃ ^-, ethylenediamine, NH _{3, ^{pyridine, H 2 O, NCS -,}} NCO -, O 3, SO 4 2-, O
H ⁻ , N ^{3 −} , S ^{2 −} , F ⁻ , Cl ⁻ , Br ⁻ , I ^{− and the} like can be used.

In the present invention, the following known techniques can be applied for incorporating a polyvalent metal into the silver halide emulsion.

For example, B. H. Carroll, "Ir
idium Sensitization, A Lit
erasure Review ", Photograph
hic Science and Engineer
ng, Vol. 24, No. 6, November / December 1980, pages 265-267, U.S. Pat. No. 1,951,933,
No. 2,628,167, No. 3,687,676
No. 3, No. 3,761,267, No. 3,890,15
No. 4, No. 3,901,711, No. 3,901,7
No. 13, No. 4,173,483, No. 4,269,
No. 927, No. 4,413, 055, No. 4,47
No. 7,561, No. 4,581,327, No. 4,6
No. 43,965, No. 4,806,462, No. 4,
No. 828,962, No. 4,835,093, No. 4,902,611, No. 4,981,780, No. 4,997,751, No. 5,057,402,
No. 5,134,060, No. 5,153,110
No. 5,164,292, No. 5,166,04
No. 4, No. 5,204,234, No. 5,166,0
No. 45, No. 5,229,263, No. 5,252,
No. 451, No. 5,252,530, EPO No. 024.
No. 4184, No. 0488737, No. 048860.
No. 1, No. 0368304, No. 0405938,
The techniques described in No. 0509674, No. 0563946, Japanese Patent Application No. 2-249588, WO 93/02390 and the like can be applied. Further, U.S. Pat. No. 4,847,
191, No. 4,933,272, No. 4,981,7
81, 5,037,732, 937,180
Issue No. 4,945,035 Issue 5,112,732
No., EPO No. 0509674, No. 0513738
No., WO 91/10166, No. 92/16876
, German Patent No. 298,320, US Patent No. 5,
The techniques described in No. 360,712, No. 5,024,931 and the like can be applied.

Research Disclosure (R
esearch Disclosure (hereinafter, also referred to as RD) Volume 367, November 1994, Item 36
736 has a clear description of the criteria for selecting shallow electron trap dopants. In the present invention, it is preferable to use a hexacoordinated complex ion as shown below among at least one selected from the group consisting of a polyvalent metal atom, its ion and its complex, and its ion.

[0085] [ML _6] ⁿ where, M is filled frontier orbital polyvalent metal ion, preferably ^{Fe 2+, Ru 2+, Os 2+} , Co 3+, Rh 3+, Ir
³⁺ , Pd ⁴⁺ or Pt ⁴⁺ ; L ₆ represents an independently selectable 6-coordination complex ligand, provided that
At least four of the ligands are anionic ligands,
At least one (preferably at least 3 and optimally at least 4) of the ligands is more electronegative than either halide ligand; and n is 2-, 3-
Or represents 4-. Specific examples of hexacoordinated complex ions that can provide a shallow electron trap are shown below.

SET-1 [Fe (CN) ₆ ] ^4- SET-2 [Ru (CN) ₆ ] ^4- SET-3 [Os (CN) ₆ ] ^4- SET-4 [Rh (CN) ₆ ] ^{3 -} SET-5 [Ir (CN) _6] ^3- SET-6 [Fe (pyrazine) (CN) _5] ^4-SET-7 [RuCl (CN) _5] ^4-SET-8 [OsBr (CN) _5] ^4-SET-9 [RhF (CN) _5] ^3- SET-10 [IrBr (CN) _5] ^3- SET-11 [FeCO (CN) _5] ^3- SET-12 [RuF ₂ (CN) _4] ^{4 -} SET-13 [OsCl ₂ (CN) _4] ^4-SET-14 [RhI ₂ (CN) _4] ^3- SET-15 [IrBr ₂ (CN) _4] ^3- SET-16 [Ru (CN) ₅ ( OCN)] ^4-SET-17 _{[Ru (CN) 5 (N 3} ) ] ^4-SET-18 [Os (CN) ₅ (SCN ] ^4-SET-19 [Rh (CN) ₅ (SeCN)] ^3- SET-20 [Ir (CN) ₅ (HOH)] ^2-SET-21 [Fe (CN) ₃ Cl _3] ^3- SET-22 _{[Ru (CO) 2 (CN)} 4 ] ^3- SET-23 [Os (CN) Cl _5] ^4-SET-24 [Co (CN) _6] ^3- SET-25 [Ir (CN) ₄ (oxalate) ] ^3- SET-26 [In (NCS) ₆ ] ^3- SET-27 [Ga (NCS) ₆ ] ^{3-In the} present invention, when Ir compounds are used, preferred examples of the compounds are K ₂ IrCl ₆ and K ₃ IrCl. ₆ , K ₂ Ir
Br ₆ etc.

Specific examples of other polyvalent metal compounds preferably used in the present invention include InCl ₃ and K ₄
Fe (CN) ₆ , K ₃ Fe (CN) ₆ , K ₄ Ru (C
N) ₆ , Pb (NO ₃ ) ₂ and hydrates of these.

In the present invention, at least one selected from the group consisting of polyvalent metal atoms, their ions and their complexes.
Although a seed is used, Ir, Ru, Os, Fe, Rh, C
Each atom such as o, In, Ga, Ge, Pd, or Pt, its ion, and its complex are particularly preferably used.

In the present invention, the silver halide emulsion may contain at least one selected from the group consisting of polyvalent metal atoms, their ions and their complexes, and their ions by doping during the physical ripening of silver halide grains. May be carried out, or doping may be carried out during the process of forming silver halide grains (generally, during the addition of a water-soluble silver salt and a water-soluble alkali halide), or the formation of silver halide grains may be temporarily stopped. Doping may be performed in this state, and then grain formation may be continued. Further, doping may be carried out after the formation of the silver halide grains to introduce at least one selected from the group consisting of polyvalent metal atoms, their ions and their complexes, and their ions on the surface of the silver halide grains. The introduction of at least one selected from the group consisting of a polyvalent metal atom, its ion and its complex, and its ion is carried out by nucleation and physical aging in the presence of the polyvalent metal atom, its ion and its complex, and its ion, It can be carried out by forming particles.

The concentration of at least one selected from the group consisting of polyvalent metal atoms used in the present invention, ions thereof and complexes thereof, and ions thereof is generally 1 × 10 ⁻⁷ to 1 mol / mol of silver halide. A range of 1 × 10 ⁻² mol is suitable, a range of 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol is more preferable, and a range of 2 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol is particularly preferable. .

In the present invention, in order to contain the polyvalent metal in the silver halide emulsion, they may be dispersed directly in the emulsion, or they may be dissolved in a solvent such as water, methanol or ethanol alone or in a mixed solvent. What was added may be added, and the method of adding an additive to a silver halide emulsion can be generally applied in the art. Further, at least one selected from the group consisting of polyvalent metal atoms, their ions and their complexes, and their ions may be added to the silver halide emulsion together with the silver halide fine grains, or the polyvalent silver halide fine grains may be polyvalent. A silver halide emulsion containing a metal atom, an ion thereof, a complex thereof, and at least one selected from the group consisting of the ions can be added to the silver halide emulsion.

Regarding the production method of adding silver halide fine grains containing at least one selected from the group consisting of polyvalent metal atoms, their ions and their complexes, and their ions, JP-A-11-212201 describes. Can be referred to.

The silver halide emulsion of the present invention is preferably silver bromide, silver iodobromide or silver iodobromochloride, and silver iodobromide,
Particularly preferred is silver iodobromochloride. The silver chloride content is preferably 0 to 50 mol%, and 0 to 30 mol%
Is more preferable, and 0 to 10 mol% is even more preferable. The silver halide emulsion of the present invention preferably contains silver halide grains having a plurality of silver halide phases having different silver iodide contents inside the silver halide grains, and the tabular grains have different halide compositions. A core-shell type particle having a plurality of phases is preferable. The core-shell type particles preferably have three or more phases having different halide composition ratios, more preferably have four or more phases, and particularly preferably have five or more phases. Halide composition ratio of adjacent phase is 1mo
The difference is preferably 1%, more preferably 3 mol% or more. The silver halide emulsion of the present invention can have any halide composition, but is preferably silver iodobromide or silver iodochlorobromide. Adjacent phases of the core-shell type grains preferably differ in silver iodide content by 1 mol% or more, preferably 3 mol% or more. The volume ratio of each phase of the core-shell type particles to the whole particles is 1% or more, preferably 3% or more,
It is more preferably at least 5%. The core-shell type particles may have a lower iodine or a higher iodine inside, and may alternately have a phase having a high iodine composition and a phase having a low iodine composition. The outermost layer of the core-shell type grains is preferably a low iodide phase having a silver iodide content of less than 3 mol%,
It is more preferably less than 1 mol%, and particularly preferably contains no silver iodide.

