JP2001264912A - Silver halide photographic emulsion, method for preparing the same and silver halide photographic sensitive material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin flat platy grain emulsion further excellent in sensitivity to color sensitization, a method for preparing the emulsion and a silver halide photographic sensitive material using the emulsion. SOLUTION: The silver halide photographic emulsion has <=40% coefficient of variation of equivalent circular diameter of all grains and >=50% of the total projected area is occupied by flat platy grains which satisfy the following requirements (i)-(vi); (i) silver iodobromide or silver iodochlorobromide grains having (111) faces as the principal surfaces, (ii) >=1.0 μm equivalent circular diameter and <=0.1 μm thickness, (iii) each of the grains comprises a core a shell containing >=10 dislocation lines ranging from the interface between the shell and the core to the edge of the grain, (iv) when each of the flat platy grains is seen from a direction perpendicular to the principal surfaces, the shell forming region is a circular region corresponding to >=10% of the length from a side of the grain to the center, (v) when the average silver iodide content of the grains is represented by I mol% (0.3<I<20), the silver iodide content of each of the grains is in the range of 0.7 I to 1.3 I and (vi) >=0.5 μm equivalent spherical diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tabular silver halide emulsion having improved color sensitization sensitivity, a method for producing the same, and a silver halide photographic material using the same.

[0002]

2. Description of the Related Art Tabular silver halide grains (hereinafter referred to as "tabular grains") have the following photographic properties: (1) a large ratio of surface area to volume (hereinafter referred to as specific surface area); Therefore, the color sensitization sensitivity is relatively higher than the intrinsic sensitivity.

(2) When an emulsion containing tabular grains is coated and dried, the grains are arranged parallel to the upper surface of the support, so that the thickness of the coating layer can be reduced and the photographic material has good sharpness.

(3) In a radiographic system, when a sensitizing dye is added to tabular grains, silver halide crossover light can be remarkably reduced, and deterioration of image quality can be prevented.

(4) An image with little light scattering and high resolution can be obtained.

(5) The sensitivity to blue light is low.
When used in a green photosensitive layer or a red photosensitive layer, the yellow filter can be removed from the emulsion.

Because of these many advantages, they have been used in high-sensitivity commercial photosensitive materials.

[0008] Japanese Patent Publication No. 6-44132, Japanese Patent Publication No. 5-16
No. 015 discloses a tabular grain emulsion having an aspect ratio of 8 or more. Here, the aspect ratio is indicated by the ratio of the grain diameter to the thickness of the tabular grains. Further, the grain diameter refers to the diameter of a circle having an area equal to the projected area of the grain when the emulsion is observed with a microscope or an electron microscope. The thickness is indicated by the distance between two parallel surfaces constituting the tabular silver halide.

Also, the present invention relates to tabular silver halide grains having dislocations. Regarding dislocations of silver halide crystals, CR Berry J. Apply. Phys. 27, 636 (1956) CR Berry J. Apply. Phys. 35, 2165 (1964) JF Hamilton Photo. Sci. Eng. 11, 57 (1967) T. Shiozawa J. Soc. Photo. Sci. Jpn. 34, 16 (1971) T. Shiozawa J. Soc. Photo. Sci. Jpn. 35, 213 (1972), etc., that it is possible to observe dislocations in a crystal by X-ray diffraction or low-temperature transmission electron microscopy and to give distortion to the crystal. Describes that various dislocations occur in the crystal.

JP-B-6-70708, JP-A-1-20
No. 149 discloses tabular silver halide grains into which dislocations are intentionally introduced. It has been shown that tabular grains into which dislocations have been introduced are superior to tabular grains without dislocations in photographic properties such as sensitivity and reciprocity, and that when these are used in a photosensitive material, they are excellent in sharpness and graininess. . Further, techniques for increasing the density of dislocation introduction into tabular grains, limiting the introduction position, and making the silver iodide content distribution uniform among grains are disclosed in, for example, JP-A-6-27564 and JP-A-6-258745. I have.

In recent years, in the field of silver halide color photographic materials, ultra-high sensitivity represented by ISO1600-3200 and small format represented by a new standard (Advanced Photo System: APS) have been developed. Increasingly, higher image quality is required. For this reason, silver halide emulsions having higher sensitivity and more excellent graininess are required. Conventional silver halide emulsions are insufficient to meet these requirements, and further improvement in performance is desired. Was rare.

As one method of further improving the performance of a silver halide emulsion, it is conceivable to make the grains thinner and to introduce dislocation lines, but ultrathin tabular grains having a thickness of 0.1 μm or less can be considered. In the preparation of, the growth in the thickness direction due to the shell formation after the introduction of the fringe dislocations has been a major obstacle. That is, the dislocation lines generated at the core / shell interface prevent the tabular grains from growing in the lateral direction, so that the tabular grains grow exclusively in the thickness direction. It is not clear why this dislocation suppresses the lateral growth, but this effect significantly increases the thickness of the tabular grains due to the introduction of dislocations and the formation of shells, making it difficult to achieve both the target thinning and the introduction of dislocation lines. Becomes Especially thickness 0.1μ
For ultrathin tabular grains of m or less, depending on the silver content ratio of the shell, the rate of increase in grain thickness due to the introduction of dislocations and the formation of the shell increases, making it more difficult to achieve both thinning and introduction of dislocation lines. Was needed.

A method of greatly reducing the silver content ratio of the shell to suppress the increase in thickness is conceivable. However, when the shell phase is extremely reduced, the silver iodide content near the grain surface increases and the developability deteriorates. This is not realistic because there is a problem that dislocations introduced by re-dissolution of the particle surface disappear. It is also conceivable that the thickness of the resulting tabular grains can be reduced by making a very thin and small core and forming a shell, but the underlying core grains must be very thin, and such thin It is difficult and practical to introduce sufficient dislocations into the grains.

On the other hand, with the increase in sensitivity of silver halide emulsions, the demand for pressure resistance has become stronger than ever. In general, it is known that when various pressures are applied to a silver halide photographic light-sensitive material, photographic performance is changed. For example, fogging and desensitization occur when pressure is applied to or bent when a silver halide photographic light-sensitive material is manufactured or transported in a camera, which has been a practical problem. In particular, when a photosensitive material is folded, tabular grains having a large equivalent circle diameter and a small grain thickness are more likely to cause fogging and desensitization, and it has been desired to achieve both high sensitivity and improved pressure resistance for such grains. .

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thin tabular grain emulsion having further excellent color sensitization sensitivity, a method for producing the same, and a silver halide photographic material using the same. .

[0016]

The above object has been attained by the following means.

(1) The variation coefficient of the circle equivalent diameter of all particles is 4
A silver halide photographic emulsion characterized in that tabular grains of 0% or less and satisfying the following (i) to (vi) account for 50% or more of the total projected area.

(I) Silver iodobromide or silver iodochlorobromide grains having a (111) plane as a main surface. (Ii) A circle-equivalent diameter of 1.0 μm or more and a thickness of 0.1 μm or less. In the shell, dislocation lines reaching the grain edge from the interface between the core and the shell are set at 1 grain per grain.
(Iv) When the tabular grains are viewed from a direction perpendicular to the main surface, the shell-constituting region is an annular region having a length of 10% or more from the side to the center of the tabular grains. (V) The average silver iodide content of all grains is I mol% (0.3 <
I <20), the silver iodide content is in the range of 0.7I to 1.3I. (Vi) The equivalent sphere diameter is 0.5 μm or more.

(2) The silver halide photographic emulsion according to the above (1), wherein the number of dislocation lines in the above (iii) is 20 or more.

(3) The coefficient of variation of the equivalent circle diameter of all particles is 2
The silver halide photographic emulsion according to the above (1) or (2), wherein the content is 5% or less.

(4) The variation coefficient of the circle equivalent diameter of all particles is 1
The silver halide photographic emulsion according to the above (1) or (2), wherein the content is 5% or less.

(5) The method for producing a silver halide photographic emulsion according to any one of the above (1) to (4), wherein a shell containing dislocations is grown in the presence of a crystal habit controlling agent. .

(6) The silver halide photographic emulsion according to the above (5), wherein a high molecular weight gelatin containing 30% or more of a component having a molecular weight of 280,000 or more in a molecular weight distribution measured by a PAGI method is used. Production method.

(7) The method for producing a silver halide photographic emulsion according to the above (5) or (6), wherein tabular grains formed by adding a silver halide fine grain emulsion are used as a core.

(8) A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to any one of the above (1) to (4).

(9) A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion prepared by the production method according to any one of the above (5) to (7).

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

Tabular silver halide grains satisfying the requirements (i) to (vi) defined in the present invention (hereinafter, also referred to as “tabular grains of the present invention”) are two opposing parallel main surfaces. A particle having a diameter equivalent to a circle of the main surface (diameter of a circle having the same projected area as the main surface) is at least 10 times larger than the distance of the main surface (that is, the thickness of the particle). In the emulsion of the present invention,
The ratio of the sum of the projected areas of the tabular grains satisfying the requirements (i) to (vi) to the total projected area is 50% or more, and 70%.
Or more, more preferably 80% or more.

The average grain diameter / grain thickness ratio of the emulsion containing tabular grains of the present invention is preferably from 10 to 50, and more preferably from 10 to 35.
Is more preferable, and more preferably 10 to 25. Here, the average particle diameter / particle thickness ratio is:
It can be obtained by averaging the grain diameter / thickness ratio of all tabular grains, but as a simple method, it can also be determined as the ratio of the average diameter of all tabular grains to the average thickness of all tabular grains.

The diameter (corresponding to a circle) of the tabular grains of the present invention is preferably from 1 to 20 μm, more preferably from 1 to 20 μm.
It is 10 μm, more preferably 1 to 5 μm. The thickness of the tabular grains of the present invention is 0.1 μm or less, preferably 0.08 μm or less, more preferably 0.08 μm or less.
6 μm or less. The lower limit of the particle thickness is about 0.01 μm in consideration of maintaining the shape of the particles.

In the present invention, the equivalent sphere diameter is a particle diameter determined as the diameter of a sphere having the same volume as the silver halide grains. The sphere equivalent diameter of the tabular grains of the present invention is preferably 0.5 μm or more and 1.5 μm or less, and more preferably 0.6 μm or more and 1.0 μm or less.

In the present invention, the measurement of the particle diameter and the particle thickness can be obtained from an electron micrograph of the particles as in the method described in US Pat. No. 4,434,226. That is, the measurement of the particle thickness is easy by evaporating a metal from the oblique direction of the particles together with the reference latex, measuring the shadow length on an electron micrograph, and calculating by referring to the shadow length of the latex. You can know.

The tabular grains of the present invention have dislocations. The dislocation of tabular grains is described, for example, in JF Hamilton, Photo. Sc.
i. Eng. 11, 57 (1967) and T. Shiozawa, J. Soc. Photo.
Sci. Jpn. 35, 213 (1972) can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out under safety light are placed on a mesh for electron microscopic observation, taking care not to apply enough pressure to generate dislocations in the grains from the emulsion to prevent damage (print-out, etc.) by electron beams. The observation is performed by the transmission method in a state where the sample is cooled as described above. In this case, the thicker the particles, the more difficult it is for an electron beam to pass through.
The use of an electron microscope (at 200 kV or more) for particles having a thickness of 25 μm enables more clear observation.
From the photograph of the particles obtained by such a method, it is possible to know the position and the number of dislocations in each particle when viewed from the direction perpendicular to the main surface.

The position where the dislocation of the tabular grain of the present invention exists is the shell part. Dislocations occur at the boundary between the core and the shell and extend as the shell grows. At this time, the direction in which the dislocation proceeds may be almost perpendicular to the side of the tabular grain, but may not be a right angle but may be a curve.

The region constituting the shell where the dislocation lines exist in the tabular grain of the present invention is, when the tabular grain is viewed from a direction perpendicular to the main surface, the region constituting the shell is the side of the tabular grain. It consists of an annular region that is at least 10% of the length from the center to the center. In other words, when the radius of a circle having an area equivalent to the main surface area of the tabular grain is L, the region constituting the core is a region from 0 to less than 0.9L.

With respect to the number of dislocation lines in the tabular grains of the present invention, each grain contains 10 or more dislocation lines, and preferably contains 20 or more dislocation lines.

The tabular grains of the present invention are a general term for silver halide grains having one twin plane or two or more twin planes. The twin plane refers to the (111) plane when ions at all lattice points on both sides of the (111) plane are in a mirror image relationship.
These tabular grains have a triangular shape, a hexagonal shape or a rounded shape when viewed from above, and a triangular shape is triangular, and a hexagonal shape is hexagonal or rounded. Tabular grains have mutually parallel outer surfaces with rounded corners.

In forming the emulsion of the present invention, silver iodobromide or silver chloroiodobromide is used as the silver halide. When there is a phase containing iodide or chloride, these phases may be uniformly distributed in the grains or may be localized.

Other silver salts, for example, rhodan silver, silver sulfide,
Silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as part of silver halide grains.

The preferred range of the silver bromide content of the emulsion of the present invention is 80 mol% or more, more preferably 90 mol%.
It is.

The average silver iodide content of all grains of the emulsion of the present invention is in the range of 0.3 mol% to less than 20 mol%, preferably 2 to 15 mol%, more preferably 3 mol%.
To 10 mol%. If it is less than 1 mol%, it is not preferable because effects such as enhancement of dye adsorption and increase in intrinsic sensitivity are hardly obtained. If it exceeds 20 mol%, the developing speed is generally slow, which is not preferable.

Structures relating to the halogen composition of the emulsion of the present invention include X-ray diffraction, EPMA (also referred to as XMA) method (a method of detecting silver halide composition by scanning silver halide grains with an electron beam), It can be confirmed by combining ESCA (a method of irradiating X-rays to split photoelectrons emitted from the particle surface) or the like. In the present invention, the grain surface refers to a region up to a depth of about 50 ° from the surface, and its halogen composition can be usually measured by the ESCA method. The inside of the particle refers to a region other than the above-described surface region.

In the emulsion of the present invention, silver halide grains having a silver iodide content in the range of 0.7I to 1.3I, when the average silver iodide content of all grains is I mol%, are totally projected. It preferably occupies 100 to 50% of the area, more preferably 100 to 80%, even more preferably 100 to 80%.
Or 90%. Outside of this range, the effects of the present invention cannot be easily obtained, which is not preferable.

Further, in the emulsion of the present invention, it is also preferable that silver halide grains having a silver iodide content in the range of 0.8I to 1.2I occupy 100 to 50% of the total projected area, more preferably. Accounts for 100 to 80%, more preferably 100 to 90%.

The "average silver iodide content of all grains (I mol%)" of the emulsion of the present invention means a specific iodide value which is close to the average silver iodide content calculated from the formulation of the emulsion. It is a silver content. The silver iodide content was measured for a specific emulsion grain group isolated from a specific emulsion layer of a silver halide photographic light-sensitive material, and as many grains as possible contained 0.7I to 1.3.
I can be specified. Generally, the value is close to the arithmetic average value of the silver iodide content for the above specific emulsion grain group. The I value can be set to the average silver iodide content in the formulation or the actually measured average silver iodide content, but it is usually practical to employ the arithmetic average value.

The silver iodide content of each emulsion grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer. The measuring method is described, for example, in EP 147,868.