The silver halide emulsion of the present invention is preferably nucleated in the presence of low molecular weight gelatin having an average molecular weight of 5,000 to 70,000 and / or gelatin having a methionine content of less than 30 μmol / g. The methionine content of gelatin during nucleation is more preferably 2
Less than 0 μmol / g, more preferably 0.1
It is 10 μmol / g. The average molecular weight of the low molecular weight gelatin is more preferably 6,000 to 50,000, more preferably 7,000 to 5,000.
30,000 is more preferable.

The content of methionine in gelatin was 30 μm.
To reduce the amount to less than ol / g, it is effective to oxidize the alkali-treated gelatin with an oxidizing agent. Examples of the oxidizing agent that can be used for the gelatin oxidation treatment include:
Examples thereof include hydrogen peroxide, ozone, peroxy acids, halogens, thiosulfonic acid compounds, quinones, and organic peracids, and hydrogen peroxide is preferable in the present invention.

There are many documents on the method for measuring the methionine content of gelatin. For example, Journal of
Photographic Science Vol. 28, 111, 40, 149, 41, 172, 42, 117
Page, Journal of Imaging Science No. 3
Volume 3, page 10, Journal of Imaging Science and Technology, Vol. 39, page 367, etc., can be used for amino acid analysis, HPLC, gas chromatography, silver ion titration, and the like.

In the present invention, the methionine content is 30.
The low methionine-containing gelatin of less than μmol / g is preferably used at the time of nucleation of silver halide grains, but may be further added to the ripening step and the growth step following the nucleation step.

The above-mentioned low molecular weight gelatin can be obtained by a method such as hydrolysis of ordinary gelatin, enzymatic decomposition using gelatin degrading enzyme, and cross-linking cutting using ultrasonic irradiation.

In the silver halide emulsion of the present invention, the content of low molecular weight gelatin and / or methionine is 30 μm.
Any dispersion medium can be used in the steps other than the nucleation step using gelatin of less than ol / g.
Examples of the dispersion medium that can be preferably used in the silver halide emulsion of the present invention include gelatin and hydrophilic colloid. As gelatin, alkali-processed gelatin or acid-processed gelatin having a molecular weight of about 100,000, oxidized gelatin, or Bull. Soc. Sci. Photo.
Japan. No. 16. The enzyme-treated gelatin as described in P30 (1966) can be preferably used. Examples of hydrophilic colloids include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sodium alginate and starch. Sugar derivatives such as derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N
-A variety of synthetic hydrophilic polymeric substances such as single or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole can be used.

It is also preferable to use chemically modified gelatin in the step of growing silver halide grains. Examples of chemically modified gelatin that can be used in the silver halide emulsion of the present invention include those disclosed in JP-A-5-72658 and JP-A-9-1.
Examples thereof include gelatin substituted with an amino group described in each publication such as No. 97595 and No. 9-251193.

In the production of the silver halide emulsion of the present invention, it is preferable to provide a desalting step once or more during grain formation. The desalting step here is to wash the silver halide emulsion with water to remove soluble salts. For the desalting process, see Research Disclosure 176.
Reference can be made to Item 43, Item II, and it can be preferably carried out by a flocculation method using an inorganic salt, an anionic surfactant or an anionic polymer (for example, polystyrene sulfonic acid). The desalting step is preferably performed at a time point of less than 10% by volume, and more preferably at a time point of less than 5% by volume, based on the volume of the silver halide grain after growth.

In the production of the silver halide emulsion of the present invention, the temperature at the nucleation of silver halide grains is preferably lower than 30 ° C, more preferably lower than 21 ° C. The temperature of ripening and growth of the silver halide emulsion of the present invention is preferably 30 ° C or higher and 90 ° C or lower, more preferably 40 ° C or higher and lower than 80 ° C.

The silver halide emulsion of the present invention may be reduction sensitized. The reduction sensitization is carried out by adding a reducing agent to the protective colloid aqueous solution in which the silver halide emulsion grains are grown, or by adding the protective colloid aqueous solution in which the silver halide grain growth is carried out under a low pAg condition of pAg 7.0 or less. so,
Alternatively, it is carried out by aging or growing the silver halide grains under a high pH condition of pH 7.0 or higher. You may perform these methods in combination.

When a reducing agent is used in the present invention, thiourea dioxide, ascorbic acid and its derivatives, stannous salt, borane compounds, hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, sulfites and the like are used. Although it can be used, thiourea dioxide, ascorbic acid and derivatives thereof, and stannous salt are preferably used.

[0105] When using a reducing agent, addition amount per mol of silver halide ^10-2 to ^- 8 mol are preferred, 1
0 ^-3 to 10 ^-7 mol is more preferable.

In the present invention, an aqueous solution of protective colloid for reduction sensitization to grow silver halide grains is pAg 7.0.
When it is carried out under the following low pAg condition, a silver salt is added to the protective colloid aqueous solution to obtain an appropriate p
After making Ag, it is preferable to ripen or grow silver halide grains. The silver salt is preferably a water-soluble silver salt, particularly preferably an aqueous solution of silver nitrate. PAg during aging is 7.0
The following is appropriate, preferably 2.0 to 5.0. (Here, the pAg value is the common logarithm of the reciprocal of the Ag ⁺ concentration.) In the present invention, reduction sensitization is carried out under a high pH condition of pH 7.0 or more for the protective colloid aqueous solution in which silver halide grain growth is carried out. In the case of the above method, an alkaline compound is added to the protective colloid aqueous solution to adjust to an appropriate pH, and then silver halide grains are aged or grown. As the alkaline compound, for example, sodium hydroxide, potassium hydroxide, ammonia and the like can be used, but it is preferable to use a compound other than the ammonium compound.

The reducing agent, the silver salt for reduction ripening, and the alkaline compound may be added by rush addition or over a certain period of time. In this case, constant rate addition or function addition may be performed. Also, the required amount may be added in several divided portions.
Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, the soluble silver salt and / or the soluble halide may be present in the reaction vessel, or may be mixed in the soluble halide solution and added together with the halide. Furthermore, the addition may be performed separately from the soluble silver salt and the soluble halide.

In the present invention, an oxidizing agent can be used for deactivating the reducing agent and for other purposes. For example, hydrogen peroxide (water) and its adducts: H ₂ O ₂ , NaBO ₂ , H ₂ O _{2-.
3H 2 O, 2NaCO 3 -3H 2} O 2, Na 4 P 2 O 7 -2H 2
Such as _{O 2, 2Na 2 SO 4 -H} 2 O 2 -2H 2 O. Peroxy acid salt: K ₂ S ₂ O ₃ , K ₂ C ₂ O ₃ , K ₄ P ₂ O ₃ , K ₂ [Ti
_{(O 2) C 2 O 4} ] -3H 2 O, peracetic acid, ozone, I _2, etc. thiosulfonic acid.

In the present invention, the emulsion may have the above-mentioned oxidizing agent for the purpose other than deactivating the reducing agent. The addition amount of the oxidizing agent depends on the type of the reducing agent, the reduction sensitizing condition, the addition timing of the oxidizing agent, the adding condition of the oxidizing agent, etc., but it is 10 ⁻³ to 10 ⁻³ per 1 mol of the reducing agent used. ⁵ mol is preferred.

The oxidizing agent may be added at any time during the silver halide emulsion manufacturing process. It can also be added prior to the addition of the reducing agent.

As a method of adding an oxidizing agent, a method of adding an additive to a silver halide emulsion can be applied in the art. For example, it can be dissolved in advance in a suitable organic solvent represented by alcohols or added as an aqueous solution.

After adding the oxidizing agent, a reducing substance may be newly added to neutralize the excess oxidizing agent. These reducing substances are substances capable of reducing the above-mentioned oxidizing agents, and include sulfinic acids, di- and trihydroxybenzenes, chromans, hydrazine and hydrazides, p-phenylenediamines, aldehydes, aminophenols, Examples include endiols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives. The amount of the reducing substance is preferably 10 ^-3 to 10 ³ mol amount 1 mole of oxidizing agent used is.

In the present invention, a silver halide emulsion having silver halide protrusions on the surface of silver halide grains can be used.

The silver halide emulsion having silver halide protrusions on the surface of the silver halide grain as used in the present invention means that the silver halide grain having the silver halide protrusions on the surface of the silver halide grain is a silver halide grain. It refers to a silver halide emulsion that is 30% or more of the total projected area.
It is preferable that 0% or more is a silver halide grain having a silver halide projection on the surface of the silver halide grain, and 70% or more of the total projected area is a halide having a silver halide projection on the surface of the silver halide grain. More preferably, it is a silver particle. In the present invention, when the silver halide emulsion having a silver halide protrusion on the surface of the silver halide grain is used, the silver halide protrusion on the surface of the silver halide grain is preferably epitaxial.

Epitaxially arranging a silver halide protrusion on a selected portion of a silver halide grain (hereinafter also referred to as “host grain”) serving as a substrate, the emission is caused by photon absorption in imagewise exposure. It is generally said that the competition of the generated conduction band electrons for the sensitized site is reduced and thus the sensitivity is improved. US Patent 4,435,501
No. 5,968,961 discloses improving sensitivity by epitaxially depositing a silver salt on selected sites on the surface of host tabular grains. The U.S. patent alleges that the increase in sensitivity was due to limiting the epitaxial deposition of the silver salt to a small portion of the surface area of the host tabular grains. That is, epitaxial placement of tabular grains on a limited portion of the major plane is more efficient than epitaxial placement over all or most of the major plane, and even more preferred is substantially limited to the edges of the host grain. In addition, an epitaxial arrangement in which the amount of coating on the main plane is limited, and more efficient and preferable is an epitaxial arrangement that is limited to the corner of the host grain, the vicinity thereof, or another separate site. The spacing of the principal plane corners of the host particles themselves reduces optoelectronic competition enough to achieve near maximum sensitivity. U.S. Pat. No. 4,435,501 teaches that slowing the epitaxial deposition rate can reduce the number of epitaxially located sites on the host grain.

Therefore, also in the present invention, the silver halide protrusions epitaxially arranged on the surface area of the host grain are preferably limited to a small portion of the surface area of the host grain, and are limited to the corner or the vicinity thereof. Particularly preferred. Specifically, it is preferably less than 50%, more preferably less than 30%. Further, the silver amount of the silver halide protrusions arranged epitaxially is preferably 0.3 to 25%, and more preferably 0.5 to 15% with respect to the silver amount of the host grains.

In the present invention, as one of the most preferable modes of using a silver halide emulsion having a silver halide protrusion on the surface of the silver halide grain, the silver halide protrusion portion epitaxially arranged is a host grain. It is preferably formed at a limited position at a corner or in the vicinity thereof, and a known method can be applied as a method for achieving this. Said U.S. Pat.
No. 501 discloses a method of adsorbing a spectral sensitizing dye or aminoazaindenes as a site director, which is preferably applicable to the present invention.

In order to avoid structural collapse of the host grains, the silver halide protrusions arranged epitaxially are
Its total solubility is preferably higher than the total solubility of the silver halide forming the host grains. Therefore, it is preferable that the silver halide protrusions arranged epitaxially are specifically silver chloride. Silver chloride, like silver bromide, forms a face centered cubic lattice structure, thus facilitating epitaxial deposition.

To maintain the structural integrity of the host grains, epitaxial deposition is preferably conducted under conditions which limit the solubility of the halide forming the host grains. However, there are cases in which the halide of the epitaxially arranged silver halide protrusions is from the host grain. That is, it should be a silver chloride protrusion containing a small amount of bromide and, in some cases, iodide.

Various methods well known in the art can be used for forming the silver halide grains in the production of the silver halide emulsion of the present invention. That is, a single jet method, a double jet method, a triple jet method, a silver halide fine grain supply method and the like can be used in any combination. Further, a method of controlling pH and pAg in a liquid phase where silver halide is produced in accordance with the growth rate of silver halide can also be used. The silver halide grains are preferably formed under conditions close to the critical growth rate.

A seed emulsion may be used in the production of the silver halide emulsion of the present invention. When using a seed emulsion,
The silver halide grains in the seed emulsion may have a regular crystal structure such as a cube, octahedron, or tetradecahedron, or may have an irregular crystal shape such as a sphere or a plate. But it's okay. In these particles, (100) plane and (111) plane
Any surface ratio can be used. Further, these crystal forms may be a composite, and grains of various crystal forms may be mixed, but the silver halide grains in the seed emulsion used are twin crystal silver halide grains having twin planes. Is preferred, and twinned silver halide grains having two opposing parallel twin planes are particularly preferred.

In the present invention, regardless of whether a seed emulsion is used or not, a method known in the art can be applied as a condition for silver halide nucleus formation and ripening. it can.

For the production of the silver halide emulsion of the present invention, a silver halide solvent known in the art can be used. If possible, however, the silver halide solvent should not be used when forming the base tabular grains. , It should be avoided except for ripening after nucleation.

Any of an acidic method, a neutral method and an ammonia method can be used for producing the silver halide emulsion of the present invention, and the acidic method or the neutral method is preferable.

In the production of the silver halide emulsion of the present invention, even if halide ions and silver ions are simultaneously mixed,
One may be present while the other is mixed. In consideration of the critical growth rate of silver halide crystals, halide ions and silver ions may be added sequentially or simultaneously while controlling pAg and pH in the mixing vessel. The halogen composition of the silver halide grains may be changed by using a conversion method at any step of silver halide formation.

In the present invention, when silver halide fine particles are used, the silver halide fine particles may be prepared in advance prior to the preparation of the silver halide grains according to the present invention,
It may be prepared in parallel with the preparation of the silver halide grains.
In the latter case of preparing in parallel, JP-A-1-1834
No. 17, No. 2-44335, etc., the silver halide fine particles can be produced by using a mixer separately provided outside the reaction vessel in which the silver halide grains according to the present invention are formed. However, a preparation container may be provided separately from the mixer, and the silver halide fine particles once prepared in the mixer may be arbitrarily selected so as to be suitable for the growth environment in the reaction container in which the silver halide particles are prepared. It is preferable to supply it to the reaction vessel after the preparation.

As a method for preparing the fine silver halide grains, an acidic and neutral environment (pH ≦ 7) is preferable when the reduction sensitized fine grains are not intended to be prepared. When the reduction sensitized fine particles are intended to be prepared, silver halide fine particles may be prepared by appropriately combining the above-mentioned reduction sensitization techniques.

To produce the silver halide fine grains, a water-soluble silver salt containing silver ions and an aqueous solution containing halide ions may be mixed while appropriately controlling the supersaturation factor.
Regarding the control of the supersaturation factor, JP-A-63-92942
No. 63-311244 and the like can be referred to.

PAg for producing the silver halide fine grains
Is preferably 3.0 or more, more preferably 5.0 or more, and further preferably 8.0 or more, in order to suppress generation of reduced silver nuclei in the silver halide fine grains themselves. .

The temperature for producing the fine silver halide grains is
The temperature is preferably 50 ° C or lower, more preferably 40 ° C or lower, and most preferably 35 ° C or lower.

As the protective colloid used for producing the silver halide fine grains, the above-mentioned protective colloid-forming substances used for producing the silver halide grains according to the present invention can be used.

When the silver halide fine grains are formed at a low temperature, coarsening of the grain size due to Ostwald ripening after the formation of the silver halide fine grains can be suppressed, but gelatin tends to coagulate at a low temperature. 2-16642
It is preferable to use the low molecular weight gelatin described in No. 2 or the like, a synthetic molecular compound having a protective colloid action for silver halide grains, or a natural polymer compound other than gelatin. The concentration of the protective colloid is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more.

The grain size of the silver halide fine grains is 0.1 μm.
The following is preferable, and 0.05 μm or less is more preferable.

The silver halide fine grains can contain the above-mentioned reduction sensitization and optionally metal ions, if necessary.

In the production of the silver halide emulsion of the present invention, it is preferable to perform the concentration operation of the silver halide emulsion by the ultrafiltration method in at least a part of the growing step. In the case of producing a tabular emulsion having a high aspect ratio such as the silver halide emulsion of the present invention, a dilution environment is preferable, and therefore an ultrafiltration method is preferably applied in order to improve productivity. When the silver halide emulsion is concentrated by the ultrafiltration method, the silver halide emulsion production facility disclosed in JP-A-10-339923 can be preferably used.

In the present invention, the ultrafiltration concentration mechanism is connected to the reaction vessel by a pipe or the like, and the reaction solution circulation mechanism such as a pump circulates the reaction solution at an arbitrary flow rate between the reaction vessel and the concentration mechanism. It can be stopped at any time, and further, it has a device for detecting the volume of an aqueous solution containing a salt extracted from the reactant solution by the concentration mechanism, and the amount thereof can be controlled arbitrarily. It is a facility equipped with a possible mechanism. It is also possible to add other functions as needed.

In the present invention, the concentration by ultrafiltration is
The following (1), (2) or a combination of (1) and (2) can be preferably applied.

(1) In the step of forming silver halide grains, the concentration mechanism is used to reduce the volume of the reactant solution.

(2) Using the concentration mechanism described above in the step of forming silver halide grains, an aqueous solution containing a soluble substance in an amount equal to or less than the amount of the additive liquid for silver halide formation is reacted. Of the reactant solution to keep the volume of the reactant solution substantially constant, or suppress the increase in volume.

Before the step of introducing dislocation lines, the above (1)
Reducing the volume of the reactant solution by the above method leads to an improvement in the dislocation line particle ratio, which is a preferred embodiment. The ultrafiltration may be carried out by interrupting the silver halide grain growth at any point in the silver halide grain formation process, or may be carried out for an arbitrary period while continuing the silver halide grain growth. It may be carried out a plurality of times during the silver grain formation process, but preferably before the completion of silver halide grain formation, more preferably during silver halide grain growth or during silver halide grain growth. preferable.

By utilizing the ultrafiltration, unnecessary water-soluble salts can be removed and desalted in the process of forming silver halide grains. Further, a reducing agent, an oxidizing agent, a halogen ion-releasing compound, a silver halide solvent, a polyvalent metal atom, a polyvalent metal atom ion, a polyvalent metal atom complex or a polyvalent metal atom complex ion, which is added when the silver halide grains are formed. It is possible to remove and deactivate unreacted substances such as the above, undoped residues and the like. Furthermore, it controls the distance between silver halide grains, controls the growth conditions of silver halide grains, controls the growth conditions of silver halide grains, controls the volume of the reaction solution at the time of silver halide grain formation, concentration, etc. Can be carried out.