The emulsion of the present invention has a surface iodine content of 5 mol%.
It is preferably at most 4 mol%, more preferably at most 3 mol%. If the surface iodine amount exceeds 5 mol%, development inhibition and chemical sensitization inhibition occur, which is not preferable. ESCA measurement of surface iodine content
It can be confirmed by a method (also called XPS) (a method of irradiating X-rays and dispersing photoelectrons coming out of the particle surface).

As a method for producing tabular grains, US Pat.
434,226, 4,439,520, 4,4
No. 14,310, No. 4,433,048, No. 4,41
Nos. 4,306 and 4,459,353 disclose the production method and the use technology. Japanese Patent Application Laid-Open No. 6-2143
As disclosed in JP-A-31, once nucleation is performed to obtain a seed crystal emulsion, it is added to p.
Tabular grains can also be formed by setting conditions such as H and pAg, and adding and growing a silver and halogen solution. As a preferred method, tabular grains are formed by adding silver halide fine particles instead of adding an aqueous solution of a silver salt and an aqueous solution of a halide to a reaction vessel holding an aqueous solution of a protective colloid. This method is described in U.S. Pat.
79,208, JP-A-1-183644, 2-4
Nos. 435, 2-43535 and 2-68538 disclose the technology. As a method of supplying iodine ions in forming tabular grains, fine grain silver iodide (having a grain size of 0.
(1 μm or less, preferably 0.06 μm or less) An emulsion may be added. In this case, it is preferable to use a production method disclosed in US Pat. No. 4,879,208 as a method for supplying silver iodide fine particles.

The emulsion of the present invention is preferably monodispersed (the coefficient of variation of the equivalent circle diameter of all grains is 40% or less, preferably 25% or less, more preferably 15% or less). Regarding this, Japanese Patent Application Laid-Open No. 63-11928,
No. 1205 discloses monodisperse hexagonal tabular grains,
No. 31,541 discloses circular monodisperse tabular grains. In JP-A-2-838, more than 95% of the total projected area is occupied by tabular grains having two twin planes parallel to the main surface, and the size distribution of the tabular grains is monodisperse. Certain emulsions have been disclosed. European Patent No. 514742A
Discloses a tabular grain emulsion prepared using a polyalkylene oxide block polymer and having a grain size variation coefficient of 10% or less.

The dislocation of the tabular grains of the present invention can be controlled by providing a specific high iodine phase inside the grains. Specifically, base particles (hereinafter referred to as core)
Is prepared, a high iodine phase is provided by the following method, and the shell is formed by covering the outside with a phase having a lower iodine content than the high iodine phase. The iodine content of the tabular grains of the core is lower than that of the high iodine phase, and is preferably 0 to 12 mol%, more preferably 0 to 10 mol%, based on the silver content of the core. The internal high iodine phase is preferably silver iodide, silver iodobromide, or silver chloroiodobromide, and more preferably silver iodide or silver iodobromide. It is important that the internal high iodine phase is not uniformly deposited on the plane of the tabular grains of the core, but rather exists locally. Such localization (hereinafter referred to as epitaxy) may occur on the major surface of the core tabular grains, but preferably occurs at the edges and corners of the core tabular grains.

As a method for this, for example, E. Kle
in, E. Moisar, G. Murch, Photo.Korr., 102 (4) 59-63.
A so-called conversion method as described in (1966) can be used. In this method, during particle formation,
There is a method of adding a halogen ion having a lower solubility of silver salt to be formed with silver ion than a halogen ion forming a grain (or near the grain surface) at that time,
In the present invention, it is preferable that the amount of halogen ions having low solubility to be added is more than a certain amount (related to the halogen composition) with respect to the particle surface area at that time. For example, during the grain formation, it is preferable to add a certain amount or more of KI to the silver halide tabular grains at that time.

Japanese Patent Application Laid-Open Nos. 6-27564 and 5-341
As disclosed in JP-A-418, it is preferable to add an iodide ion releasing agent to the core tabular grain emulsion as a method of adding iodide ions.

Alternatively, an aqueous silver salt solution and an aqueous solution containing iodide ions are added to the core tabular grain emulsion to form epitaxy on the core tabular grains. At this time, if necessary, JP-A-59-133540 and JP-A-58-108526 may be used.
As disclosed in JP-A-59-162540, an adsorbing substance, for example, a spectral sensitizing dye can be used as a local controlling substance of epitaxy. Instead of adding the ionic solution, silver iodide or silver halide fine particles having a halogen composition having a lower solubility than the core (particle diameter 0.1 μm) are used.
m, preferably 0.06 μm or less) to the core tabular grain emulsion.

The pAg of the emulsion for forming the high iodine epitaxy is preferably 6.4 to 10.5, more preferably 7.1 to 10.2. After making high iodine epitaxy into core tabular grains, the core tabular grains are further grown to form a shell phase. At this time, the amount of silver halide forming the core is 10 to 10
80%, preferably 15-70%, and the internal high iodine phase is 20-1%, preferably 10-10%, based on the total silver amount.
１1%, more preferably 5-1%, and the shell phase is
19 to 89%, preferably 30 to 8%, based on the total silver amount
0%. The iodine content of the core phase is preferably 0 to 12 mol%, more preferably 0 to 12 mol%, based on the silver content of the core.
10 mol%, and that of the internal high iodine phase is 20 to 100 mol%, preferably 30 to 100 mol%, based on the silver content of the internal high iodine phase.
-100 mol%, more preferably 50-100 mol%, and most preferably 100 mol%. The iodine content of the shell phase is lower than that of the internal high iodine phase, and is 0 to 12 mol%, preferably 0 to 10 mol%, based on the silver amount of the shell phase.
More preferably, it is 0 to 5 mol%. The iodine content of the shell phase and the internal high iodine phase is at least 10 mol% or more,
Preferably, the latter is higher than 20 mol%.
The iodine content of the core and the internal high iodine phase is preferably 5 mol%, preferably 10 mol%.

In the tabular grains of the present invention, when forming the shell, a crystal habit controlling agent is present in some or all of the steps.

The crystal habit control agent is a reagent which controls the growth direction of silver halide grains by selectively adsorbing silver halide to a specific crystal plane and suppressing the growth of grains in the crystal plane direction. It is. For example, in the case of producing high silver chloride {111} tabular grains having an (AgCl content ≧ 50 mol%) or octahedral grains, {111} because the equilibrium crystal habit of silver chloride is always a {100} plane. It is essential to use a crystal habit-controlling agent that is selectively adsorbed on the surface.

Specific examples of the crystal habit controlling agent include azaindenes (7-azaindole and the like; US Pat. No. 5,17
No. 8,997 and the like. ), Aminoazaindenes (adenine, 4-aminopyrazolo (3,4-
d) pyrimidine and the like; described in US Pat. No. 5,183,732 and the like. ), Xanthines (xanthine, urea, etc .; described in U.S. Pat. No. 5,178,998), triaminopyrimidines (4,5,6-triaminopyrimidine, etc .; U.S. Pat. No. 5,185,239)
No. etc. ), Iodine-substituted compounds (diiodo-substituted phenol, iodo-substituted-8-hydroxyquinoline, etc .; JP-A-8-87087 and JP-A-8-87088)
And U.S. Pat. No. 5,411,851. ), Thioureas (described in JP-A-62-218959, etc.), pyridinium quaternary salts (described in JP-A-2-32, etc.) and the like.

In forming the shell in the tabular grains of the present invention, preferably, a crystal habit controlling agent represented by the following general formulas (I) and (II) is present in some or all of the steps. Let it.

[0059]

Embedded image

In the general formulas (I) and (II), A ₁ ,
A ₂ , A ₃ and A ₄ each represent a group of nonmetallic atoms necessary for forming a 5- to 6-membered nitrogen-containing heterocyclic ring, and may contain O, N, and S atoms, and a benzene ring is a fused ring May be. A ₁ , A ₂ , A ₃ and A ₄ may be the same or different. B represents a divalent linking group. m is 0 or 1
Represents R ₁ and R ₂ each represent an alkyl group. X ^- represents an anion. n represents 0 or 1, and in the case of an internal salt, n
Is 0.

Hereinafter, the general formulas (I) and (II) will be described in more detail.

In the general formulas (I) and (II), A ₁ ,
A 5- to 6-membered nitrogen-containing heterocyclic ring formed by A ₂ , A ₃ and A ₄ is preferably a pyridine ring,
Examples include an imidazole ring, a thiazole ring, an oxazole ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a benzothiazole ring, a benzoxazole ring, a quinazolidine ring, a phthalazine ring, and a cinnoline ring, with a pyridine ring being more preferred.

The hetero ring composed of A ₁ , A ₂ , A ₃ and A ₄ may have a substituent and may be the same or different. As the substituent, a halogen atom (for example, fluorine, chlorine, bromine, iodine), an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 carbon atom)
-20, particularly preferably 1-12 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl and cyclohexyl. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 carbon atoms)
-20, particularly preferably 2-12 carbon atoms, including allyl, 2-butenyl and 3-pentenyl. ),
An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 12 carbon atoms and including propargyl and 3-pentynyl), and an aralkyl group (preferably having 7 carbon atoms) -30, more preferably 7-20 carbon atoms, particularly preferably 7 carbon atoms
To 12, for example, benzyl, phenethyl and the like. ), An aryl group (preferably having 6 to 30 carbon atoms,
More preferably, it has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl and naphthyl. ), A heterocyclic group (for example,
Ruffle, imidazolyl, piperidyl, morpholino. ), An alkoxy group (preferably having 1 to 2 carbon atoms)
It has 0, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, and butoxy. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 12 carbon atoms, such as phenyloxy and 2-naphthyloxy), and amino. Preferably C0-20, more preferably C0
12, particularly preferably 0 to 8 carbon atoms, for example, unsubstituted amino, dimethylamino, ethylamino, anilino. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and particularly preferably having 2 to 10 carbon atoms, such as acetylamino and benzoylamino), and an aminocarbonylamino group ( Preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms,
For example, carbamoylamino, N, N-dimethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino, preferably having 2 to 20 carbon atoms,
More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 carbon atoms)
To 16, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms)
2, for example, methanesulfonylamino and benzenesulfonylamino. ), A sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably having 0 carbon atoms)
To 16, particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl. ), A carbamoyl group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl. ), Sulfonyl group (preferably having 1 to carbon atoms)
20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl. ), A sulfinyl group (preferably having 1 to 2 carbon atoms)
It has 0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfinyl. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms,
Examples include methoxycarbonyl and ethoxycarbonyl. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 10 carbon atoms, for example, phenyloxycarbonyl), and an acyl group (preferably, phenyloxycarbonyl). It has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and includes, for example, acetyl, benzoyl, formyl, pivaloyl and the like.)
Acyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 10 carbon atoms)
And examples thereof include acetoxy and benzoyloxy. ), A phosphoric amide group (preferably having 1 to 2 carbon atoms)
It has 0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethylphosphoramide and phenylphosphoramide. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 carbon atom)
To 16, particularly preferably 1 to 10 carbon atoms, such as methylthio and ethylthio. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 10 carbon atoms, such as phenylthio), a cyano group, a sulfo group, a carboxyl group, Examples include a hydroxy group, a phosphono group, a nitro group, a sulfino group, an ammonium group (for example, trimethylammonio), a phosphonio group, and a hydrazino group. These substituents may be further substituted.

The substituents for A ₁ , A ₂ , A ₃ and A ₄ are preferably a halogen atom, an alkyl group, an alkenyl group,
Alkynyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, amino group, cyano group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, alkylthio group, arylthio group, more preferably halogen Atoms, alkyl groups,
An alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylthio group, and an arylthio group, more preferably an alkyl group, an aralkyl group, and an aryl group. Group, alkoxy group,
An aryloxy group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyl group.

B represents a divalent linking group. The divalent linking group is an alkylene (preferably having 1 to 30, more preferably 1 to 20, and particularly preferably 1 to 12 carbon atoms, for example, methylene, ethylene, propylene and the like), Arylene (preferably 6 to 30, more preferably 6 to 20, particularly preferably 6 to 12 carbon atoms, such as phenylene, etc.), alkenylene (preferably 2 to 30 carbon atoms, more preferably 2 to 2 carbon atoms) 20, particularly preferably 1 to 12 carbon atoms, e.g., ethynylene and the _{like), -. SO 2 -,} - S
O -, - O -, - S -, - C (= O) -, - N (R 3)
— (R ₃ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. 2
The number of combinations of the valent linking groups is not particularly limited,
It is preferably 2 to 10, more preferably 2 to 5, and still more preferably 2 to 3. Also,
Linking groups in which chemical stability is problematic in the above combinations, for example, —O—O— bonds and the like are excluded from the above combinations of the above linking groups. Preferred examples include alkylene, alkenylene, and arylene.

R ₁ and R ₂ each represent an alkyl group having 1 to 20 carbon atoms. R ₁ and R ₂ may be the same or different.
The alkyl group represented by R ₁ and R ₂ preferably has a substituent. Examples of the substituent include those which A ₁ , A ₂ , A ₃ and A ₄ can take. Is the same, and particularly preferably an aryl group.

X ^- represents an anion (a negatively charged atom or atomic group). Examples thereof include an acid group, an OH group, and a halogen ion, and specific examples thereof include Cl, Br, NO ₃ , 1/2
_{(SO 4), CH 3 COO} , such as p- toluenesulfonate and the like.

N represents 0 or 1, and n = 0 when the compound represented by formula (I) or (II) forms an internal salt. The case where an inner salt is formed is, for example,
Examples include a case where the hetero ring formed by A1 has an acid group such as a carboxyl group or a sulfo group as a substituent.

Specific examples of the compound represented by formula (I) or (II) are listed below, but the present invention is not limited to these compounds.

[0070]

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With respect to examples of the compound represented by formula (I) or (II), reference can be made to JP-A-2-32. In the present invention, the compound represented by the general formula (I) or (II)
Can be used in the range of 10 ^{-5 to} 3 × 10 ^-1 mol per mol of silver halide in the finished emulsion, and 2 × 10 ^-4 to 1 × 10 ^-1 mol can be used. Particularly preferred.

Further, a crystal habit controlling agent represented by the general formula (III) can be used.

[0073]

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In the general formula (III), R_FourIs an alkyl group,
Represents a kenyl group or an aralkyl group; _Five, R₆, R₇, R₈Ma
Or R₉Represents a hydrogen atom or a substituent. R_FiveAnd R₆, R₆
And R ₇, R₇And R₈Or R₈And R₉May be fused. X^-
Represents a counter anion; n represents 0 or 1;
In this case, n is 0.

Next, the general formula (III) will be described in detail. R ₄ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, isopropyl, t
-Butyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group having 2 to 20 carbon atoms (e.g., allyl, 2-butenyl, 3-pentenyl and the like), and an aralkyl group having 7 to 20 carbon atoms (e.g., benzyl, phenethyl and the like). Represent. Each group represented by R ₄ may have a substituent. Examples of the substituent include A ₁ , A ₂ , and A _{3 in the} general formula (I) or (II).
And A ₄ include those can take, the preferred range is also the same.

R ₅ , R ₆ , R ₇ , R ₈ or R ₉ may be the same or different and represent a hydrogen atom or a substituent. Examples of the substituent include the groups defined as R ₄ . These groups may be further substituted. When there are two or more substituents, they may be the same or different.
May be condensed to form a quinoline ring, isoquinoline ring or acridine ring.

[0077] X ^- represents an anion (negative charge atom or group of atoms). Examples thereof include an acid group, an OH group, and a halogen ion, and specific examples thereof include Cl, Br, NO ₃ , 1/2
_{(SO 4), CH 3 COO} , such as p- toluenesulfonate and the like.