Regarding ultrafiltration using membrane separation, Handbook of Chemical Engineering, 5th revised edition (edited by Chemical Engineering Society, Maruzen) 924
~ 954, RD 102 vol 10208 and 131 vol 1
3122, or Japanese Patent Publication Nos. 59-43727 and 62.
-27008, JP-A-62-113137, 57
No. 209823, No. 59-43727, No. 62-1
No. 13137, No. 61-2199948, No. 62-23
035, 63-40137, 63-40039.
No. 3, JP-A-3-140946 and JP-A-2-172816.
The methods described in No. 2, No. 2-172817, No. 4-22942, etc. can also be referred to. In the present invention,
For ultrafiltration, it is preferable to use the apparatus or method described in JP-A No. 11-339923 or JP-A No. 11-231448.

In the production of the silver halide emulsion of the present invention, desalting is preferably carried out after the formation. Desalting can be performed, for example, by the method of RD17643 item II.

More specifically, in order to remove unnecessary soluble salts from the precipitation product or the emulsion after physical ripening,
The Nudel water washing method in which gelatin is gelled may be used. Inorganic salts, anionic surfactants, anionic polymers (such as polystyrene sulfonic acid), or gelatin derivatives (such as acylated gelatin and carbamoylated gelatin) may be used. The precipitation method utilized can be used. Further, ultrafiltration utilizing the above-mentioned membrane separation can also be preferably used for desalting.

In the formation of nuclei in the silver halide emulsion of the present invention and / or the formation of silver halide grains using the supply of fine silver halide grains, the above nucleation and / or silver halide are formed using a mixer provided outside the reaction vessel. It is preferable to form fine particles. The mixer provided outside the reaction vessel is a continuous process nucleation facility for continuously forming the nuclei and / or silver halide fine particles and continuously supplying the nuclei and / or silver halide fine particles to the reaction vessel. It is preferable. Regarding the continuous process nucleation facility, Japanese Patent Laid-Open No. 2000-11
The description of No. 2049 and the like can be referred to.

In the present invention, US Pat.
It is preferable to use the polyalkylene oxide compounds described in No. 3 and the like.

In the present invention, US Pat.
No. 6, No. 4684607, No. 4680254, No. 4
The surface index control agent for silver halide grains described in, for example, 680255 can also be used.

In the present invention, any ratio of (111) faces and (100) faces on the side faces of the tabular silver halide grain can be used, but (100) faces on all side faces are 2.
It is preferably 0% or more, and more preferably 30% or more.

In the present invention, when reduction sensitization is carried out during the formation of silver halide grains, radical scavengers and other additives for controlling the oxidation of silver nuclei can be used.

In the production of the silver halide emulsion of the present invention, the conditions other than the above are described in JP-A-61-6643.
No. 61, No. 61-14630, No. 61-112142,
62-157024, 62-18556, 6
No. 3-92942, No. 63-151618, No. 63-
163451, 63-220238, 63-3
No. 11244, I and III terms of RD38957, RD
Appropriate conditions can be selected by referring to the XV item of 40145 and the like.

The silver halide emulsion of the present invention comprises an n-valent cation radical and an intramolecular cyclization reaction (n + m).
It is preferable to contain at least one organic compound capable of forming a valent cation (provided that n and m each independently represent an integer of 1 or more and 100 or less).

In the present invention, “an organic compound capable of forming an (n + m) -valent cation from an n-valent cation radical through an intramolecular cyclization reaction” is a specific example of the Society of Synthetic Organic Chemistry. Magazine, Vol. 49, No. 7 (1991)
Pp. 636-644, and the following reaction mechanism causes cyclization reaction from an n-valent cation radical (a monovalent cation radical in the following example) to a (n + m) valent cation (2 in the following example). A cation).

Each of n and m is preferably 1. Specifically, it is an organic compound capable of forming a divalent cation from a monovalent cation radical through an intramolecular cyclization reaction. Is preferred.

The intramolecular cyclization reaction in the present invention is preferably a reaction involving transring formation.

Organic compounds capable of forming an (n + m) -valent cation from an n-valent cation radical by an intramolecular cyclization reaction are represented by the following general formula (1), general formula (2) or general formula The compound represented by (3) can be preferably used.

Formula (1) A ¹ -X ¹ -B ¹ -X ² -A ^{2 In the} formula, X ¹ and X ² each independently represent an N atom, a P atom, an S atom, a Se atom or a Te atom. , A ¹ and A ² each independently represent a substituent, and B ¹ represents a linking group.

[0157]

[Chemical 2]

In the formula, X ³ and X ⁴ are each independently an N atom,
Represents a P atom, S atom, Se atom, Te atom, Y ¹ , Y ²
Represents an atomic group necessary for forming a 6- to 12-membered ring with X ³ and X ⁴ .

In the general formula (2), X ³ , X ⁴ , Y ¹ ,
Atoms forming a ring other than X ³ and X ⁴ of the ring structure formed by Y ² are preferably carbon atoms.

General formula (3) (Z-) _k1 -[-(-L-) _k3- X] _k2 Z represents a silver halide adsorbing group or a light absorbing group, L represents a linking group, and X represents n. A substituent having a partial structure of a compound capable of forming an (n + m) -valent cation from a valent cation radical by an intramolecular cyclization reaction, a substituent having the general formula (1) as a partial structure, or It represents a substituent having the formula (2) as a partial structure. k1 is 0
Represents an integer of 4; k2 represents an integer of 1 to 4; k3 represents 0 or 1.

The light absorbing group represented by Z in the general formula (3) of the present invention is a FM Harme (FM Harme).
r) "Heterocyclic Compounds-Cyanine and Relative Compounds (He
terocyclic Compounds-Cyan
ine Dyes and Related Comp
Sounds, "John Wiley &Sons; New York London, 1964, DM Sturmer," Heterocyclic Compounds-Special Topics in Hetero. " Cyclic chemistry (Hetero)
cyclic Compounds-Special
topics in heterocyclic ch
18) Chapter 14 Section 14-482
515, John Willie & Sons (Joh
nWiley &amp; Sons, Inc. New York London, 1977, "Rods Chemistry of Carbon Compounds (Rodd's Che
MISRY OF CARBON COMPOUND
s) "2 ^nd. Ed. vol. IV, part B, 1977
Published Chapter 15 369-422 tribute, Elsevier Science Publishing Company, Inc. (Els
EvierScience Publishing C
company Inc. ) It can be synthesized based on the method described in, for example, New York published by the company, and the adsorptive group to the silver halide represented by Z in the general formula (3) is described in US Pat. No. 5,538,843. It can be synthesized based on the method described in the patents, etc. described on page 37 to page 29, line 29.

In the present invention, as an organic compound capable of forming an (n + m) -valent cation from an n-valent cation radical in association with an intramolecular cyclization reaction, Japanese Patent Application No. Hei.
00-047160 and Japanese Patent Application No. 2001-23912
It is preferred to use the compounds described in 8.

Specific examples of compounds are shown below, but the invention is not limited thereto.

[0164]

[Chemical 3]

[0165]

[Chemical 4]

[0166]

[Chemical 5]

[0167]

[Chemical 6]

[0168]

[Chemical 7]

[0169]

[Chemical 8]

When a color light-sensitive material is formed by using the silver halide emulsion of the present invention, the silver halide emulsion which has been physically ripened, chemically ripened and spectrally sensitized is used.

The additive used in such a step is R
It is described in the IV and V terms of D38957 and the XV term of RD40145.

Known photographic additives that can be used in the present invention are also the same as those of RD38957, items II to X and RD4014.
The items I to XIII of 5 can be used.

The silver halide photographic light-sensitive material of the present invention comprises
Red, green and blue light sensitive silver halide emulsion layers can be provided and each layer can contain a coupler. The color-forming dyes formed from the couplers contained in each of these layers preferably have spectral absorption maxima separated by at least 20 nm. As the coupler, it is preferable to use a cyan coupler, a magenta coupler and a yellow coupler. As a combination of each emulsion layer and the coupler, usually, a combination of a yellow coupler and a blue photosensitive layer, a magenta coupler and a green photosensitive layer, a cyan coupler and a red photosensitive layer are used, but not limited to these combinations. , Other combinations may be used.

In the present invention, a DIR compound can be used. Specific examples of DIR compounds that can be used include D-1 to D-34 described in JP-A-4-114153, and these compounds can be preferably used in the present invention.

DIR that can be used in the present invention
Specific examples of the compound include, in addition to the above, for example, US Pat. Nos. 4,234,678 and 3,227,554,
3,647,291, 3,958,993, 4,419,886, 3,933,500, JP-A-57-56837, 51-13239, and US Pat. 072,363, 2,070,266, R
Examples thereof include those described in Section XIV of D40145.

Specific examples of the coupler which can be used in the present invention are described in Section II of RD40145.

The additive used in the present invention is RD4014.
It can be added by the dispersion method described in Section VIII of item 5.