N represents 0 or 1, and n = 0 when the compound represented by formula (III) forms an inner salt. The case where an inner salt is formed includes, for example, R ₅ ,
Examples include the case where R ₆ , R ₇ , R ₈ or R ₉ has an acid group such as a carboxyl group or a sulfo group as a substituent.

In the general formula (III), preferably, R_FourBut
Represents an aralkyl group;_Five, R₆, R ₇, R₈Or R₉of
At least one compound representing an aryl group,
Preferably R_FourRepresents an aralkyl group;₇Is an aryl group
And X^-Is a halogen ion.

Specific examples of the compound represented by formula (III) are listed below, but the present invention is not limited to these compounds.

[0081]

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In the present invention, the addition amount of the compound represented by the general formula (III) can be used in the range of 10 ^{-5 to} 3 × 10 ^-1 mol per mol of silver halide in the finished emulsion. × 10 ^-4 to 1 × 10 ^-1 mol is particularly preferred.

Further, a crystal habit controlling agent represented by the general formula (IV) can also be used.

[0084]

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In the general formula (IV), Y represents a sulfur atom or an oxygen atom, and is preferably a sulfur atom. Q represents a group of atoms necessary to complete a 5- or 6-membered hetero ring, for example, thiazolidine-2-thione ring, 4-thiazoline-2-thione ring, 1,3,4-thiadiazoline-2
-Thione ring, benzothiazoline-2-thione ring, benzoxazoline-2-thione ring and the like. In formula (IV), the heterocyclic ring formed by Q and YCN is preferably a thiazoline-2-thione ring.

R ₁₀ is an alkyl group (eg, methyl, ethyl, propyl, butyl, octyl, etc.), an alkenyl group (eg, allyl, 2-propenyl, etc.), an aralkyl group (eg, benzyl, Phenethyl and the like), an aryl group (for example, phenyl, naphthyl and the like),
Or a heterocyclic ring (eg, pyridyl and the like). R ₁₀ is preferably an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and more preferably an alkyl group or an aryl group. Further, the heterocyclic ring formed by Q and R ₁₀ may be unsubstituted or further substituted. As the substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
Sulfonyl group, sulfonamide group, amide group, acyl group, sulfamoyl group, carbamoyl group, ureido group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, hydroxy group, mercapto group, carboxy group, sulfo group, nitro group, amino group, alkylthio group, arylthio group, heterocyclic group And the like can be appropriately selected.

The specific examples of the compounds represented by formula (IV) are listed below, but the present invention is not limited to these compounds.

[0088]

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As the compound represented by the general formula (IV),
In addition to the compounds described in JP-A-1-155332
Can be used. In the present invention, in the general formula (IV)
The amount of the compound represented is the amount of silver halide 1 in the finished emulsion.
10 per mole^-Five~ 3 × 10 ^-1Use in mole range
2 × 10^-Four~ 1 × 10^-1Moles are particularly preferred.

Further, a crystal habit controlling agent represented by the general formula (V) can also be used.

[0091]

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In the general formula (V), Z represents a nonmetallic atom group necessary for forming a 5- to 6-membered nitrogen-containing heterocyclic ring;
It may contain O, N, and S atoms, and the benzene ring may be condensed. As the 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z in the general formula (V),
For example, pyridine ring, imidazole ring, thiazole ring,
Oxazole ring, pyrazine ring, pyrimidine ring, quinoline ring, benzothiazole ring, benzoxazole ring, quinazolidin ring, phthalazine ring, cinnoline ring and the like, among which pyridine ring and pyrimidine ring are more preferable,
Pyrimidine rings are more preferred.

In the general formula (V), R ₁₁ may be condensed with a heterocyclic ring represented by Z to form a 5-membered heterocyclic ring, wherein the heterocyclic ring is 1,2,3-triazole , Imidazole, pyrazole, pyrrole, 2-imidazolidinone,
2-imidazolidinethione and the like.

Preferred examples of the nitrogen-containing hetero-fused ring formed by Z and R ₁₁ in the formula (V) include, for example, adenine, 7-azaindole, xanthine, purine, guanine, cytosine, uracil, thymine and the like. .

When R ₁₁ does not form a condensed ring with Z in the formula (V), R ₁₁ represents a hydrogen atom, an alkyl group or an aryl group.

Examples of the compound represented by the general formula (V) include aminoazaindenes disclosed in US Pat. No. 4,400,463, and 4,713,323 and 4,804, No. 621, 4-aminopyrazolo [3,4-d] pyrimidine;
No. 5,185,239.
And the like. Specific examples of the compound represented by the general formula (V) are shown below,
The present invention is not limited to these compounds.

[0097]

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In the present invention, the amount of the compound represented by the formula (V) can be in the range of 10 ^{-5 to} 3 × 10 ^-1 mol per mol of silver halide in the finished emulsion.
2 × 10 ^-4 to 1 × 10 ^-1 mol is particularly preferred.

In the silver halide grains, the compounds represented by formulas (I) to (V) can be used as (1)
It has an action of selectively adsorbing on the 11) plane and stabilizing the (111) plane. The tabular grains of the present invention can be obtained by the presence of the crystal habit controlling agent during shell formation. The control agent used in the present invention only needs to have this (111) plane selective adsorption property, and the compound used is not limited to the above general formula. The (111) plane selective crystal phase controlling effect useful in the present invention can be easily found by the following test method. That is, when normal alkali-treated bone gelatin is used as a dispersion medium, silver nitrate and potassium bromide are formed at 75 ° C. by a control double jet method at +90 mV using a silver electrode and a saturated calomel electrode as a reference electrode. Are obtained. At this time, when the (111) crystal habit controlling agent is added during the formation of the particles, the (111) plane starts to appear in the cube and becomes a tetrahedron (the corner may be rounded), and all the planes become (111). ), The effect of this (111) crystal habit controlling agent can be clearly known.

The crystal habit controlling agent used in the present invention is preferably a compound represented by formulas (I), (II), (III) and (V), more preferably a compound represented by formula (I):
It is a quaternary salt compound represented by (II) and (III), and among the quaternary salt compounds, a pyridinium salt compound is more preferable.

The high-molecular-weight gelatin used in the present invention means that a component having a molecular weight distribution of at least 280,000 is 30%
It is an alkali-treated bone gelatin containing at least 35%, preferably at least. Gelatin is obtained by decomposing the structure of collagen tissue with alkali or acid to impart water solubility. In the case of lime-processed gelatin, Zab α (low molecular weight), α (molecular weight 100,000) ), Β (molecular weight 200,000), γ (molecular weight 300,000), and a large polymer portion (void; molecular weight greater than 300,000). The ratio of each component, that is, the molecular weight distribution is determined by the internationally determined P
It is measured by the AGI method. When lime-processed bone gelatin having an isoelectric point of 5.0 used for photography was measured by this measurement, the molecular weight was 280,000 or more, that is, the ratio of the sum of γ and voids to the whole was 21%. As the high molecular weight gelatin used in the present invention, the sum of the γ and the void component preferably accounts for 30% or more, more preferably 35%, particularly preferably 37% or more.

As a method for producing high molecular weight gelatin used in the present invention, a method in which gelatin is not cross-linked (the molecular weight distribution of gelatin is adjusted by adjusting extraction conditions) as described in JP-A-11-237704 And methods using various gelatin crosslinking agents (enzymes, inorganic or organic crosslinking agents).

The gelatin of the present invention may be added at any point during grain formation, but is preferably added after nucleation, more preferably before shell formation.
The addition amount is at least 10% by weight, preferably at least 30%, more preferably at least 50%, based on the total dispersion medium during the formation of the particles. Further, the gelatin of the present invention has an effect even when added as a dispersed gelatin which is added after washing the emulsion with water. The addition amount is at least 10% by weight, preferably at least 30%, more preferably at least 50% of the dispersed gelatin added after washing with water.

The silver halide grains of the present invention are prepared using the gelatin of the present invention alone or in combination with another gelatin. As the gelatin to be used in combination, lime treatment is commonly used. In particular, it is preferable to use lime-processed gelatin that has been subjected to deionization treatment or ultrafiltration treatment for removing impurity ions and impurities. In addition to lime-processed gelatin, acid-processed gelatin, derivative gelatin such as phthalated gelatin and esterified gelatin, low-molecular-weight gelatin (molecular weight of 1000 to 8)
As specific examples, gelatin, acid and / or
Or gelatin hydrolyzed with alkali, gelatin decomposed by heat, high molecular weight gelatin (molecular weight of 110,000 to 300,000), and a methionine content of 50 μmol / g.
The following gelatin, gelatin having a tyrosine content of 20 μmol / g or less, oxidized gelatin, and gelatin in which methionine is inactivated by alkylation can be used.
A mixture of two or more of these can also be used. In the present invention, the amount of gelatin used in the particle forming step is
The amount is 1 to 100 g / silver mole, preferably 3 to 70 g.
The concentration of gelatin in the chemical sensitization step of the present invention is 1-1.
00 g / silver mole is preferred, and 1-70 g / silver mole is more preferred.

The original gelatin to be crosslinked in the present invention is a lime-processed bone gelatin. As the original gelatin used in the present invention, various modified lime-processed bone gelatins described below are used. Amino group-modified phthalated gelatin, ambered gelatin, trimellit gelatin,
Pyromellitic gelatin, esterified gelatin represented by carboxyl-modified methyl esterified gelatin, and amidated gelatin, imidazole-modified gelatin such as ethoxyformylated gelatin, oxidized gelatin with reduced methionine groups, Alkylated gelatin modified with methionine groups.

In the tabular grains of the present invention, the shell region occupying the main surface of the tabular grains is expanded and thinned by the presence of a (111) plane-selective crystal habit controlling agent in the shell forming step. Therefore, in order to perform spectral sensitization or chemical sensitization by sensitizing dye adsorption, it is necessary to desorb the crystal habit controlling agent from silver halide tabular grains after grain formation.

The method for desorbing the crystal habit controlling agent includes the following (1)
Other photographically useful adsorbents (spectral sensitizing dyes, emulsion stabilizers, antifoggants, strongly adsorbing dispersion media, surfactants)
(2) Emulsion pH, pX (X
= Cl, Br, I), when the adsorption equilibrium of the crystal habit modifier changes depending on the temperature, a method of combining and desorbing them, (3) adding an oxidizing agent or a reducing agent to oxidize the crystal habit controlling agent or Methods for reduction, deactivation, desorption and the like are known, and in the actual production of emulsions, the above methods are combined in accordance with the properties of the crystal habit controlling agent used.

On the other hand, it is known that the adsorption of gelatin to silver halide grains occurs at specific amino acid residues constituting gelatin, and the adsorption mode is at specific residues in the polymer molecule. So-called "Loop and Bri"
dge Model ". It is self-evident that the larger the molecular weight, the larger the number of adsorption points per gelatin polymer molecule.The higher the number of γ and void components, the higher molecular weight gelatin molecules having more adsorbed residues, the higher the adsorption power and The amount of adsorption increases.

In the formation of silver halide grains using the crystal habit controlling agent of the present invention, the use of the high molecular weight gelatin enhances the adsorptivity of the gelatin to the silver halide grains. Desorption is promoted, so that spectral sensitization and chemical sensitization by the subsequent sensitizing dye can be performed more easily.

In the formation of the shell of the dislocation-introduced particles, the use of the (111) plane-selective crystal phase controlling agent as a method of growing the particles in the lateral direction and consequently forming particles having a large shell area ratio is described. JP-A 8-220
No. 664, there is no description in the examples of the patent publication regarding the preparation of ultrathin tabular grains having a thickness of 0.1 μm or less referred to in the present invention. That is, the tabular grains disclosed in the present invention, which are ultrathin tabular grains having a thickness of 0.1 μm or less and having a large ratio of shell area where dislocations are present, are not disclosed.

As a result of intensive studies, it has become clear for the first time that the ratio of the side area of the tabular grains necessary for the lateral growth is extremely small, and that the above-mentioned technique can be applied to the tabular grains into which dislocations are introduced. Thereby, the thickness of 0.1
In the preparation of ultrathin tabular grains of μm or less, it has become possible to achieve both thinning of tabular grains and introduction of dislocation lines.

However, a circle equivalent diameter of 1.0 μm or more,
The equivalent spherical diameter is 0.5 μm or more, and the particle thickness is 0.1 μm
In the front and rear silver halide tabular grain emulsions, increasing the area ratio of the shell portion where dislocation lines exist and making the plate thinner only has a small rate of improvement in sensitivity to surface area increase, and the pressure resistance due to the thinner grain. Higher sensitivity and improved pressure resistance have not been achieved due to both the reduction in thickness of tabular grains and the introduction of dislocation lines.

Therefore, further studies were carried out. As a result, the average silver iodide content between grains was made uniform in the silver halide tabular grain emulsion in which both thinning and introduction of dislocation lines were achieved, and high molecular weight By using gelatin, it was found that remarkably high sensitivity can be achieved with respect to conventional tabular grain emulsions, and that pressure resistance was also improved, and the present invention was completed.

The emulsions of the present invention and photographic emulsions other than the present invention used in combination therewith are described in Grafkid, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkids,
Chemie et Physique Photog
raphique, Paul Montel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographi).
c Emulsion Chemistry (Foca
l Press, 1966)), "Production and Coating of Photographic Emulsions", by Zerikman et al., published by Focal Press (VL.
Zelikman et al. , Making an
d Coating Photographic Em
ulsion, Focal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

A method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion, US Pat. Nos. 4,334,012, 4,301,241, and 4,150,994. Is optionally preferred. These can be used as seed crystals,
It is also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from the method of adding the whole amount at a time, adding in a plurality of times or adding continuously. It is also effective in some cases to add particles of various halogen compositions to modify the surface.

A method for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is disclosed in US Pat. Nos. 3,477,852 and 4,1.
No. 42,900, European Patent 273,429, No. 27
No. 3,430, West German Patent No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a sparingly soluble silver salt. It can be selected from methods such as converting at once, converting into a plurality of times, or converting continuously.

As a method of grain growth, besides a method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate, British Patent No. 1,469,480 and US Pat.
The particle forming method of changing the concentration or changing the flow rate as described in U.S. Pat. Nos. 0,757 and 4,242,445 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is.

A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in US Pat. No. 2,996,287.
No. 3,342,605 and No. 3,415,65
No. 3,785,777, West German Patent 2,5
No. 56,885 and 2,555,364.

A silver halide solvent is useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts,
A halide salt, silver salt or deflocculant can be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

The ripening agents include, for example, ammonia, thiocyanates (eg, rhodankali, rhodammonium), and organic thioether compounds (eg, US Pat. Nos. 3,574,628, 3,021,215, No. 3,057,724, No. 3,038,805,
Nos. 4,276,374 and 4,297,439
No. 3,704,130, No. 4,782,01
No. 3, the compound described in JP-A-57-104926. ), Thione compounds (for example, JP-A-53-8240)
No. 8, No. 55-77737, U.S. Pat.
No. 863, compounds described in JP-A-53-144319) and the growth of silver halide grains described in JP-A-57-202531. Mercapto compounds and amine compounds (for example, JP-A-54-100717).

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sodium alginate and starch derivatives. Various sugar derivatives such as mono- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole A conductive polymer substance can be used.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin and Bull. Soc. Sci. Ph
oto. Japan. No. 16. Enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

In some cases, a method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is also useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

The silver halide grains of the present invention can be used for at least one of chalcogen sensitization such as sulfur sensitization and selenium sensitization, noble metal sensitization such as gold sensitization and palladium sensitization, and reduction sensitization. It can be applied in any step of the production process of the silver emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

One of the chemical sensitizations which can be preferably carried out in the present invention is a chalcogen sensitization and a noble metal sensitization alone or in combination, and is described in TH James, The Photographic Process, No. 4. Edition, published by Macmillan, 1
977, (TH James, The Theor)
y of the Photographic Pro
cess, 4th ed, Macmillan, 197
7) can be performed using active gelatin as described on pages 67-76, and can also be performed by Research Disclosure, Vol. 120, Apr. 1974, 12008; Research Disclosure, Vol. 34, Jun. 1975,
13452; U.S. Pat. Nos. 2,642,361; 3,297,446; 3,772,031; 3,857,711; 3,901,714; No. 3,266,018 and No. 3,904,41.
5, pAg 5-10, pH 5-8 and temperature 30-8 as described in GB 1,315,755.
At 0 ° C., it can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. In precious metal sensitization, gold, platinum,
Noble metal salts such as palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are R
It is represented by ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

More specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ P
dCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li
₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
Nos. 711, 4,266,018 and 4,0
No. 54,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine,
Compounds known to suppress fog and increase sensitivity during the process of chemical sensitization are used. Examples of the chemical sensitization aid modifier are described in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526 and the above-mentioned duffin. "Photographic emulsion chemistry", pp. 138-143.

The emulsion of the present invention is preferably used in combination with gold sensitization.
Good. The preferred amount of the gold sensitizer is 1 mole of silver halide.
1 × 10 per le^-Four~ 1 × 10^-7Mole and more preferred
What's new is 1 × 10^-Five~ 5 × 10^-7Is a mole. Paraziu
The preferred range of the compound is 1 × per mole of silver halide.
10^-3From 5 × 10^-7Is a mole. Thiocyanate compound
Or the preferred range of selenocyan compound is halogenated
5 × 10 per mole of silver ^-2From 1 × 10^-6Is a mole.

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mole of silver halide.
10 ^-4 to 1 × 10 ^-7 mol, more preferably 1
It is from × 10 ^{-5 to} 5 × 10 ^-7 mol.

Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea), selenoketones And selenium compounds such as selenoamides. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, reduction sensitization is a method in which a reduction sensitizer is added to a silver halide emulsion, or pAg 1 called silver ripening.
Growing or ripening in a low pAg atmosphere of ~ 7,
Any method of growing or ripening in a high pH atmosphere of pH 8 to 11, which is called high pH ripening, can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

Examples of the reduction sensitizer include stannous salts,
Ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide.

The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth.
It may be added to the reaction vessel in advance, but a method of adding at an appropriate time during the particle growth is preferable. Alternatively, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

During the production process of the emulsion of the present invention, an acid for silver is used.
It is preferable to use an agent. The oxidizing agent for silver is
Has the effect of converting to silver ions by acting on metallic silver
Refers to a compound. Especially the formation process of silver halide grains and
Extremely small silver particles by-produced during chemical sensitization
Is a compound that can be converted into a silver ion. here
The silver ions generated in, for example, silver halide, sulfide
May form poorly soluble silver salts such as silver and silver selenide.
And may form a silver salt easily soluble in water such as silver nitrate.
No. The oxidizing agent for silver can be inorganic or organic.
There may be. As the inorganic oxidizing agent, for example, Ozo
Hydrogen peroxide and its adducts (eg, NaBO)_Two
・ H_TwoO_Two・ 3H_TwoO, 2NaCO_Three・ 3H_TwoO_Two, Na_FourP_Two
O₇・ 2H_TwoO_Two, 2Na_TwoSO_Four・ H_TwoO_Two・ 2H_TwoO), pe
Leuoxy acid salt (for example, K_TwoS_TwoO₈, K_TwoC_TwoO₆, K_TwoP_Two
O₈), Peroxy complex compounds (eg, K_Two[Ti (O
_Two) C_TwoO _Four] ・ 3H_TwoO, 4K_TwoSO_Four・ Ti (O_Two) OH
・ SO_Four・ 2H_TwoO, Na_Three[VO (O_Two) (C_TwoH_Four)_Two]
・ 6H_TwoO), permanganate (eg, KMnO)_Four),
Chromate (eg, K_TwoCr_TwoO₇Oxygen acid like)
Salts, halogen elements such as iodine and bromine, perhalates
(Eg, potassium periodate), high valent metal salts
(Eg potassium hexacyanoferrate) and thio
There are sulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds which release active halogen (eg, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example.

Preferred oxidizing agents of the present invention are inorganic oxidizing agents such as ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates, and organic oxidizing agents such as quinones.
It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) known as antifoggants or stabilizers, such as titraazaindenes) and pentaazaindenes;
Many compounds can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,947,
Those described in JP-B-52-28660 can be used. One of the preferred compounds is disclosed in JP-A-63-21.
2932. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized by a methine dye or the like to exhibit the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used as basic heterocyclic nuclei in cyanine dyes can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus,
Thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and aromatic hydrocarbon rings in these nuclei Fused nuclei, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus it can. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye includes, as a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-
A 5- or 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a rhodanine nucleus and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
No. 7,229, No. 3,397,060, No. 3,5
No. 22,052, No. 3,527,641, No. 3,
Nos. 617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377,
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,70
7, UK Patent Nos. 1,344,281 and 1,50
7,803, JP-B-43-4936, 53-12
No. 375, JP-A-52-110618, JP-A-52-10
No. 9925.

In addition to the sensitizing dye, the emulsion may contain a dye having no spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-8-969 and JP-A-4225666, spectral sensitization may be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 928, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains have been formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The amount of addition was 4 × / mol of silver halide.
Although it can be used in an amount of 10 ^-6 to 8 × 10 ^-3 mol, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is effective when the silver halide grain size is more preferably 0.2 to 1.2 μm. is there.

Various additives can be used in the silver halide photographic material to which the present invention can be applied, depending on the purpose.

These additives are described in more detail in Research Disclosure (RD) Item 17643 (1
Item 18716 (November 1979), Item 308119 (December 1989)
Mon) and Item 40145 (September 1997)
The relevant locations are summarized below.

Additive Type RD17643 RD18716 RD308119 Chemical sensitizer page 23 page 648 right column page 996 2. Sensitivity increasing agent Same as above 3. 3. Spectral sensitizer, page 23-24, page 648, right column-996 right, -998 right Supersensitizer, page 649, right column Brightener 24 pages 998 right 5. 5. Antifoggant page 24 to 25 page 649 right column 998 right to 1000 right and stabilizer 6. Light absorber, pages 25 to 26, page 649, right column to 1003, left to 1003 right, filter dye, page 650, left column, UV absorber 7. Stain inhibitor 25 pages right column 650 left to right column 1002 right Dye image stabilizer page 25 1002 right 9. Hardening agent Page 26 Page 651 Left column 1004 right to 1005 left 10. Binder page 26 Same as above 1003 right to 1004 right 11. Plasticizers, lubricants 27 pages 650 pages right column 1006 left to 1006 right 12. Coating aid, pages 26 to 27 Same as above 1005 left to 1006 left Surfactant 13. Static page 27 Same as above 1006 right to 1007 left Inhibitor 14. Matting agent 1008 left to 1009 left.

Techniques such as a layer arrangement which can be used in a silver halide photographic light-sensitive material which can adopt the present invention, functional couplers such as silver halide emulsions, dye-forming couplers, DIR couplers, various additives, etc. And development processing are described in EP 056596 A1 (October 1993).
And published patents cited therein. The following is a list of each item and the corresponding places.

1. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14, 2. Intermediate layer: page 61, lines 36 to 40, 3. Multilayer effect imparting layer: page 62, lines 15 to 18, 4. Silver halide composition: page 62, lines 21 to 25; 5. Silver halide grain habit: page 62, lines 26 to 30, 6. Silver halide grain size: page 62, lines 31 to 34, 7. Emulsion production method: page 62, lines 35 to 40, Silver halide grain size distribution: page 62, 41 to 42
Row, 9. Tabular grains: page 62, lines 43 to 46,10. 10. Internal structure of particle: page 62, lines 47 to 53, Emulsion latent image forming type: page 62, line 54 to page 63, 5
Line, 12. 12. Physical ripening / chemical ripening of emulsion: p. 63, lines 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogged emulsion: p. 63, lines 14 to 31, Non-light-sensitive emulsion: page 63, lines 32-43, 16. Silver coating amount: page 63, lines 49 to 50.

17. Photographic additives: Research Disclosure (RD) Item 17643 (Dec. 1978)
), Item 18716 (November 1979), and Item 307105 (November 1989). The following items and the relevant places are shown below. Additive type RD17643 RD18716 RD307105 (1) Chemistry Sensitizer page 23, page 648, right column, page 866 (2) Sensitivity enhancer, page 648, right column (3) Spectral sensitizer, page 23-24, page 648, right column-866-868, supersensitizer page 649, right Column (4) Brightener page 24, page 647, right column, page 868 (5) Antifoggant, page 24-25, page 649, right column 868-870, stabilizer (6) Light absorber, page 25-26, page 649, right Column to page 873 Filter dye, page 650 left column UV absorber (7) Stain inhibitor page 25 right column 650 left column to right column page 872 (8) Dye image stabilizer page 25 650 page left column page 872 (9) Hardener page 26, page 651, left column, pages 874 to 875 (10) Binder page 26, page 651, left column, 873 to 874 (11) plasticizer, lubricant page 27, page 650, right column page 876 (12) Coating aid, 26-27 page 650 page right Columns 875-876 Surfactants (13) Static page 27 Page 650 Right column 876-877 Inhibitors (14) Matting agents 878-879.

18. Formaldehyde scavenger: 6
Page 4, lines 54-57; 20. Mercapto antifoggant: page 65, lines 1 and 2, Release agent such as fogging agent: page 65, lines 3-7, 21. Dye: page 65, lines 7-10, 22. General color couplers: p. 65, lines 11 to 13, 23. Yellow, magenta and cyan couplers: page 65, 1
Lines 4 to 25, 24. Polymer coupler: page 65, lines 26 to 28, 25. Diffusible dye-forming couplers: p. 65, lines 29 to 31, 26. Colored coupler: page 65, lines 32-38, 27. General functional couplers: p. 65, lines 39 to 44, 28. Bleach accelerator releasing coupler: page 65, lines 45-48, 29. Development accelerator releasing coupler: page 65, lines 49 to 53, 30. Other DIR couplers: page 65, line 54 to page 66, 4
Line, 31. Coupler dispersion method: page 66, lines 5-28, 32. Preservatives / fungicides: page 66, lines 29-33, 33. Type of photosensitive material: page 66, lines 34 to 36, 34. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, 1
Row, 35. Back layer: page 67, lines 3 to 8, 36. Overall development processing: page 67, lines 9-11, 37. Developer and developer: page 67, lines 12 to 30, 38. 39. Developer additive: page 67, lines 31 to 44, Reverse processing: page 67, lines 45 to 56, 40. Processing solution opening ratio: page 67, line 57 to page 68, line 12, 41. Developing time: page 68, lines 13 to 15, 42. Bleach-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 43. Automatic developing machine: page 69, lines 32 to 40, 44. Rinsing, rinsing, stabilization: page 69, line 41 to page 70, line 18
Row, 45. Processing solution replenishment, reuse: page 70, lines 19-23, 46. 47. Built-in developer sensitive material: page 70, lines 24-33, Developing temperature: 70 pages 34-38, 48. Use for film with lens: page 70, lines 39-41.

[0155]

Examples of the present invention will be described below. However, it is not limited to this embodiment.

Gelatins 1 to 4 used as dispersion media in the following emulsion preparations are gelatins having the following attributes.

Gelatin-1: Normal alkali-treated ossein gelatin made from bovine bone. -NH ₂ in the gelatin
No chemical modification of the group.

Gelatin-2: In an aqueous solution of gelatin-1,
A gelatin obtained by adding phthalic anhydride at 50 ° C. and a pH of 9.0 to cause a chemical reaction, removing residual phthalic acid, and drying. 95% of the number of —NH ₂ groups chemically modified in gelatin.

Gelatin-3: In an aqueous solution of gelatin-1,
Gelatin obtained by adding trimellitic anhydride under conditions of 50 ° C. and pH 9.0 to cause a chemical reaction, and then removing remaining trimellitic acid and drying. 95% of the number of —NH ₂ groups chemically modified in gelatin.

Gelatin-4: Gelatin obtained by lowering the molecular weight of gelatin-1 by the action of an enzyme to make the average molecular weight 15,000, then inactivating the enzyme and drying. No chemical modification of -NH ₂ groups in the gelatin.

After the above gelatin-1 to 4 were all deionized, the pH of a 5% aqueous solution at 35 ° C. was 6.
Adjustment was made so as to be zero.

Example 1 (Preparation of Emulsion A-1) 1300 ml of an aqueous solution containing 0.5 g of KBr and 1.1 g of the above gelatin-4 (hereinafter also referred to as “mL”) was heated to 35 ° C. It kept and stirred (1st liquid preparation). 18 mL of an aqueous solution of Ag-1 (containing 4.9 g of AgNO ₃ in 100 ml) and an aqueous solution of X-1 (containing 5.2 g of KBr in 100 mL) 14
mL and 4.5 mL of an aqueous G-1 solution (containing 8.0 g of the above gelatin-4 in 100 mL) were added at a constant flow rate over 30 seconds by a triple jet method (addition 1). Thereafter, 6.5 g of KBr was added, and the temperature was reduced to 7
The temperature was raised to 5 ° C. After the aging process for 12 minutes after the temperature rise,
G-2 aqueous solution (1 part of the above gelatin-3 in 100 mL)
300 mL (containing 2.7 g) are added and then 4,
2.1 g of disodium 5-dihydroxy-1,3-disulfonate monohydrate and 0.002 g of thiourea dioxide were sequentially added at intervals of 1 minute.

Next, an aqueous solution of Ag-2 (A in 100 mL)
157 mL of gNO ₃ (containing 22.1 g) and an X-2 aqueous solution (containing 15.5 g of KBr in 100 mL) were added by a double jet method over 14 minutes. At this time, the final flow rate of addition of the Ag-2 aqueous solution is 3.
The flow rate was accelerated so as to be four times, and the addition of the X-2 aqueous solution was performed so that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 8.3 (addition 2). Then, an Ag-3 aqueous solution (1
(Contains 32.0 g of AgNO ₃ in 00 mL)
L and X-3 aqueous solution (21.5 KBr in 100 mL)
g, KI containing 1.2 g) by the double jet method.
Added over 7 minutes. At this time, the addition of the Ag-3 aqueous solution accelerates the flow rate so that the final flow rate becomes 1.6 times the initial flow rate, and the addition of the X-3 aqueous solution reduces the pAg of the bulk emulsion solution in the reaction vessel to 8.3. This was done to keep (addition 3). Further, an Ag-4 aqueous solution (Ag in 100 mL)
80 mL of NO ₃ (containing 32.0 g of NO ₃ ) and an aqueous solution of X-4 (containing 22.4 g of KBr in 100 mL) were added by a double jet method over 9 minutes. At this time, Ag
The aqueous solution X-4 was added at a constant flow rate, and the aqueous solution X-3 was added such that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 8.3 (addition 4).