In the present invention, the above-mentioned RD38957 is used.
Known supports described in the section XV and the like can be used.

The light-sensitive material of the present invention includes the above-mentioned RD3895.
Auxiliary layers such as a filter layer and an intermediate layer described in Section XI of 7 can be provided.

The light-sensitive material can have various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the item XI of RD38957.

The silver halide emulsion of the present invention can be used in various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. It can be preferably applied.

To develop the silver halide color light-sensitive material of the present invention, for example, T.W. H. By james the
Theory of the Photographic Process 4th Edition (The Theory of The Photo)
graphical Process Forth Edi
page 291 to page 334, and the Journal of the American Chemical Society (Jour).
na1 of the American Chemi
Cal Society) Vol. 73, p. 3,100 (1951), known developers can be used, and the above-mentioned RD38957 can be used.
The development processing can be carried out by a usual method described in Sections XVII to XX and Section XXIII of RD40145.

[0183]

[Examples] The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 << Preparation of tabular silver halide emulsion Em-1 >> [Nucleation / nuclear ripening step] The following gelatin aqueous solution-1 in the reaction vessel was kept at 40 ° C., and JP-A-62-160128 was used. The following silver nitrate aqueous solution-1 and halide aqueous solution-1 were added at a constant flow rate for 1 minute using a double jet method to perform nucleation while vigorously stirring using the described mixing and stirring apparatus.

<Aqueous gelatin solution-1> Alkali-treated inert gelatin (average molecular weight: 100,000) 9.02 g Potassium bromide 2.75 g H ₂ O 3.6 L <Aggregate nitrate solution-1> Silver nitrate 14.0 g H ₂ O 62. 8 ml <halide solution -1> potassium bromide 9.82g H ₂ O 62.4ml the addition finished, immediately following aqueous gelatin solution -2 addition, the temperature was raised to 60 ° C. over a period of 30 minutes, the pH 5 ．
It was adjusted to 0 and aged for 20 minutes in that state.

<Gelatin aqueous solution-2> Alkali-treated inactive gelatin (average molecular weight 100,000) 38.7 g 10% by weight methanol solution of surfactant (EO-1) 1.3 ml H ₂ O 908.6 ml * EO-1 _{: HO (CH 2 CH 2 O} ) m [CH (CH 3) CH 2 O] 19.8 (CH 2 C H 2 O) n H (m + n = 9.77) [ grain growth step -1] after nuclear maturation step ends Then, using a double jet method, silver nitrate aqueous solution-2 and halide aqueous solution-2 were added while accelerating the flow rate. After the addition was completed, gelatin aqueous solution-3 was added, and subsequently silver nitrate aqueous solution-3 and halide aqueous solution-3 were added while accelerating the flow rate. During this period, the silver potential in the reaction vessel (measured with a silver ion selective electrode using a saturated silver-silver sulfide electrode as a reference electrode) was controlled to 12 mV using a 1 mol / L potassium bromide solution.

[0187] <nitrate aqueous -2> nitrate 178.0g H ₂ O 795.0ml <halide solution -2> Potassium bromide 124.7g H ₂ O 792.7ml <gelatin solution -3> alkali-treated inert gelatin (average molecular weight of 100,000) 175.9 g 10 wt% methanol solution of surfactant _{(EO-1) 0.67ml H 2} O 4260.1ml < nitrate aqueous -3> nitrate 1907.6g H ₂ O 2769.5ml <halide solution - 3> Potassium bromide 1322.7 g Potassium iodide 18.6 g H ₂ O 2721.6 ml [Particle growth step-2] After the completion of the particle growth step-1, the following aqueous solution-A1 and then aqueous solution-B1 were added to give 1 mol. /
The pH was adjusted to 9.0 using an L potassium hydroxide aqueous solution, and iodine ions were released while aging for 4 minutes. Then adjust the pH to 5.0 with 1 mol / L nitric acid aqueous solution,
Then, the silver potential in the reaction vessel was adjusted to -19 mV using a 3.5 mol / L potassium bromide aqueous solution, and subsequently, a silver nitrate aqueous solution-4 and a halide aqueous solution-4 were added while accelerating the flow rates. In addition, addition of silver nitrate aqueous solution-4 is 865 ml.
Upon completion, the following aqueous solution-C1 was added, and then the rest of the silver nitrate aqueous solution-4 and the halide aqueous solution-4 were added.

[0188] <aqueous -A1> p-iodoacetamide sodium benzenesulfonate 83.5g H ₂ O 660.1ml <aq -B1> sodium sulfite 29.0g H ₂ O 312.9ml <aq -C1> K ₄ [Ru (CN) ₆ ] 195.6 mg aqueous solution 110 ml <silver nitrate aqueous solution-4> silver nitrate 900.3 g H ₂ O 1307.0 ml <halide aqueous solution-4> potassium bromide 627.4 g potassium iodide 4.4 g H ₂ O 1284 .8 ml Throughout the grain growth steps-1 and 2, the addition rate of the silver nitrate aqueous solution and the halide aqueous solution was adjusted so that no new silver halide grains were generated and the grain was ripened by Ostwald ripening between the growing silver halide grains. The optimum control was performed so that the diameter distribution would not deteriorate.

After the completion of the above-mentioned grain growth step, JP-A-5-7
Chemically modified gelatin in which amino group is phenylcarbamoylated according to the method described in 2658 (modification rate 95%) 2
An aqueous solution containing 24 g was added, desalted and washed with water, gelatin was added to disperse well, and pH was adjusted to 5.8 and pAg was adjusted to 8.9 at 40 ° C.

As described above, a tabular silver halide emulsion Em-1 (hereinafter, also simply referred to as emulsion Em-1) was obtained. As a result of analyzing silver halide grains contained in the tabular silver halide emulsion Em-1, 90% of the projected area of all grains was analyzed.
Are tabular silver halide grains, have an average aspect ratio of 6.5, an average projected area circle-equivalent grain size of 2.0 μm, a projected area circle-equivalent grain size distribution of 20%, and an average grain thickness of 0. Three
The average distance between twin planes was 1 μm, 220Å, and tabular silver halide grains having two twin planes parallel to the main plane accounted for 85% of the number of grains. In the tabular silver halide grains contained in the tabular silver halide emulsion Em-1, 92% had dislocation lines, 32% had dislocation lines in the outer peripheral portion and the main plane, and 50% in number. Had 30 or more dislocation lines in the outer peripheral portion, 22% had 30 or more dislocation lines in the outer peripheral portion, and had dislocation lines in the main plane. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-1 was 2.1 mol%, and the average surface iodide content was 5.3 mol%. The variation coefficient of the distance between twin planes is 34%, the variation coefficient of the grain thickness is 32%, the (100) plane ratio of all the side surfaces of the tabular silver halide grain is 35%, Hexagonal tabular silver halide grains accounted for at least 83%.

<< Preparation of tabular silver halide emulsion Em-2 >> [Preparation of tabular seed emulsion T-A1] A tabular seed emulsion T-A1 was prepared by the following procedure.

[Nucleation Step] 10.7 g of oxidized gelatin A (methionine content 0.3 μmol / g gelatin) and 12.3 g of potassium bromide were added in the reaction vessel.
A 47 L aqueous solution was kept at 20 ° C.
While stirring at high speed using the mixing and stirring apparatus described in Japanese Patent Publication No. 28, the pH was adjusted to 1.90 with 0.5 mol / L sulfuric acid.
Adjusted to. After that, using the double jet method, the following S
Solution-01 and solution X-01 below were added at a constant flow rate over 1 minute to form nuclei, and then solution G-01 below was added.

S-01 liquid: 1.25 mol / L aqueous silver nitrate solution 88.75 ml X-01 liquid: 1.25 mol / L aqueous potassium bromide solution 8
8.75 ml G-01 liquid: 52.0 g of oxidized gelatin A and 3.78 ml of a 10 mass% methanol solution of the following surfactant A
1260 ml of aqueous solution containing A: HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ).
CH ₂ O] ₂₀ (CH ₂ CH ₂ O) _n H (m + n = 10) [Aging step] It takes 73 minutes after completion of the nucleation step to obtain 7
The temperature was raised to 5 ° C. Immediately after the start of temperature rise, pAg was measured using a 1.75 mol / L potassium bromide aqueous solution over 45 minutes.
Was adjusted to 8.6. Forty-five minutes after the start of temperature increase, which is in the middle of heating to 75 ° C., 96.8 ml of an aqueous solution containing 9.68 g of ammonium nitrate was added, and then 285 ml of a 10% potassium hydroxide aqueous solution was added and held for 6 minutes and 30 seconds. Then, the pH was adjusted to 7.6 with a 56% acetic acid aqueous solution.

[Growth step] After completion of the ripening step, pAg was adjusted to 8.6 by using a 1.75 mol / L potassium bromide aqueous solution, and the pH was kept at 6.1 by using a 56% acetic acid aqueous solution. Meanwhile, the following liquid S-02 and liquid X-02 were added using a double jet method in 8 minutes while accelerating the flow rate.