Then, 0.0025 g of sodium benzenethiosulfonate and 125 mL of an aqueous G-3 solution (containing 12.0 g of the above gelatin-1 in 100 mL)
Were added sequentially at one minute intervals. Then 55 ° C
And 160 mL of a 0.3 M KI aqueous solution was added over 2 minutes (addition 5). Two minutes later, Ag-
325 mL of the 4 aqueous solutions and the X-4 aqueous solution were added by the double jet method. At this time, the Ag-4 aqueous solution is
The X-4 aqueous solution was added over the first 4.3 minutes over a period of 2 minutes.
The pAg of the bulk emulsion solution in the reaction
The addition was carried out so as to maintain the pAg of the bulk emulsion solution in the reaction vessel to be finally 7.8 (addition 6). Thereafter, desalting is performed by a normal flocculation method, and then water, NaOH, and the above-mentioned gelatin-1 are added while stirring.
It adjusted so that it might become pH6.4 and pAg8.6 at 56 degreeC.

The obtained emulsion had a circle equivalent diameter (Dc) of 1.5.
.mu.m, a grain thickness (th) of 0.13 .mu.m, an average AgI content of 4.5 mol%, and tabular silver halide grains having (111) parallel main planes, and a halogen measured by XPS. The AgI content on the surface of the silver halide grains was 2.1 mol%. The coefficient of variation of the equivalent circle diameter of all particles is 24%
Met. Table 101 shows the characteristic values of the emulsion grains. In Table 101, AR is equivalent circle diameter / particle thickness (Dc /
th), and Dsph represents a sphere equivalent diameter.

Subsequently, the following sensitizing dye Exs-1, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were successively added and optimally subjected to chemical sensitization. Mercapto compound MER-
Chemical sensitization was terminated by adding a total of 3.6 × 10 ^-4 mol of 1 and MER-2 at a ratio of 4: 1 per mol of silver halide.

The sensitizing dye of the present invention is disclosed in JP-A-11-525.
This was used as a solid fine dispersion prepared by the method described in No. 07.

For example, a solid fine dispersion of the sensitizing dye Exs-1 was prepared as follows.

0.8 parts by weight of NaNO ₃ and Na ₂ SO ₄
Dissolve 3.2 parts by weight in 43 parts of ion-exchanged water, add 13 parts by weight of a sensitizing dye, and disperse at 2000 rpm for 20 minutes using a dissolver blade at 60 ° C.
A solid fine dispersion of the sensitizing dye Exs-1 was obtained.

[0170]

Embedded image

[0171]

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(Preparation of Emulsion A-2) Emulsion A-2 was prepared by changing the preparation conditions of Emulsion A-1 described above as follows.

Instead of adding 160 mL of a 0.3 M KI aqueous solution over 2 minutes after cooling to 55 ° C. in (addition 5) of A-1 (addition 5), the temperature was lowered to 40 ° C. and then p, which is an iodide ion releasing agent, was added. An aqueous solution containing 0.048 mol of sodium iodoacetamidobenzenebenzenesulfonate was added thereto, and then a 0.8M aqueous sodium sulfite solution was added to 60 m
L was added in a fixed amount for 1 minute to generate iodide ions while controlling the pH at 9.0. After 2 minutes, the temperature was raised to 55 ° C. over 15 minutes, and then the pH was lowered to 5.5.

(Preparation of Emulsion A-3) Emulsion A-3 was prepared by changing the preparation conditions of Emulsion A-2 as described below.

The p added in (addition 5) of A-2
-Change the amount of sodium iodoacetamidobenzenesulfonate to 0.018 mol. The amount of the 0.8 M aqueous sodium sulfite solution is also changed to 40 mL.

(Preparation of Emulsion A-4) Emulsion A-4 was prepared by changing the preparation conditions of Emulsion A-1 described above as follows.

In (addition 6), an aqueous solution containing a crystal habit controlling agent (Exemplified Compound I-1) in an amount of 1.5 mmol per Ag mol with respect to the total silver is added in a quantitative manner in accordance with the addition of the Ag-4 aqueous solution. .

(Preparation of Emulsion A-5) Emulsion A-5 was prepared by changing the preparation conditions of Emulsion A-2 described above as follows.

In (Addition 6), an aqueous solution containing a crystal phase controlling agent (Exemplified Compound I-1) in an amount of 1.5 mmol / Ag mol with respect to the total silver is added in a quantitative manner in accordance with the addition of the Ag-4 aqueous solution. .

(Preparation of Emulsion A-6) Emulsion A-6 was prepared by changing the preparation conditions of Emulsion A-3 described above as follows.

In (Addition 6), an aqueous solution containing a crystal phase controlling agent (Exemplified Compound I-1) in an amount of 1.5 mmol / Ag mol with respect to the total silver was added in a quantitative manner in accordance with the addition of the Ag-4 aqueous solution. .

(Preparation of Emulsion A-7) Emulsion A-7 was prepared by changing the preparation conditions of Emulsion A-5 described above as follows.

The content of the aqueous solution G-3 added after (addition 4) was changed to an aqueous solution containing 18 g of gelatin-1 in 100 mL, and the amount added was changed to 250 mL.

(Preparation of Emulsion A-8) An emulsion A-8 was prepared by changing the preparation conditions of the emulsion A-5 described above as follows.

Gelatin-1 in G-3 aqueous solution added after (addition 4) was prepared using the vinyl sulfone crosslinking agent [H-2] described in Example 1 of JP-A-11-237704. High-molecular-weight gelatin (cross-linked lime-processed gelatin in which components having a molecular weight of 280,000 or more in the molecular weight distribution measured by the PAGI method account for 40% of the total) is changed.

[0186]

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(Preparation of Emulsions A-9 to 24) In Emulsion A-1, (1st solution preparation) and (Addition 1) to (Addition 4)
(PAg, addition rate, gelatin type and amount, silver and halogen by continuous addition of silver halide ultrafine particles simultaneously prepared by another stirring mixer outside the reaction vessel into the reaction vessel) ), And base grain emulsions having different circle equivalent diameters and thicknesses are prepared, and the subsequent (addition 5) and subsequent steps are performed as described below to obtain tabular grain emulsions A-12.
~ 31 were prepared.

For Emulsions A-9 and 17, (Addition 5)
Thereafter, the same procedure as in emulsion A-1 was carried out to prepare the emulsion. Emulsions A-10 and E18 were prepared in the same manner as in Emulsion A-2 after (addition 5). Emulsions A-11 and 19 were prepared in the same manner as Emulsion A-3 after (addition 5). Emulsions A-12 and 20 were prepared in the same manner as Emulsion A-4 after (addition 5).

Emulsions A-13 and 21 were prepared in the same manner as Emulsion A-5 after (addition 5). Emulsions A-14 and 22 were prepared in the same manner as in Emulsion A-6 after (addition 5). For the emulsions A-15 and A-23, the aqueous solution G-3 was added to the emulsion A
-7 was prepared in the same manner as in Emulsion A-5 except that (addition 5) was repeated. For the emulsions A-16 and A-24, the aqueous solution G-3 was added to the emulsion A
-8 was prepared in the same manner as in Emulsion A-5 except for (addition 5).

In the preparation of these emulsions, the addition rates of the aqueous silver nitrate solution and the aqueous halide salt solution are each set at a rate commensurate with the critical growth rate of the silver halide grains so that renucleation and polydispersion due to Ostwald ripening do not occur. Properly controlled.

Tables 101, 102 and 103 show the characteristic values of the emulsion grains of Emulsions A-2 to A-24.

[0192]

[Table 1]

[0193]

[Table 2]

[0194]

[Table 3]

The shape of the grains in the emulsion was determined by taking a transmission electron micrograph by a replica method and measuring 1000 grains. The coefficient of variation of the equivalent circle diameter distribution of all the grains was 40% or less for each emulsion. In addition, the electron beam spot interval was set to 50 n for 20 grains of each emulsion by a method using an analytical electron microscope described in JP-A-7-219102.
When the silver iodide content distribution in the grains was measured at m, the average silver iodide content of the shell phase was 2.0 mol% or more higher than the average silver iodide content of the core phase in all emulsions. .

Further, regarding the dislocation line, the grain 2 in the emulsion was used.
Observation (introduction position, density, distribution) of 00 pieces was performed by a high-pressure type (acceleration voltage: 400 kV) electron microscope according to the method described in the text (sample tilt angle -1 for each particle).
Observation was made in five ways: 0 °, −5 °, 0 °, + 5 °, and + 10 °. ).

The distribution of silver iodide content between grains was determined by measuring 200 grains by the method using EPMA described in European Patent No. 147,868 (I = average silver iodide content).

(Emulsion grain characteristics in Examples described later were measured in the same manner.) These emulsions A-2 to 24 were also subjected to the same chemical sensitization as in emulsion A-1.

As can be seen from Tables 101, 102 and 103, the emulsion grains prepared using the crystal habit controlling agent have a large proportion of the shell phase in the main surface of the tabular grains, the equivalent particle diameter of the grains and the silver content of the core / shell. When the ratios are adjusted, it can be seen that the thickness of the tabular grains decreases as the proportion of the shell phase in the main surface of the tabular grains increases.

Regarding the silver iodide content distribution between grains,
Emulsion particles prepared using an iodide ion releasing agent have a KI
It can be seen that the distribution between grains is narrower than that of emulsion grains prepared by adding an aqueous solution.

Emulsions A-1 to A-24 were prepared by disodium 4,5-dihydroxy-1,3-disulfonate monohydrate and thiourea dioxide immediately before (addition 2) in the emulsion preparation step. Is sensitized by reduction.

Further, the emulsions A-1 to A-24 were subjected to the sensitizing dye Exs-1 in the chemical sensitization step in the emulsion preparation.
Was added to perform spectral sensitization, whereby a green-sensitive silver halide emulsion having a wavelength at which the spectral sensitivity was maximized was 550 mn.

The above emulsions A-1 to A-24 were coated on a cellulose triacetate film support provided with an undercoat layer under the coating conditions shown in Table A below. These are referred to as samples 101 to 124, respectively.

[0204]

[Table 4]

These samples were subjected to a hardening treatment at 40 ° C. and a relative humidity of 70% for 14 hours. Thereafter, exposure was performed for 1/100 second through a continuous wedge with a gelatin filter SC-50 (a long-wavelength light transmission filter having a cutoff wavelength of 500 nm) manufactured by Fuji Film Co., Ltd. The photographic performance was evaluated by measuring the density in the above.

Using a negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., processing was performed according to the method described below (until the cumulative replenishment amount of the liquid became three times the mother liquid tank capacity).

(Processing method) Process Processing time Processing temperature Replenishment amount Color development 2 minutes 45 seconds 38 ° C. 45 mL Bleaching 1 minute 00 seconds 38 ° C. 20 mL The entire amount of the bleach solution overflowed into the bleach-fix tank Bleach-fix 3 minutes 15 seconds 38 30 ° C water washing (1) 40 seconds 35 ° C Countercurrent piping system from (2) to (1) Water washing (2) 1 minute 00 seconds 35 ° C 30mL Stable 40 seconds 38 ° C 20mL Drying 1 minute 15 seconds 55 ° C * The replenishment amount is 35 mm width / 1.1 m length (corresponding to 24 Ex. 1 line) Next, the composition of the processing solution will be described.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Iodine 1.5 mg potassium hydroxide-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Add water and add 1.0 L 1.0 L pH (potassium hydroxide And adjusted with sulfuric acid) 10.05 10.10.

(Bleaching solution) Common to tank solution and replenisher (unit: g) Ferric ammonium ammonium diamine tetraacetate dihydrate 120.0 Ethylene diamine tetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH ₃ ) _{2 N-CH 2 -CH 2 -SS} -CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 mL water to make 1.0 L pH (adjusted with aqueous ammonia and nitric acid) 6.3 .

(Bleach-fixing solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Aqueous ammonium thiosulfate (700 g / L) 240.0 mL 400.0 mL Ammonia water (27%) 6.0 mL-Add water 1.0 L 1.0 L pH (adjusted with ammonia water and acetic acid) 7.2 7.3.

(Washing solution) Tank water and replenisher common tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400) The mixture was passed through a mixed-bed column packed with to treat the calcium and magnesium ion concentrations at 3 mg / L or less, and then 20 mg / L of sodium diisocyanurate and 0.15 g / L of sodium sulfate were added. P of this liquid
H was in the range 6.5-7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1.0 L with water added to pH 8.5.

The results are shown in Tables 201, 202 and 203 below.
Shown in The sensitivity was represented by a relative value of the reciprocal of the exposure necessary to reach the density of fog density plus 0.2. Table 20
From the results of Nos. 1 and 202, it can be seen that the tabular grains satisfying the requirements (i) to (vi), which have a variation coefficient of the equivalent circle diameter of all the grains of 40%, significantly improve the photographic sensitivity.
(In Table 201, the sensitivity of Sample 101 was 100, and in Table 202, the sensitivity of Sample 109 was 100.) That is, in Table 201, Samples 104 to 108 (Emulsion A)
-4 to 8) are as follows. By using the crystal habit controlling agent I-1, the shell region occupying the main surface of the tabular grains is expanded, and the thickness of the tabular grains is reduced accordingly. Coefficient of variation of equivalent circle diameter and requirements (i) to (vi), particle shape ((111) tabular grain, equivalent circle diameter, thickness, equivalent sphere diameter) and particle structure (core / shell structure, wide shell area) Sa).

However, among these samples, sample 1
In No. 06, the number of dislocation lines contained in the shell region was less than 10, which did not satisfy the conditions of the present invention, and the relative sensitivity was significantly reduced. In sample 104, the uniformity of the average intergranular silver iodide content does not satisfy the requirement (v), so that the sensitivity is not significantly improved.

Samples 105, 107 and 108 have a variation coefficient of the circle equivalent diameter of all the particles defined in the present invention of 40%,
In addition, requirements (i) to (vi) are satisfied, a clear improvement in sensitivity is recognized, and pressure resistance is also improved. Further, Sample 105 using Emulsion A-8 in which gelatin added before shell formation was changed to high molecular weight gelatin was Sample 105,
The sensitivity was further improved as compared with 107, which is considered to be the result of promoting the desorption of the crystal habit-controlling agent by improving the adsorption power of gelatin to silver halide grains.

When the grain thickness and the shell region do not satisfy the requirement (iv) defined in the present invention as in the samples 101 to 103, the sensitivity due to the difference in the uniformity of the average silver iodide content among the grains. The impact was not so great.

In Table 202, samples 109 to 110,
112 to 113, 115, 116 (emulsions A-9 to 10,
A-12-13, A-15, and 16) require that the variation coefficient of the equivalent circle diameter of all the particles defined in the present invention be 40%, and the requirements (i) to
In (vi), the shapes of the grains ((111) tabular grains, equivalent circle diameters,
Thickness, equivalent spherical diameter) and particle structure (core / shell structure), but the variation coefficient of the equivalent circular diameter of all the particles specified in the present invention is 40%, and the requirements (i) to (vi) It can be seen that only the samples 113, 115 and 116 satisfying all of ()) clearly have improved sensitivity. From these results, it can be seen that the sensitivity and pressure property of the grain emulsion in which the shell region occupying the main surface is wide and the uniformity of the silver iodide content between grains is high are remarkable. Emulsion A-1 in which gelatin added before shell formation was changed to high-molecular-weight gelatin similarly to the results in Table 201
Sample 116 using Sample No. 6 showed further improvement in sensitivity as compared with Samples 113 and 115.

From Table 203, it can be seen that in the case of thick grains having a thickness of 0.1 μm or more, even when the proportion of the shell phase occupying the main surface of the tabular grains is increased, no remarkable effect of improving the sensitivity is observed. In 203, the sensitivity of the sample 117 is set to 10
0 was set. ).

With respect to the pressure property, a compulsory test was performed by bending the film sample before exposure at a certain pressure and at an angle of 120 ° for 3 seconds to a side opposite to the emulsion surface with a certain portion of the film sample as a fulcrum. After the development, the pressure fog and pressure desensitization generated in the bent portion of the sample were visually evaluated.

From the results of Tables 201 and 202, tabular grains having a variation coefficient of the equivalent circle diameter of all the grains defined in the present invention of 40% and satisfying the requirements (i) to (vi) have a remarkable pressure resistance. It turns out that it improves. In particular, in Table 201, among emulsions composed of grains having a thickness of 0.1 μm or less as the proportion of the shell phase increased, the variation coefficient of the equivalent circle diameter of all grains defined in the present invention was 40%, Further, it can be seen that tabular grains satisfying the requirements (i) to (vi) have improved pressure resistance as compared with emulsions comprising grains having a standard thickness of 0.1 μm or more.

(Table 101 is based on Sample 101, and Table 202 is based on Sample 109.)

From Table 203, it can be seen that in the case of thick grains having a thickness of 0.1 μm or more, even if the proportion of the shell phase occupying the main surface of the tabular grains is increased and the distribution of the silver iodide content between grains is made uniform, the pressure is remarkable. It can be seen that no improvement in resistance was observed.
(Based on sample 117).

From the above results, it was found that the region having dislocation lines was expanded and the distribution of the silver iodide content between grains was made uniform with respect to the tabular grains having a small grain thickness according to the present invention, whereby high sensitivity and pressure resistance were obtained. It is clear that an improved emulsion is obtained.

[0224]

[Table 5]

[0225]

[Table 6]

[0226]

[Table 7]

Example 2 (Preparation of Emulsions A-25 to 28) Emulsions A-25 to 28 were prepared by changing the preparation conditions of Emulsion A-8 of Example 1 as follows. did.

In (Addition 6), instead of adding the crystal habit-controlling agent (Exemplary Compound I-1) in accordance with the addition of the Ag-4 aqueous solution, Exemplified Compounds II-2, III-2, and IV, respectively.
-2, V-3, 1.5 to Ag total mol
An aqueous solution containing mmol is added in a fixed amount.

[0229]

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Emulsion A-25-2 was prepared in the same manner as in Example 1.
8 was applied to prepare Samples 125 to 128, and the photographic performance was evaluated in the same manner as in Example 1. As a result, good performance was exhibited as in Emulsion A-8 (Sample 108).

Example 3 (Preparation of Emulsion B-1) 0.96 g of gelatin-4, KB
1192 mL of an aqueous solution containing 0.9 g of r was maintained at 40 ° C. and stirred vigorously (1st liquid preparation). AgNO ₃ ,
37.5 mL of an aqueous solution containing 1.49 g and 1.0 KBr
30 g of an aqueous solution containing 5 g of 37.5 mL by the double jet method
It was added over a second (addition 1). After adding 1.2 g of KBr, the temperature was raised to 75 ° C. to ripen. After ripening, 35 g of gelatin-3 was added to adjust the pH to 7. 6 mg of thiourea dioxide were added. 116 mL of an aqueous solution containing 29 g of AgNO ₃ and an aqueous KBr solution were added by double jet method at an accelerated flow rate such that the final flow rate was three times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was
Was maintained at 8.15 (addition 2). AgNO ₃ to 11
440.6 mL of an aqueous solution containing 0.2 g and an aqueous KBr solution were added over a period of 30 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time,
An AgI fine grain emulsion having a grain size of 0.037 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 15.8 mol%, and p of the bulk emulsion solution in the reaction vessel was added.
Ag was kept at 7.85. (Addition 3) 2 AgNO ₃
96.5 mL of an aqueous solution containing 4.1 g and an aqueous KBr solution were added over 3 minutes by a double jet method. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.85 (addition 4). After adding 26 mg of sodium ethylthiosulfonate, the temperature was lowered to 55 ° C., an aqueous KBr solution was added, and
The pAg of the bulk emulsion solution in the reaction vessel was adjusted to 9.80. 7. The above AgI fine grain emulsion was converted to KI weight by 8.
5 g was added (addition 5). Immediately after the addition is completed, AgNO
228 mL of an aqueous solution containing 57 g of ₃ was added over 5 minutes. At this time, an aqueous KBr solution was used to adjust the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition to 8.75 (addition 6). After washing with water, gelatin-1 was added and 4
The pH was adjusted to 5.8, pAg, and 8.7 at 0 ° C.

Subsequently, the following sensitizing dye Exs-1, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were successively added and optimally subjected to chemical sensitization. Mercapto compound MER-
Chemical sensitization was terminated by adding a total of 3.6 × 10 ^-4 mol of 1 and MER-2 at a ratio of 4: 1 per mol of silver halide.

The sensitizing dye of the present invention is disclosed in JP-A-11-525.
This was used as a solid fine dispersion prepared by the method described in No. 07.

For example, a solid fine dispersion of the sensitizing dye Exs-1 was prepared as follows.

0.8 parts by weight of NaNO ₃ and Na ₂ SO ₄
Dissolve 3.2 parts by weight in 43 parts of ion-exchanged water, add 13 parts by weight of a sensitizing dye, and disperse at 2000 rpm for 20 minutes using a dissolver blade at 60 ° C.
A solid fine dispersion of the sensitizing dye Exs-1 was obtained.

[0236]

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[0237]

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(Preparation of Emulsion B-2) Emulsion B-2 was prepared by changing the preparation conditions of Emulsion B-1 described above as follows.

After the temperature was lowered to 55 ° C. in (addition 5) of B-1, 8.5 g of the AgI fine grain emulsion was converted to KI weight by 8.5 g.
Instead of the addition, the temperature was lowered to 40 ° C., and an aqueous solution containing 0.051 mol of sodium p-iodoacetamidobenzenesulfonate, an iodide ion releasing agent, was added. To generate iodide ions while controlling the pH to 9.0. After 2 minutes, the temperature was raised to 55 ° C. over 15 minutes, and then the pH was lowered to 5.5.

(Preparation of Emulsion B-3) Emulsion B-3 was prepared by changing the preparation conditions of Emulsion B-1 described above as follows.

The addition of the AgI fine grain emulsion of (addition 5) of B-1 is not performed.

(Preparation of Emulsion B-4) Emulsion B-4 was prepared by changing the preparation conditions of Emulsion B-2 described above as follows.

In (Addition 6), an aqueous solution containing the crystal habit-controlling agent (Exemplified Compound I-1) in an amount of 1.3 mmol per Ag mol with respect to the total silver amount is added at the same time as the Ag-4 aqueous solution is added. .

(Preparation of Emulsion B-5) Emulsion B-5 was prepared by changing the preparation conditions of Emulsion B-3 described above as follows.

In (Addition 6), an aqueous solution containing the crystal habit controlling agent (Exemplified Compound I-1) in an amount of 1.3 mmol per Ag mol with respect to the total silver amount is added at the same time as the addition of the Ag-4 aqueous solution. .

(Preparation of Emulsion B-6) Emulsion B-6 was prepared by changing the preparation conditions of Emulsion B-5 described above as follows.

(Addition 6) Gelatin-1 to be added after washing with water was mixed with a high molecular weight gelatin prepared using a vinyl sulfone crosslinking agent [H-2] described in Example 1 of JP-A-11-237704. In the molecular weight distribution measured by the PAGI method, the composition is changed to a crosslinked lime-processed gelatin in which a component having a molecular weight of 280,000 or more accounts for 40% of the whole.

(Preparation of Emulsion B-7) Emulsion B-7 was prepared by changing the preparation conditions of Emulsion B-2 described above as follows.

The amount of AgNO _{3 in} (Addition 2) is changed to 20 g. The amount of AgNO _{3 in} (Addition 3) was changed to 80.2 g. The amount of AgNO _{3 in} (Addition 4) was changed to 14.1 g. The amount of AgNO _{3 in} (Addition 6) was changed to 106 g.

(Preparation of Emulsion B-8) Emulsion B-8 was prepared by changing the preparation conditions of Emulsion B-7 as described below.

In (Addition 6), an aqueous solution containing 1.3 mmol of the crystal habit-controlling agent (Exemplified Compound I-1) per 1.3 mol of Ag with respect to the total silver was added in a quantitative manner in accordance with the addition of the aqueous solution of Ag-4. .

(Preparation of Emulsion B-9) Emulsion B-9 was prepared by changing the preparation conditions of Emulsion B-8 described above as follows.

(Addition 6) The gelatin-1 to be added after washing with water was mixed with a high molecular weight gelatin prepared using a vinyl sulfone crosslinking agent [H-2] described in Example 1 of JP-A-11-237704. In the molecular weight distribution measured by the PAGI method, the composition is changed to a crosslinked lime-processed gelatin in which a component having a molecular weight of 280,000 or more accounts for 40% of the whole.

(Preparation of Emulsion B-10) Emulsion B-2
Emulsion B-8 was prepared under the following changes to the preparation conditions of

In (1st liquid preparation), the amount of KBr to be added is changed to 1.2 g. The amount of AgNO _{3 in} (addition 1) was changed to 3.5 g.

(Preparation of Emulsion B-11) Emulsion B-1
Emulsion B-11 was prepared under the following modification with respect to the preparation condition 0.

In (Addition 6), an aqueous solution containing the crystal habit-controlling agent (Exemplified Compound I-1) in an amount of 1.3 mmol per Ag mol with respect to the total silver amount is added at the same time as the Ag-4 aqueous solution is added. .

[0258]

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Table 301 shows the characteristic values of the emulsion grains of Emulsions B-1 to B-11. These emulsions B-2 to B-11 were also subjected to the same chemical sensitization as in emulsion B-1. In the preparation of these emulsions, the addition rates of the aqueous silver nitrate solution and the aqueous halide salt solution were each controlled at a rate commensurate with the critical growth rate of the silver halide grains, and were appropriately controlled so as not to cause renucleation or polydispersion due to Ostwald ripening. did.

[0260]

[Table 8]

As can be seen from Table 301, in the emulsion grains prepared using the crystal habit controlling agent, the proportion of the shell phase in the main surface of the tabular grains was large. It can be seen that the thickness of the tabular grains decreases as the proportion of the occupied shell phase increases.

With respect to the silver iodide content distribution between grains,
Emulsion particles prepared using an iodide ion releasing agent have a KI
It can be seen that the distribution between grains is narrower than that of emulsion grains prepared by adding an aqueous solution or adding a silver iodide fine grain emulsion.

Emulsions B-1 to B-11 were prepared in the same manner as in Example 1.
Was applied to prepare Samples 301 to 311. Further, photographic performance was evaluated in the same manner as in Example 1. The results are shown in Table 302.

The sensitivity was represented by a relative value of the reciprocal of the exposure required to reach a density of fog density plus 0.2. From the results in Table 302, the variation coefficient of the circle equivalent diameter of all the particles was 40.
%, And tabular grains satisfying the requirements (i) to (vi) have a remarkable effect on photographic sensitivity improvement (Table 3).
In 02, the sensitivity of the sample 301 was set to 100. ).

That is, in Table 302, samples 304 and 30
Nos. 6 to 309 have a variation coefficient of the equivalent circle diameter of all the particles defined in the present invention of 40% and satisfy the requirements (i) to (vi).
11) Tabular grains, equivalent circle diameter, thickness, equivalent spherical diameter) and grain structure (core / shell structure, uniformity of silver iodide content between grains) are satisfied, but under another condition of the present invention. Sample 30 that also satisfies the size of the shell area occupying a certain main surface
It can be seen that only 4, 306, 308 and 309 have greatly improved sensitivity. Sample 30 in which gelatin-1 added after washing with water in the emulsion preparation was changed to high molecular weight gelatin.
Samples Nos. 6 and 309 showed further improvements in sensitivity as compared with Samples 304 and 308.

The samples 304, 306 and 308, 30
9, the core / shell silver content ratio is different, but the variation coefficient of the circle equivalent diameter of all grains defined in the present invention is 40%,
Further, the particles satisfy the requirements (i) to (vi), and a similar improvement in sensitivity was observed. From this, it can be said that the amount of core / shell silver does not limit the present invention.

Also, from the results of Samples 310 and 311 that the effect of the width of the shell region occupying the main surface of the tabular grains as described in the present invention is not so large for the small-sized grains having an equivalent sphere diameter of less than 0.5. It was not noticeable.

With respect to the pressure property, a compulsory test was performed by bending the film sample before exposure at a certain pressure and at an angle of 120 ° for 3 seconds to a side opposite to the emulsion surface with a certain portion as a fulcrum. After the development, the pressure fog and pressure desensitization generated in the bent portion of the sample were visually evaluated.

From the results shown in Table 302, the coefficient of variation of the equivalent circle diameter of all the particles defined in the present invention was 40%, and the requirement was satisfied.
It can be seen that tabular grains satisfying (i) to (vi) significantly improve the pressure resistance (in Table 302, sample 301 was used as a reference).

Further, in grains having an equivalent sphere diameter of less than 0.5, remarkable pressure resistance can be obtained even if the ratio of the shell phase to the main surface of the tabular grains is increased and the silver iodide content distribution between grains is made uniform. It can be seen that no improvement was observed (based on sample 310).

From the above results, as in Example 1, the region having dislocation lines was expanded with respect to the tabular grains having a small grain thickness according to the present invention, and the silver iodide content distribution between grains was made uniform. It is clear that an emulsion having high sensitivity and improved pressure characteristics can be obtained.

[0272]

[Table 9]

Example 4 Silver halide emulsions DG, H-1-4, IM and NR were prepared by the following production methods.