S-02 liquid: 1.25 mol / L silver nitrate aqueous solution 1130 ml X-02 liquid: 1.25 mol / L potassium bromide 1130
ml After completion of addition of each of the above solutions, coagulation precipitation desalting and washing with an aqueous solution of demole (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate were carried out, and alkali-treated inactive gelatin B (methionine content 50.0 μmol / g) Was added and dispersed well to prepare a tabular seed emulsion T-A1.

In the tabular seed emulsion T-A1 described above, 50% of the projected area of all grains are tabular grains having an aspect ratio of 11 or more, the average aspect ratio is 10, and the average projected area circle conversion grain size is 0.62 μm. , Projected area circle equivalent particle size distribution is 27%,
The average grain thickness was 0.06 μm, and the average distance between twin planes was 120Å. The silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains.

[Preparation of tabular silver halide emulsion Em-2] Using the above-mentioned tabular seed emulsion T-A1, grain growth was carried out in the following procedure to obtain a tabular silver halide emulsion Em-2.
-2 was prepared.

As the stirring device, the mixing stirring device described in JP-A-62-160128 was used. Further, when removing soluble components from the reaction solution by ultrafiltration, JP-A-10-
The device described in Japanese Patent No. 339923 was used.

Tabular Seed Emulsion TA equivalent to 0.411 mol
1 and a 10% by mass methanol solution of the surfactant A.
The reaction mother liquor obtained by adding 125.4 ml of pure water and 285.4 g of gelatin B to make the volume 29.9 L was prepared at a temperature of 60 ° C. and 1.
While maintaining the pAg at 9.1 with a 75 mol / L potassium bromide aqueous solution, the following liquid S-11 and liquid X-11 were added by a double jet method over 86 minutes while accelerating the flow rate. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant.

S-11 liquid: 1.75 mol / L silver nitrate aqueous solution 7296 ml X-11 liquid: 1.741 mol / L potassium bromide and 0.
Aqueous solution 7296 containing 009 mol / L potassium iodide
ml Next, the soluble component 1 of the reaction solution is subjected to ultrafiltration over 30 minutes.
2.0 L was removed.

Then, while decelerating the following S-12 solution,
It was added in minutes and the pAg was adjusted to 8.6.

S-12 solution: 727 ml of 1.75 mol / L silver nitrate aqueous solution, the following SA-12 solution and SB-12 solution were added over 2 minutes, and then the following I-11 solution and the following Z-11 solution were added. Was added and the pH was adjusted to 9.3 with a 10% aqueous potassium hydroxide solution and held for 6 minutes, and then the pH was adjusted to 5.0 with a 56% aqueous acetic acid solution and pA with a 1.75 mol / L aqueous potassium bromide solution.
The g was adjusted to 9.4.

SA-12 solution: 0.5 mol / L silver nitrate aqueous solution 847 ml SB-12 solution: 0.5 mol / L sodium chloride aqueous solution 847 ml I-11 solution: sodium p-iodoacetamidobenzenesulfonate of 100. Aqueous solution containing 0 g 806 ml Z-11 solution: 358 ml aqueous solution containing 34.7 g sodium sulfite Subsequently, the following S-13 solution and the following X-13 solution were added over 16 minutes while accelerating the addition flow rate. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. During the addition, the pH was adjusted to 5.0 with a 56% aqueous acetic acid solution, and the pAg was controlled to 9.4 with an aqueous 1.75 mol / L potassium bromide solution.

S-13 solution: 1.90 mol / L silver nitrate aqueous solution 1090 ml X-13 solution: 1.663 mol / L potassium bromide and 0.
Aqueous solution 1090 containing 088 mol / L potassium iodide
ml Subsequently, the following S-14 solution was added over 15 minutes while decelerating to adjust the pAg to 8.4.

S-14 solution: 727 ml of 1.75 mol / L silver nitrate aqueous solution. Then, the following M-11b solution was added, and then S
Solution -15 and solution X-15 below were added over 24 minutes while accelerating the flow rate. During the addition, the pH was adjusted to 5. with a 56% acetic acid aqueous solution.
The pAg was controlled to 8.4 with 0, 1.75 mol / L potassium bromide aqueous solution. Then, pAg was adjusted to 9.4 with a 1.75 mol / L potassium bromide aqueous solution. Subsequently, the following S-16 solution and the following X-16 solution were added over 17 minutes while accelerating the flow rate. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. During the addition, the pH was adjusted to 5.0 with a 56% aqueous acetic acid solution.
The pAg was controlled at 9.4 with an aqueous 75 mol / L potassium bromide solution.

M-11b solution: K ₄ [Ru (CN) ₆ ] was added to 2
Aqueous solution containing 34.7 mg, 132 ml S-15 solution: 1.75 mol / L silver nitrate aqueous solution 605 m
l X-15 solution: 1.663 mol / L potassium bromide and 0.
Aqueous solution containing 088 mol / L potassium iodide 605 m
1 S-16 solution: 1.75 mol / L silver nitrate aqueous solution 1211
ml X-16 solution: 1.75 mol / L potassium bromide aqueous solution 1
211 ml After the completion of the above addition, an aqueous solution containing 360 g of chemically modified gelatin (modification rate 95%) in which an amino group was phenylcarbamoylated was added according to the method described in JP-A-5-72658, and desalting and washing treatment were performed. , Gelatin was added to disperse well, pH was 5.8 and pAg was 8.9 at 40 ° C.
Adjusted to.

As described above, a tabular silver halide emulsion Em-2 (hereinafter simply referred to as emulsion Em-2) was obtained. As a result of analyzing silver halide grains contained in the tabular silver halide emulsion Em-2, 95% of the projected area of all grains was analyzed.
The tabular silver halide grains account for the above, the average aspect ratio is 11, the average projected area circle conversion grain size is 2.4 μm,
The projected area circle-equivalent grain size distribution is 35%, the average grain thickness is 0.22 μm, and the average twin plane distance is 120Å.
The tabular silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains. In the tabular silver halide grains contained in the tabular silver halide emulsion Em-2, 72% have dislocation lines, 33% have dislocation lines in the outer peripheral portion and the main plane, and 55% in terms of the number of grains. Had 30 or more dislocation lines in the outer peripheral portion, 25% had 30 or more dislocation lines in the outer peripheral portion, and had dislocation lines in the main plane. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-2 was 2.3 mol% and the average surface iodide content was 5.6 mol%. The variation coefficient of the distance between twin planes is 30%, and the variation coefficient of the grain thickness is 3
3%, which is (10% on all sides of the tabular silver halide grain).
The 0) plane ratio was 34%, and 90% or more of the number of grains was occupied by hexagonal tabular silver halide grains.

<< Preparation of Tabular Silver Halide Emulsion Em-3 >> In the preparation of the above emulsion Em-2, the following I-11a solution and Z-11 solution were used in place of the I-11 solution and Z-11 solution.
A tabular silver halide emulsion Em-3 (hereinafter also simply referred to as emulsion Em-3) was prepared in the same manner except that the liquid a was used.

Solution I-11a: 1550 ml aqueous solution containing 192.3 g of sodium p-iodoacetamidobenzenesulfonate Z-11a solution: 688 ml aqueous solution containing 66.7 g of sodium sulfite Halogen contained in tabular silver halide emulsion Em-3. As a result of analyzing the silver halide grains, tabular silver halide grains occupy 95% or more of the projected area of all grains, the average aspect ratio is 11, the average projected area circle converted grain size is 2.4 μm, and the projected area circle converted. Particle size distribution is 35%, average particle thickness is 0.22
μm, the average distance between twin planes was 120Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains. Further, in the tabular silver halide grains contained in the tabular silver halide emulsion Em-3, 92% had dislocation lines, 83% had dislocation lines in the outer peripheral portion and main plane, and 75% in terms of the number of grains. Has 30 or more dislocation lines in the outer periphery, 65% has 30 or more dislocation lines in the outer periphery, has dislocation lines in the main plane, and dislocation lines are localized near the apex. It was The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-3 is 3.5.
%, And the average surface silver iodide content was 7.6 mol%. The variation coefficient of the distance between twin planes is 30%, the variation coefficient of the grain thickness is 33%, the (100) plane ratio of all side surfaces of the tabular silver halide grain is 34%, and Hexagonal tabular silver halide grains accounted for 90% or more.

<< Preparation of Tabular Silver Halide Emulsion Em-4 >> In the preparation of the above-mentioned emulsion Em-3, the pAg at the time of addition of the S-11 solution and the X-11 solution was controlled to 9.4. Similarly, tabular silver halide emulsion Em-4
(Hereinafter, also simply referred to as emulsion Em-4) was prepared. As a result of analyzing the silver halide grains contained in the tabular silver halide emulsion Em-4, tabular silver halide grains occupy 95% or more of the projected area of all grains, and the average aspect ratio is 1.
5, average projected area circle converted particle size is 2.6 μm, projected area circle converted particle size distribution is 36%, average particle thickness is 0.19 μm
m, the average distance between twin planes was 120Å, and tabular silver halide grains having two twin planes parallel to the main plane accounted for 95% of the number of grains. The tabular silver halide grains contained in the tabular silver halide emulsion Em-4 had a dislocation line of 94%, a dislocation line of 88%, and a dislocation line of 78%. Has 30 or more dislocation lines in the outer periphery, 74% has 30 or more dislocation lines in the outer periphery, has dislocation lines in the main plane, and dislocation lines are localized near the apex. It was The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-4 was 3.5 mol%, and the average surface iodide content was 7.8 mol%. The variation coefficient of the distance between twin planes is 31%, the variation coefficient of the grain thickness is 32%, the (100) plane ratio of all side surfaces of the tabular silver halide grain is 30%, Hexagonal tabular silver halide grains accounted for 90% or more.