(Preparation method of emulsion D) 31.7 phthalated low molecular weight gelatin having a phthalation rate of 97% and a molecular weight of 15,000
g, 32.2 g of KBr and 42.2 L of an aqueous solution at 35 ° C.
And stirred vigorously. 1583 mL of an aqueous solution containing 316.7 g of AgNO ₃ , 221.5 g of KBr, and 1583 m of an aqueous solution containing 52.7 g of gelatin-4 of Example 1.
L was added over 1 minute by the double jet method. Immediately after the addition was completed, 52.8 g of KBr was added, and 2485 mL of an aqueous solution containing 398.2 g of AgNO ₃ and 29 Br of KBr were added.
2,581 mL of an aqueous solution containing 1.1 g was added by a double jet method over 2 minutes. Immediately after the addition is completed, KBr,
44.8 g were added. Thereafter, the temperature was raised to 40 ° C. and the product was aged. After ripening, 923 g of gelatin-2 of Example 1
And 79.2 g of KBr were added, and AgNO ₃ , 5103
g of an aqueous solution containing 15947 mL and an aqueous KBr solution were added over a period of 10 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.4 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.90.
After washing with water, gelatin-1 of Example 1 was added thereto to adjust pH, 5.
7, pAg, 8.8, the weight in terms of silver per kg of emulsion, 131.8 g, and the weight of gelatin, 64.1 g, were prepared as a seed emulsion. 46 g of gelatin-2 of Example 1, KBr
1211 mL of an aqueous solution containing 1.7 g was maintained at 75 ° C. and stirred vigorously. After adding 9.9 g of the seed emulsion described above, modified silicone oil (L760, manufactured by Nippon Unicar Co., Ltd.)
0.3 g of 2) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , the final flow rate becomes 5.1 times the initial flow rate by a double jet method using 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and an aqueous KBr solution. The flow rate was accelerated as described above and added over 6 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.15. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 105.6 g of AgNO ₃ , 32
8 mL and an aqueous KBr solution were added by a double jet method over a period of 56 minutes by accelerating the flow rate so that the final flow rate was 3.7 times the initial flow rate. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 27 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.60. Was. AgN
121.3 mL of an aqueous solution containing 45.6 g of O ₃ and an aqueous KBr solution were added over 22 minutes by a double jet method. At this time, the pAg of the bulk emulsion solution in the reaction vessel was 7.60.
Kept. After raising the temperature to 82 ° C. and adding KBr to adjust the pAg of the bulk emulsion solution in the reaction vessel to 8.80,
6.33 g of the above AgI fine grain emulsion in terms of KI weight
Was added. Immediately after the end of the addition, 66.4 of AgNO ₃ was added.
206.2 mL of an aqueous solution containing g were added over 16 minutes. During the initial 5 minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.80 with an aqueous KBr solution. After washing with water, gelatin-1 of Example 1 was added, and the pH was adjusted at 40 ° C.
Adjusted to 5.8, pAg, 8.7. After the addition of TAZ-1, the temperature was raised to 60C. After adding the sensitizing dyes Exs-2 and Exs-3, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimal chemical sensitization. At the end of the chemical sensitization, compound 3 and compound 4 were added. Here, the optimal chemical sensitization means that the sensitizing dye and each compound are selected from the range of 10 ^-1 to 10 ^-8 mol per mol of silver halide.

[0275]

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[0276]

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[0277]

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(Preparation of Emulsion E) In the preparation of Emulsion B-1 of Example 3, a step of adding TAZ-1 was added before chemical sensitization, and added at the beginning of chemical sensitization. The sensitizing dye was changed to a combination of sensitizing dyes Exs-2 and Exs-3. Other than that, it was prepared in substantially the same manner as in emulsion B-1.

[0279]

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[0280]

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(Preparation of Emulsion F) Gelatin-2 of Example 1
Aqueous solution containing 1.02 g of KBr and 0.9 g of KBr
L was kept at 35 ° C. and stirred vigorously. AgNO ₃ , 4.4
An aqueous solution containing 7 g, 42 mL and KBr, and an aqueous solution containing 3.16 g, 42 ml, were added by a double jet method over 9 seconds. After adding 2.6 g of KBr, the temperature was raised to 63 ° C. to ripen. After ripening, 4 parts of gelatin-3 of Example 1 were added.
1.2 g and 18.5 g of NaCl were added. After adjusting the pH to 7.2, dimethylamine borane, 8 mg, was added. 203 mL of an aqueous solution containing 26 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.65. AgN
440.6 mL of an aqueous solution containing 110.2 g of O ₃ and KBr
4. The final flow rate of the aqueous solution is the initial flow rate by the double jet method.
The flow rate was accelerated so as to be 1 times, and the addition was performed over 24 minutes. At this time, the AgI fine grain emulsion used in the preparation of Emulsion D was simultaneously added at an accelerated flow rate such that the silver iodide content became 2.3 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was 8.50. Kept. After adding 10.7 mL of a 1N aqueous solution of potassium thiocyanate, AgNO ₃ , 2
153.5 mL of an aqueous solution containing 4.1 g and an aqueous KBr solution were added by a double jet method over 2 minutes and 30 seconds. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.05. The aqueous KBr solution was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.25. AgI mentioned above
6.4 g of the fine grain emulsion was added in terms of KI weight. Immediately after the addition, 404 mL of an aqueous solution containing 57 g of AgNO ₃
Was added over 45 minutes. At this time, an aqueous KBr solution was used so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 8.65. The emulsion was washed with water in almost the same manner as in Emulsion D and chemically sensitized.

(Preparation of Emulsion G) In the preparation of Emulsion F, the amount of AgNO ₃ added during nucleation was changed to 2.3 times. Then, a change was made so that the KBR aqueous solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition of 404 mL of an aqueous solution containing 57 g of AgNO ₃ was 6.85. Other than that, it was prepared almost in the same manner as Emulsion F.

(Preparation of Emulsion H-1) Emulsion A- of Example 1
In the preparation of compound (1), a step of adding TAZ-1 is added before chemical sensitization, and sensitizing dyes added at the beginning of chemical sensitization are Exs-1, Exs-4 and Exs-5.
Changed to a combination. Other than that, it was prepared in substantially the same manner as in emulsion C1. The amount of each sensitizing dye used was such that Exs-1 was 5.50 × 10 ⁻⁴ per mol of silver halide.
Mol, Exs-4 1.30 × 10 ^-4 mol, Exs-5
Is 4.65 × 10 ^-5 mol.

[0284]

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[0285]

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(Preparation of Emulsions H-2 to 15) In the preparation of Emulsions A-2 to A-8 in Example 1 and Emulsions A-25 to E-28 in Example 2, TAZ-1 was added before chemical sensitization. Emulsions H-2 to 12 were prepared by adding an addition step and changing the sensitizing dye added at the beginning of chemical sensitization to a combination of Exs-1, Exs-4 and Exs-5. Other than that, it was prepared almost in the same manner as emulsions A-2 to 8 and A-25 to 28. The amount of each sensitizing dye used was the same as that of the emulsion H
Same as -1.

(Preparation of Emulsion Ia) Gelatin of Example 1
Aqueous solution 12 containing 0.75 g of KB-4 and 0.9 g of KBr
Keep 00mL at 39 ° C, adjust pH to 1.8 and vigorously
Stirred. AgNO_ThreeAqueous solution containing 1.85 g of
Double jet of KBr aqueous solution containing 5mol% KI
The method was added over 16 seconds. At this time, the excess concentration of KBr
The degree was kept constant. The temperature was raised to 54 ° C. and ripened. Aging end
Thereafter, 20 g of gelatin-2 of Example 1 was added. pH
After adjusting to 5.9, 2.9 g of KBr was added. A
gNO_Three, 288 mL of aqueous solution containing 27.4 g and KBr water
The solution was added by the double jet method over 53 minutes. This
In this case, the AgI fine grain emulsion having a grain size of 0.03 μm was
Simultaneously added so that the silver iodide content becomes 4.1 mol%
And the pAg of the bulk emulsion solution in the reaction vessel was 9.4.
It was kept at zero. After adding 2.5 g of KBr, AgNO
_ThreeAqueous solution containing 87.7 g and KBr aqueous solution
So that the final flow rate is 1.2 times the initial flow rate
The flow was accelerated and added over 63 minutes. At this time,
AgI fine grain emulsion having a silver iodide content of 10.5 mol%
At the same time, accelerate the flow rate and add
The pAg of the bulk emulsion solution in was kept at 9.50. Ag
NO_Three, 132 mL of aqueous solution containing 41.8 g and KBr aqueous solution
The liquid was added by the double jet method over 25 minutes. Addition
The pAg of the bulk emulsion solution in the reaction vessel at the time of completion is 8.1.
The addition of the aqueous KBr solution was adjusted to be 5. pH
Adjusted to 7.3 and added 1 mg of thiourea dioxide.
Add KBr and add pAg of bulk emulsion solution in reaction vessel
Was adjusted to 9.50, and the above AgI fine grain emulsion was adjusted to K
8.78 g in terms of I weight was added. Immediately after addition is complete
AgNO_Three609 mL of an aqueous solution containing 63.3 g for 10 minutes
Added over time. For 6 minutes at the beginning of addition, use KBr aqueous solution
The pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.50.
Was. After washing with water, gelatin-1 of Example 1 was added and added.
PH was adjusted to 6.5, pAg, and 8.2 at ℃. Emulsion H1
Chemical sensitization was performed in almost the same manner. The amount of sensitizing dye used
Means that Exs-1 is 1.08 per mole of silver halide.
× 10^-32.56 x 10 mol, Exs-4^-FourMol, e
xs-5 is 9.16 × 10^-FiveIs a mole.

(Preparation of Emulsion J) Gelatin-4 of Example 1
0.70 g, KBr, 0.9 g, KI, 0.175
g, modified silicone oil 0.2 used in the preparation of Emulsion D
g, an aqueous solution containing 1200 g was maintained at 33 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred. 1.8 g of AgNO ₃
And an aqueous KBr solution containing 3.2 mol% of KI were added by a double jet method over 9 seconds. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 62 ° C. and ripened. After ripening, 2 parts of gelatin-3 of Example 1 were added.
7.8 g were added. After adjusting the pH to 6.3, KB
r, 2.9 g were added. 270 mL of an aqueous solution containing 27.58 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 37 minutes. At this time, the aqueous solution of gelatin-4, the aqueous solution of AgNO _{3, and the} aqueous solution of KI of Example 1 were mixed in a separate chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570, immediately before the addition, to prepare. The AgI fine grain emulsion having a grain size of 0.008 μm was simultaneously added so that the silver iodide content became 4.1 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.15. After adding 2.6 g of KBr, A
An aqueous solution containing 87.7 g of gNO ₃ and an aqueous KBr solution were added by a double jet method over a period of 49 minutes while accelerating the flow rate so that the final flow rate was 3.1 times the initial flow rate. At this time,
The AgI fine grain emulsion prepared by mixing immediately before the above-mentioned addition was simultaneously accelerated so that the silver iodide content became 7.9 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.30. . After adding 1 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and K were added.
An aqueous Br solution was added over 20 minutes by the double jet method. PAg of bulk emulsion solution in reaction vessel at the end of addition
Was adjusted to 7.90. After the temperature was raised to 78 ° C and the pH was adjusted to 9.1, KB
r was added to bring the pAg of the bulk emulsion solution in the reaction vessel to 8.70. The AgI fine grain emulsion used in the preparation of Emulsion D was added in an amount of 5.73 g in terms of KI weight. Immediately after the addition, an aqueous solution 321 containing 66.4 g of AgNO ₃
mL was added over 4 minutes. KB for 2 minutes at the beginning of addition
7. The pAg of the bulk emulsion solution in the reaction vessel was adjusted to 8.
It was kept at 70. It was washed with water and chemically sensitized almost in the same manner as in Emulsion H1. The amount of the sensitizing dye used was such that Exs-1 was 1.25 × 10 ^-3 mol and Exs-
2.85 × 10 ^-4 mol, Exs-5 3.29 × 1
0 ^-5 mol.

(Preparation of Emulsion K) Gelatin-1 of Example 1
And an aqueous solution containing 17.8 g, KBr, 6.2 g, KI and 0.46 g was kept at 45 ° C. and stirred vigorously. AgN
An aqueous solution containing 11.85 g of O ₃ and an aqueous solution containing 3.8 g of KBr were added by a double jet method over 45 seconds. After the temperature was raised to 63 ° C, gelatin-1 of Example 1 was added to 24.
1 g was added and the mixture was aged. After aging, AgNO ₃ , 13
An aqueous solution containing 3.4 g and an aqueous KBr solution were added by a double jet method over 20 minutes so that the final flow rate was 2.6 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.60. Ten minutes after the start of the addition, 0.1 mg of K ₂ IrCl ₆ was added. NaCl 7
g of an aqueous solution containing 45.6 g of AgNO ₃ and K
The aqueous Br solution was added by the double jet method over 12 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 6.90. Further, 100 mL of an aqueous solution containing 29 mg of yellow blood salt was added over 6 minutes from the start of the addition. KB
After adding 14.4 g of r, A used in the preparation of emulsion D
6.3 g of the gI fine grain emulsion was added in terms of KI weight. Immediately after the addition was completed, an aqueous solution containing 42.7 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 11 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was
Was maintained at 6.90. It was washed with water and chemically sensitized almost in the same manner as in Emulsion H1. The amount of the sensitizing dye used was 5.79 × 10 ⁻⁴ mol of Exs-1 per mol of silver halide, and
xs-4 is 1.32 × 10 ^-4 mol, Exs-5 is 1.5
2 × 10 ^-5 mol.

(Preparation of Emulsion L) Emulsion K was prepared in substantially the same manner except that the temperature during nucleation was changed to 35 ° C. The amount of the sensitizing dye used was 1 silver halide.
9.66 × 10 ⁻⁴ mol of Exs-1 per mol, Ex
2.20 × 10 ^-4 mol for s-4, 2.54 for Exs-5
× 10 ^-5 mol.

(Preparation of Emulsion M) Gelatin-4 was added at 0.75
g, KBr, and 0.9 g of an aqueous solution containing 0.9 g of 39 g.
C., adjusted to pH 1.8 and stirred vigorously. Ag
An aqueous solution containing 0.34 g of NO ₃ and KI of 1.5 mol%
Was added over 16 seconds by the double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 54 ° C. and ripened. After ripening, gelatin
2 of 20 g was added. After adjusting the pH to 5.9, K
2.9 g of Br were added. After addition of thiourea dioxide 3 mg, AgNO _3, an aqueous solution containing 28.8 g 28
8 ml and an aqueous KBr solution were added by a double jet method over 58 minutes. At this time, Ag having a particle size of 0.03 μm was used.
The I fine grain emulsion was simultaneously added so that the silver iodide content became 4.1 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.40. After adding 2.5 g of KBr, an aqueous solution containing 87.7 g of AgNO ₃ and KBr were added.
The final flow rate of the aqueous solution is 1.
The flow rate was accelerated so as to be doubled, and added over 69 minutes. At this time, the AgI fine grain emulsion described above was simultaneously added at an accelerated flow rate such that the silver iodide content became 10.5 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was adjusted to 9.
It was kept at 50. Aqueous solution 1 containing 41.8 g of AgNO ₃
32 mL and an aqueous KBr solution were added by a double jet method over 27 minutes. The addition of the KBr aqueous solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition became 8.15. Sodium benzenethiosulfonate 2m
g, KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.50, and then the above Ag was added.
5.73 g of the I fine grain emulsion was added in terms of KI weight. Immediately after the addition was completed, 609 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 11 minutes. During the initial 6 minutes of the addition, the pA of the bulk emulsion solution in the reaction vessel was treated with an aqueous KBr solution.
g was kept at 9.50. After washing with water, gelatin was added and the pH was adjusted to 6.5, pAg, and 8.2 at 40 ° C. Thereafter, TAZ-1 was added, and the temperature was raised to 56 ° C. The sensitizing dyes Exs-1 and Exs-6 were added, followed by potassium thiocyanate, chloroauric acid, sodium thiosulfate, N,
N-Dimethylselenourea was added and ripened for optimal chemical sensitization. MER-1 and MER-3 at the end of chemical sensitization
Was added. The amount of the sensitizing dye used was 3.69 × 10 ⁻⁴ mol of Exs-1 per mol of silver halide, and
xs-6 is 8.19 × 10 ⁻⁴ mol.