<< Preparation of tabular silver halide emulsion Em-5 >> [Preparation of tabular seed emulsion T-A2] A tabular seed emulsion T-A2 was prepared by the following procedure.

[Nucleation Step] The tabular seed emulsion T-A1 described above.
For the nucleation in the preparation of the above, using the continuous method nucleation facility described in JP-A 2000-112049, the following S-01a solution and the following X-01a solution were added at 20 ° C. at a constant flow rate for 4 minutes to form nuclei. A tabular seed emulsion T-is prepared in the same manner as above except that it is introduced into a reaction vessel, heated, ripened and grown.
A2 was prepared.

S-01a solution: An aqueous solution 249 containing 18.85 g of silver nitrate and 29.0 ml of 0.5 mol / L sulfuric acid.
4 ml X-01a solution: aqueous solution containing 28.2 g of potassium bromide and 23.8 g of oxidized gelatin A (methionine content 0.3 μmol / g gelatin) 2494 ml The above tabular seed emulsion T-A2 has a projected area of all grains. Of 50
% Are tabular grains having an aspect ratio of 25 or more, the average aspect ratio is 119, and the average of projected area circle conversion grain sizes is 0.7.
The average grain size was 6 μm, the projected-area-circle equivalent grain size distribution was 27%, the average grain thickness was 0.04 μm, and the average distance between twin planes was 100 Å. The silver halide grains having two twin planes parallel to the principal plane accounted for 95% of the number of grains.

[Preparation of tabular silver halide emulsion Em-5] Using the above-mentioned tabular seed emulsion T-A2, grain growth was continued in the following procedure to obtain tabular silver halide emulsion Em.
-5 was prepared.

As the stirring device, the mixing stirring device described in JP-A-62-160128 was used. Further, when removing soluble components from the reaction solution by ultrafiltration, JP-A-10-
The device described in Japanese Patent No. 339923 was used.

Tabular Seed Emulsion TA equivalent to 0.411 mol
2 and a 10% by mass solution of the surfactant A in methanol.
A reaction mother liquor having a volume of 59.8 L obtained by adding 428.1 g of gelatin B to 12 ml and pure water was prepared at a temperature of 60 ° C. and 1.
While maintaining the pAg at 9.6 with a 75 mol / L potassium bromide aqueous solution, the following liquid S-11a and the following liquid X-11a were added in 66 minutes while accelerating the flow rate using a double jet method. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant.

S-11a solution: 1.75 mol / L silver nitrate aqueous solution 7114 ml X-11a solution: an aqueous solution 71 containing 1.741 mol / L potassium bromide and 0.009 mol / L potassium iodide 71
14 ml Next, the soluble component 4 of the reaction solution was subjected to ultrafiltration over 30 minutes.
2.0 L was removed.

Then, while decelerating the following S-12 solution,
It was added in minutes and the pAg was adjusted to 8.6.

S-12 solution: 727 ml of 1.75 mol / L silver nitrate aqueous solution, the following SA-11a solution and SB-11b solution were added over 2 minutes, and then the following I-11b solution and the following Z-11 solution were added.
Solution b was added, the pH was adjusted to 9.3 with a 10% aqueous potassium hydroxide solution, and the mixture was held for 6 minutes, then, with a 56% aqueous acetic acid solution, the pH was adjusted to 5.0 with a 1.75 mol / L aqueous potassium bromide solution. The pAg was adjusted to 9.4.

SA-11a solution: 0.5 mol / L silver nitrate aqueous solution 1484 ml SB-11b solution: 1.741 mol / L sodium chloride aqueous solution 1484 ml I-11b solution: sodium p-iodoacetamidebenzenesulfonate was added 192. Aqueous solution containing 3 g 1550 ml Z-11b solution: Aqueous solution containing 66.7 g sodium sulfite 688 ml Subsequently, the following S-13 solution and the following X-13 solution were added over 14 minutes while accelerating the addition flow rate. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. During the addition, the pH was adjusted to 5.0 with a 56% aqueous acetic acid solution, and the pAg was controlled to 9.4 with an aqueous 1.75 mol / L potassium bromide solution.

S-13 solution: 1.75 mol / L silver nitrate aqueous solution 1090 ml X-13 solution: 1.663 mol / L potassium bromide and 0.
Aqueous solution 1090 containing 088 mol / L potassium iodide
ml Subsequently, the following S-14 solution was added over 12 minutes while decelerating to adjust the pAg to 8.4.

S-14 solution: 727 ml of 1.75 mol / L silver nitrate aqueous solution. Then, after adding M-11b solution shown below, S-solution shown below was added.
Solution -15 and solution X-15 below were accelerated in flow rate and added over 20 minutes. During the addition, the pH was adjusted to 5.0 with a 56% acetic acid aqueous solution,
PAg was adjusted to 8.75 mol / L potassium bromide aqueous solution.
Controlled to 4. Then, pAg was adjusted to 9.4 with a 1.75 mol / L potassium bromide aqueous solution. Subsequently, while accelerating the flow rates of the following S-16 solution and the following X-16 solution (the ratio of the addition flow rate at the end to the addition start flow rate is 1:
1.6) Added over 13 minutes. At this time, the soluble component of the reaction solution was removed by ultrafiltration to keep the volume of the reaction solution constant. During the addition, the pH was adjusted to 5. with a 56% acetic acid aqueous solution.
The pAg was controlled to 9.4 with 0, 1.75 mol / L potassium bromide aqueous solution.

Solution M-11b: K ₄ [Ru (CN) ₆ ] was added to 2
Aqueous solution containing 34.7 mg, 132 ml S-15 solution: 1.75 mol / L silver nitrate aqueous solution 605 m
l X-15 solution: 1.663 mol / L potassium bromide and 0.
Aqueous solution containing 088 mol / L potassium iodide 605 m
1 S-16 solution: 1.75 mol / L silver nitrate aqueous solution 1211
ml X-16 solution: 1.75 mol / L potassium bromide aqueous solution 1
211 ml After the completion of the above addition, an aqueous solution containing 360 g of chemically modified gelatin (modification rate 95%) in which an amino group was phenylcarbamoylated was added according to the method described in JP-A-5-72658, and desalting and washing treatment were performed. , Gelatin was added to disperse well, pH was 5.8 and pAg was 8.9 at 40 ° C.
Adjusted to.

As described above, a tabular silver halide emulsion Em-5 (hereinafter simply referred to as emulsion Em-5) was obtained. As a result of analyzing silver halide grains contained in the tabular silver halide emulsion Em-5, 97% of the projected area of all grains was analyzed.
Tabular silver halide grains account for the above, and 50% of the projected area of all grains are tabular grains having an aspect ratio of 70 or more,
The average aspect ratio is 60, the average projected area circle converted grain size is 4.3 μm, the projected area circle converted grain size distribution is 27%, the average grain thickness is 0.07 μm, and the twin plane distance average is 100.
Å, and tabular silver halide grains having two twin planes parallel to the principal plane accounted for 94% of the number of grains. Further, in the tabular silver halide grains contained in the tabular silver halide emulsion Em-5, 92% of the grains have dislocation lines,
84% has dislocation lines in the outer peripheral portion and the main plane, 74% has 30 or more dislocation lines in the outer peripheral portion, and 70% has 3 dislocation lines in the outer peripheral portion.
It had 0 or more dislocation lines, had dislocation lines on the main plane, and dislocation lines were localized near the apex. The average silver iodide content of the silver halide grains contained in the tabular silver halide emulsion Em-5 was 3.5 mol% and the average surface iodide content was 7.3 mol%.

The inter-grain distribution of the distance between the twin planes was 20%, the inter-grain distribution of the grain thickness was 10%, and the (100) face ratio of all the side faces of the tabular silver halide grains was 30%.
%, And 90% or more of the number of grains was occupied by hexagonal tabular silver halide grains.

Other features of Emulsions Em-1 to Em-5 are shown in Table 1.

[0227]

[Table 1]

Each of the emulsions Em-1 to Em-5 prepared above was heated to 57 ° C. and then silver potential 50 mV and pH.
The sensitizing dye and trifrylphosphine selenide described in the ninth layer of the color light-sensitive material sample described later in 6.5, chloroauric acid
Add potassium thiocyanate and sodium thiosulfate pentahydrate to ripen the mixture so that the sensitivity is optimized.
-Methyl-4hydroxy-1,3,3a, 7-tetrazaindene, the compound (1-6) described in Japanese Patent Application No. 2000-281888, and silver iodide fine particles are added, followed by cooling to solidify by cooling. Color sensitization and chemical sensitization were performed.

Each of the emulsions of Em-1 to Em-5 was subjected to color sensitization and chemical sensitization, and then at 38 ° C., the compounds T-28 and T- of the general formulas (1) to (3) of the present invention were used. 36, T-5
1, (each amount shown in Table 6) was added as a mixed solution of water / methanol, the mixture was stirred for 5 minutes, cooled, and cooled to solidify the emulsions Em-1a to Em-5a and Em-1b to, respectively.
It was set to Em-5b and Em-1c to Em-5c. << Preparation of color light-sensitive material >> Thickness of 120μ with undercoat layer
On the triacetyl cellulose film support of m, each layer having the composition shown in Tables 2 to 4 below was sequentially formed from the support side to prepare a multilayer color light-sensitive material sample 101. The addition amount of each material listed in the table is 1 m ² unless otherwise specified.
It is shown in grams per unit. In addition, silver halide and colloidal silver are shown in terms of the amount of silver, and a sensitizing dye (indicated by SD)
Is the number of moles per mole of silver.

Here, silver iodobromide emulsion G described in the ninth layer below is used.
As the emulsion E which has been subjected to the above-mentioned color sensitization and chemical sensitization,
m-1 was used. The coating liquid for each constituent layer was coated within 1 hour after the addition of each additive listed in the table was completed.

[0231]

[Table 2]

[0232]

[Table 3]

[0233]

[Table 4]

Table 5 shows the characteristics of silver iodobromide emulsions other than the above-mentioned emulsions used for the preparation of each sample described above.

[0235]

[Table 5]

To each emulsion other than Emulsion M shown in Table 5, sensitizing dyes shown in Tables 2 to 4 were added and ripened, and then fog and sensitivity were optimized in accordance with a conventional method. What was chemically sensitized was used.

Incidentally, among the emulsions shown in Table 5, Emulsions H to K were subjected to reduction sensitization treatment. Also, emulsions A to F
Contains a metal ion or a metal ion complex in a silver halide grain, Emulsions A to K have dislocation lines in the grains, and Emulsions A and D to I and K have a grain number of 50% by number or more. Have 30 or more dislocation lines in the fringe portion. Emulsions A, D to I, and K each have two twin planes in which 80% by number or more of grains are parallel to the main plane.

In the preparation of each sample, in addition to the above composition, OIL-3, coating aids SU-1, SU-2, S
U-3, dispersion aid SU-4, viscosity modifier V-1, stabilizer ST-1, weight average molecular weight: 10,000 and weight average molecular weight: 100,000 of two kinds of polyvinylpyrrolidone (AF-1, AF-2), calcium chloride, inhibitor AF
-3, AF-4, AF-5, AF-6, AF-7, hardener H-1 and preservative Ase-1 were added.

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

[0240]

[Chemical 9]

[0241]

[Chemical 10]

[0242]

[Chemical 11]

[0243]

[Chemical 12]

[0244]

[Chemical 13]

[0245]

[Chemical 14]

[0246]

[Chemical 15]

[0247]

[Chemical 16]

[0248]

[Chemical 17]

[0249]

[Chemical 18]

[0250]

[Chemical 19]

(Production of Samples 102 to 110) Sample 1 above
In the preparation of No. 01, the emulsion Em-1 of the ninth layer was replaced with the emulsion Em.
-2-Em-5 and emulsions Em-1a to Em-5a, E
Sample 10 was prepared in the same manner as Sample 101 except that m-1b to Em-5b and Em-1c to Em-5c were respectively changed.
2-120 were produced respectively.

<< Evaluation of Samples >> (Exposure and Development Processing) Each sample prepared as described above was subjected to wedge exposure through a Toshiba glass filter (Y-48) using a light source with a color temperature of 5400 ° K. Done,
Then, paragraph [0220] of JP-A-10-123652.
Color development processing was performed according to the development processing steps described in [0227] to [0227].

(Evaluation of Sensitivity, Pressure Resistance and Processing Stability) The sensitivity, pressure resistance and processing stability of each sample after development processing were evaluated according to the methods described below.

<Sensitivity> Each developed sample thus obtained was subjected to X-
The magenta density is measured with a densitometer manufactured by Rite.
A characteristic curve of density D-exposure amount LogE was prepared and the sensitivity was determined. The sensitivity is defined as the reciprocal of the exposure amount that gives an optical density of minimum density + 0.20, and is shown as a relative value with the sensitivity value of Sample 101 being 100 (the higher the value, the higher the sensitivity. , Means preferred).

<Pressure resistance> Each pressure resistance of each sample is 23.degree.
/ In the condition of relative humidity 55%, using a scratch strength tester (manufactured by Shinto Kagaku), the radius of curvature of the tip is 0.025 mm
After applying a load of 5 g to the sapphire needle and scanning at a constant speed, exposure and development processing was performed in the same manner as above, and at the exposure amount point showing the density of the minimum density +0.5 in the sample without pressure, The concentration difference between the unpressurized sample and the pressurized sample (concentration decrease due to pressurization) was calculated and shown as a relative value with the value of sample 101 being 100 (the smaller the value, the better the pressure resistance). Indicates).

<Process Stability> Three samples of each of Samples 101 to 120 were prepared and subjected to wedge exposure with white light, and the color development time was changed to 2 minutes 45 seconds, 3 minutes 15 seconds and 3 minutes 45 seconds, respectively. Color development processing is performed, and the density of the processed samples of the samples with different development times is measured with a green filter, and the sensitivity value S and the gamma of the obtained characteristic curve at the density of +0.2 G (minimum density +0.2
And the slope of the characteristic curve at the minimum concentration + plus 0.7)
From the above, the characteristic values T ₁ (S), T ₂ (S), T ₁ (G) and T ₂ (G) of the following process fluctuation widths were obtained from the following calculations.

Characteristic value of process variation width T ₁ (S) = S (3′15 ″) / S (2′45 ″) × 1
00 T ₂ (S) = S (3′15 ″) / S (3′45 ″) × 1
00 T ₁ (G) = G (3′15 ″) / G (2′45 ″) × 1
00 T ₂ (G) = G (3′15 ″) / G (3′45 ″) × 1
00 T ₁ (S), T ₂ (S), T ₁ (G), and T ₂ (G) have a numerical value closer to 100, indicating that the processing stability is excellent.

Table 6 shows the above results.

[0259]

[Table 6]

As is clear from Table 6, it can be seen that the samples of the present invention containing the silver halide emulsion of the present invention have high sensitivity, good pressure resistance and improved processing stability.

[0261]

According to the present invention, a silver halide emulsion having high sensitivity, excellent pressure resistance and improved processing stability can be provided. Further, a silver halide photographic light-sensitive material using the emulsion can be provided.

Claims (9)

[Claims] 1. The total projected area of silver halide grains is from 70 to 70.
100% are tabular silver halide grains, the tabular silver halide grains have an average aspect ratio of 8 to 500, and each tabular silver halide grain has 30 or more dislocation lines in the outer peripheral portion. Where D _{1 is} the density of dislocation lines near the apex and D ₂ is the density of dislocation lines in the fringe portion, D ₁ /
A silver halide emulsion characterized in that the ratio of tabular silver halide grains having a D ₂ value of 1.3 or more and 1000 or less is 50 to 100% by number. 2. The projected area of all silver halide grains is from 70 to 70.
100% are tabular silver halide grains, the tabular silver halide grains have an average aspect ratio of 8 to 500, and each tabular silver halide grain has 30 or more dislocation lines in the outer peripheral portion. , S _{1 is} the average length of the dislocation lines near the apex, and S _{2 is} the average length of the dislocation lines in the fringe portion.
, The ratio of tabular silver halide grains having an S ₁ / S ₂ value of 1.5 or more and 100 or less is 50 to 100% by number, and a silver halide emulsion is characterized. 3. 50 to 1 of the tabular silver halide grains
The silver halide emulsion according to claim 1 or 2, characterized in that 100% by number has a dislocation line in the main plane. 4. The projected area of all silver halide grains is from 70 to 70.
100% are tabular silver halide grains, the tabular silver halide grains have an average aspect ratio of 8 to 500, and the tabular silver halide grains have dislocation lines localized near the apex in the outer peripheral portion. And a proportion of tabular silver halide grains having dislocation lines in the main plane is 50 to 100% by number, a silver halide emulsion. 5. The silver halide emulsion according to claim 1, wherein the tabular silver halide grains have a variation coefficient of grain size distribution of 30% or less. 6. The silver halide emulsion as claimed in claim 1, wherein the tabular silver halide grains have an average aspect ratio of 15 to 500. 7. The tabular silver halide grains have an average projected area circle equivalent grain size of 1.0 to 50 μm and an average thickness of 0.005 to 0.1 μm. 7. The silver halide emulsion according to any one of 8. An organic compound capable of forming an (n + m) -valent cation from an n-valent cation radical through an intramolecular cyclization reaction (wherein n and m are independently 1
8. The silver halide emulsion according to claim 1, further comprising at least one of the above (representing an integer of 100 or less). 9. A silver halide photographic light-sensitive material comprising the silver halide emulsion according to claim 1 in at least one silver halide emulsion layer on a support.