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(Preparation of Emulsion N) Gelatin-2 of Example 1
Solution containing 0.38 g of KBr and 0.9 g of KBr
L was maintained at 60 ° C., the pH was adjusted to 2, and the mixture was stirred vigorously.
An aqueous solution containing 1.03 g of AgNO ₃ and 0.8% of KBr
An aqueous solution containing 8 g and 0.09 g of KI was added by a double jet method over 30 seconds. After completion of the ripening, 12.8 g of gelatin-3 of Example 1 was added. After adjusting the pH to 5.9, KBr, 2.99 g, NaCl, 6.2 g
Was added. An aqueous solution containing 27.3 g of AgNO ₃ 60.
7 mL and an aqueous KBr solution were added by the double jet method over 39 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.05. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were accelerated by a double jet method so that the final flow rate was 2.1 times the initial flow rate, and 46
Added over minutes. At this time, the AgI fine grain emulsion used in the preparation of Emulsion D was simultaneously added at an accelerated flow rate such that the silver iodide content became 6.5 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was adjusted to 9.05. Kept. After adding 1.5 mg of thiourea dioxide, AgNO ₃ , 4
132 mL of an aqueous solution containing 1.8 g and an aqueous KBr solution were added by a double jet method over 16 minutes. The addition of the aqueous KBr solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition became 7.70. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.80. The above AgI fine grain emulsion was added in an amount of 6.2 g in terms of KI weight. Immediately after the addition, AgNO ₃ , 8
300 mL of an aqueous solution containing 8.5 g was added over 10 minutes. PA of bulk emulsion solution in reaction vessel at the end of addition
It adjusted by adding KBr aqueous solution so that g might be set to 7.40. After washing with water, gelatin-1 of Example 1 was added and added.
PH was adjusted to 6.5, pAg, and 8.2 at ℃. TAZ-
After adding 1, the temperature was raised to 58 ° C. Sensitizing dye Exs-
7, Exs-8 and Exs-9 after addition of K ₂ I
rCl ₆ , potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimal chemical sensitization. At the end of the chemical sensitization, MER-1 and MER-3 were added.

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(Preparation of Emulsion O) In the preparation of Emulsion N,
The amount of AgNO ₃ added during nucleation is 1.96 g,
The amount of Br was changed to 1.67 g, the amount of KI was changed to 0.172 g, and the temperature at the time of chemical sensitization was changed from 58 ° C to 6 ° C.
The temperature was changed to 1 ° C. Other than that, it was prepared in substantially the same manner as in emulsion N.

(Preparation of Emulsion P) Gelatin-4 of Example 1
Solution containing 4.9 g of KBr and 5.3 g of KBr
L was kept at 40 ° C. and stirred vigorously. AgNO ₃ , 8.75
g and an aqueous solution containing KBr and 6.45 g were added by the double jet method over 1 minute. After the temperature was raised to 75 ° C., 21 mL of an aqueous solution containing 6.9 g of AgNO ₃ was added over 2 minutes. NH ₄ NO ₃ ,
After sequentially adding 26 g, 1N, NaOH and 56 mL, the mixture was aged. After aging, the pH was adjusted to 4.8. A
Gno _3, 1 of an aqueous solution 438mL and KBr containing 141g
458 mL of an aqueous solution containing 22.6 g was added by a double jet method so that the final flow rate was four times the initial flow rate. 55
After cooling to ℃, an aqueous solution 2 containing 7.1 g of AgNO ₃
An aqueous solution containing 40 mL and 6.46 g of KI was added over 5 minutes by the double jet method. After adding 7.1 g of KBr, sodium benzenethiosulfonate, 4 mg and K
0.05 mg of ₂ IrCl ₆ was added. AgNO ₃ , 5
177 mL of an aqueous solution containing 7.2 g and KBr, 40.2 g
Was added by the double jet method over 8 minutes. The emulsion was washed with water in almost the same manner as in Emulsion N and chemically sensitized.

(Preparation of Emulsions Q and R) Emulsions K and L were prepared in substantially the same manner. However, the chemical sensitization was carried out in substantially the same manner as for emulsion O.

Table 40 shows the characteristic values of the silver halide emulsion.
1 together. The surface iodine content can be determined by XPS as follows. 0.5 × 10 ^-5 sample
After cooling to −115 ° C. in a vacuum of not more than torr, MgKα was used as a probe X-ray with an X-ray source voltage of 8 kV and an X-ray current of 2
Irradiation at 0 mA, Ag3d5 / 2, Br3d, I3d5
/ 2 electrons were measured, the integrated intensity of the measured peak was corrected by a sensitivity factor, and the iodine content on the surface was determined from these intensity ratios. The emulsions D to G and H-5a to
Dislocation lines as described in JP-A-3-237450 were observed in silver halide grains g, Ia, and J to R using a high-pressure electron microscope.

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[Table 10]

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[Table 11]

1) Support The support used in this example was prepared by the following method.

100 parts by weight of polyethylene-2,6-naphthalate polymer and Tinuvin as an ultraviolet absorber
P. 326 (manufactured by Ciba-Geigy) and 2 parts by weight, and then melted at 300 ° C.
It was extruded from the die, stretched 3.3 times at 140 ° C., stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds to form a 90 μm-thick PEN (polyethylene). A naphthalate) film was obtained. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technique: I-1, I-4, I-6, I-24, I-26, I-26 described in Japanese Patent Publication No. 94-6023). 2
7, II-5) was added in an appropriate amount. Furthermore, diameter 20cm
And a heat history of 110 ° C. for 48 hours was given to obtain a support that is less likely to have a curl.

2) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV discharge treatment and a glow discharge treatment on both surfaces thereof, and then, each surface was coated with 0.1 g / m ² of gelatin and sodium α- Sulfodi-2-
Ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g
/ M ² , (CH ₂ ＣＨCHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH
₂ 0.012 g / m ² , and an undercoat solution of polyamide-epichlorohydrin polycondensate 0.02 g / m ² (10c
c / m ² , using a bar coater), and an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a slip layer having the following composition were coated as back layers on one side of the support after the undercoat.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm, a dispersion of fine particle powder (secondary aggregated particle diameter of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 N
HCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10)
Oxyethylene-p-nonylphenol 0.005 g /
It was coated with m ² and resorcin.

3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ²⁾ / G, major axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 Am ²
/ Kg, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface of which is treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.0
6 g / m ² was added to diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was performed by an open kneader and a sand mill), and C ₂ H ₅ C (CH ₂ OCONH-C ₆ H) was used as a curing agent.
0.3 g / m ² of ₃ (CH ₃ ) NCO) ₃ was applied by a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. Silica particles (0.3 μm) and 3 as matting agent
10 mg each of an abrasive aluminum oxide (0.15 μm) coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight)
/ M ² . Drying was carried out at 115 ° C for 6 minutes.
15 ° C). X- light (blue filter) saturation magnetization moment of about 0.1, and the magnetic recording layer is color density increment of D ^B of the magnetic recording layer of the 4.2Am ² / kg, a coercive force 7.3 × 10 ⁴ A / m and the squareness ratio were 65%.

3-3) Adjustment of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH
(OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg /
m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b,
9 mg / m ² ) mixture was applied. In addition, this mixture is xylene / propylene monomethyl ether (1/1 /
In 1), the mixture was melted at 105 ° C., and poured into and dispersed in propylene monomethyl ether (10-fold amount) at room temperature, and then dispersed in acetone (average particle size: 0.01 μm). As a matting agent, silica particles (0.3 μm) and aluminum oxide (0.15 μm) coated with 3-poly (degree of polymerization 15) oxyethylenepropyloxytrimethoxysilane (15% by weight) as an abrasive are each 15 mg / m 2.
² was added. Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.)
° C). The sliding layer has a dynamic friction coefficient of 0.06 (stainless steel hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.07 (clip method), and a kinetic friction coefficient of 0.12 between the emulsion surface and the sliding layer described later. Excellent characteristics.

4) Coating of Photosensitive Layer (Sample 401) Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in a multi-layered manner to obtain a color negative photosensitive material, Sample 4
01 was created. Samples in which the emulsion H-1 was replaced with H-2 to H12 are referred to as samples 402 to 412, respectively.

(Composition of photosensitive layer) The main materials used in each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow Coupler H: Gelatin hardener (Specific compounds are described below, numbers are added after symbols, and chemical formulas are listed after the numbers.) The number corresponding to each component is expressed in g / m ^2. In the case of silver halide, the amount is shown in terms of silver.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.155 Silver Iodobromide Emulsion T Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-3 0.002 Cpd-20 0.001 HBS-1 0.004 HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.066 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid Disperse Dye ExF -2 0.015 solid disperse dye ExF-3 0.020.

Third layer (intermediate layer) Silver iodobromide emulsion S 0.020 ExC-2 0.022 polyethyl acrylate latex 0.085 gelatin 0.294.

Fourth layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion R silver 0.065 silver iodobromide emulsion Q silver 0.258 ExC-1 0.109 ExC-3 0.044 ExC-40 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.17 Gelatin 0.80.

Fifth Layer (Medium Sensitivity Red-Sensitive Emulsion Layer) Silver iodobromide emulsion P silver 0.21 silver iodobromide emulsion O silver 0.62 ExC-1 0.14 ExC-2 0.026 ExC-30 0.020 ExC-4 0.12 ExC-5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18.

Sixth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion N silver 1.47 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY- 5 0.008 Cpd-2 0.046 Cpd-4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12.

Seventh layer (intermediate layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.83 Gelatin 0.84.

Eighth Layer (Layer that Gives Layering Effect to Red Sensitive Layer) Silver iodobromide emulsion M 0.560 Cpd-4 0.030 ExM-2 0.096 ExM-3 0.028 ExY-1 031 ExG-1 0.006 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion L silver 0.39 silver iodobromide emulsion K silver 0.28 silver iodobromide emulsion J silver 0.35 ExM-2 0.36 ExM-3 0.045 ExG-1 0.005 HBS-1 0.28 HBS-3 0.01 HBS-4 0.27 Gelatin 1.39.

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion Ia Silver 0.45 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY-1 0.006 ExM-4 0.028 ExG-1 0.005 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 gelatin 0.44.

Eleventh layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion Ia silver 0.30 silver iodobromide emulsion H-1 silver 0.69 ExC-6 0.004 ExM-1 0.016 ExM-3 0.036 ExM-4 0.020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 ExG-1 0.005 Cpd-4 0.007 HBS-1 0.18 Polyethyl Acrylate latex 0.099 gelatin 1.11.

Twelfth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.047 Cpd-1 0.16 Oil-soluble Dye ExF-5 0.010 Solid Dispersion Dye ExF-6 0.153 HBS-1 0.082 Gelatin 1 .057.

Thirteenth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion G silver 0.18 silver iodobromide emulsion E silver 0.20 silver iodobromide emulsion F silver 0.07 ExC-1 0.041 ExC-8 0.012 ExY-1 0.035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-10 .24 gelatin 1.41.

Fourteenth Layer (High Sensitive Blue Sensitive Emulsion Layer) Silver iodobromide emulsion D Silver 0.75 ExC-1 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd- 2 0.075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.91.

Fifteenth Layer (First Protective Layer) Silver Iodobromide Emulsion S Silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F-180 0.0009 F-19 0.005 F-20 0.005 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3.

Sixteenth layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.15 B-30 .05 S-1 0.20 gelatin 0.75.

Further, in order to improve the storability, processability, pressure resistance, fungicidal and germicidal properties, antistatic properties and coatability of each layer, W-1 to W-5, B-4 to B -6, F
-1 to F-18, and iron salts, lead salts, gold salts, platinum salts,
It contains palladium, iridium, ruthenium and rhodium salts. Further, 8.5 × 10 ^-3 g per mol of silver halide to the coating solution of the eighth layer, a 7.9 × 10 ^-3 grams of calcium in the 11th layer was added with an aqueous solution of calcium nitrate to form Sample .

Preparation of Dispersion of Organic Solid Disperse Dye ExF-3 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were put into a 700 ml pot mill. , Dye ExF-
5.0 g and zirconium oxide beads (diameter 1 mm)
500 ml was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles is 0.2
It was 4 μm.

Similarly, a solid dispersion of ExF-4 was obtained. The average particle size of the fine dye particles was 0.45 μm. E
xF-2 is disclosed in European Patent Application Publication (EP) 549,489.
Microprecipitation described in Example 1 of the specification of A (Microp
(recipitation) dispersion method.
The average particle size was 0.06 μm.

A solid dispersion of ExF-6 was dispersed by the following method.

To 2800 g of a wet cake of ExF-6 containing 18% of water, 376 g of a 3% solution of 4000 g of water and W-2 were added and stirred to obtain a 32% slurry of ExF-6. Next, 1700 ml of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd., and the slurry was passed through the slurry at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 liter / min for 8 hours. Crushed. The average particle size was 0.52 μm.

The compounds used for forming each of the above layers are as shown below.

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Each of these samples was subjected to a hardening treatment at 40 ° C. and a relative humidity of 70% for 14 hours. Thereafter, exposure was performed for 1/100 second through a continuous wedge and a gelatin filter SC-39 (a long-wavelength light transmission filter having a cutoff wavelength of 390 nm) manufactured by FUJIFILM Corporation. The development was performed as follows using an automatic developing machine FP-360B manufactured by Fuji Photo Film Co., Ltd. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-360B is an invention association disclosed technique 94-49.
No. 92 is mounted.

The processing steps and the composition of the processing solution are shown below.

(Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 ml 11.5 liter Bleaching 50 seconds 38.0 ° C 5 ml 5 liter Fixing (1) 50 seconds 38.0 ° C ─ 5 liter Fixing (2) 50 seconds 38.0 ° C 8 ml 5 liter Washing water 30 seconds 38.0 ° C 17 ml 3 liter Stable (1) 20 seconds 38.0 ° C ─ 3 liter Stable (2) 20 seconds 38.0 ° C 15 ml 3 liter Drying 1 minute 30 60.0 ° C per second * The replenishment amount is 35 mm of photosensitive material and 1.1 m width (corresponding to 24 Ex. 1 line).

The stabilizing solution and the fixing solution were of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm in width of the photosensitive material and 1.1 m in width.
2.5 ml, 2.0 ml, and 2.0 ml, respectively. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The opening area of the above-mentioned processing machine was 10
0cm ² , 120cm ^{2 for} bleaching solution, about 1 other processing solution
00 cm ² .

The following shows the composition of the processing solution.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 5.9. 3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy -6-methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino Aniline sulfate 4.5 6.5 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Add water 1.0 liter 1.0 liter pH [adjusted with aqueous ammonia] 4.6 4.0.

(Fixing (1) tank liquid) A 5:95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid.

(PH 6.8).

(Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 ml 720 ml (750 g / l) imidazole 721 ammonium methanethiosulfonate 515 ammonium methanesulfinate 10 30 ethylenediaminetetraacetic acid 13 39 Add water 1.0 liter 1.0 liter pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45.

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 m.
g / liter or less, followed by sodium diisocyanurate 20 mg / liter and sodium sulfate 1
50 mg / liter was added. The pH of this solution is 6.5
〜7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) 1,2-benzo Isothiazolin-3-one sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0. 75 Add water 1.0 liter pH 8.5.

The photographic performance was evaluated by measuring the density of these samples with a green filter. Table 4 shows the results
02. The sensitivity was represented by a relative value of the reciprocal of the exposure necessary to reach the density of fog density plus 0.2.
(The sensitivity of the sample 401 was set to 100.) Regarding the pressure property, an angle of 120 with a constant pressure on the opposite side to the emulsion surface with a certain portion of the film sample before exposure as a fulcrum.
The compulsory test was performed by bending for only 3 seconds. After the development, the pressure fog and pressure desensitization generated in the bent portion of the sample were visually evaluated (based on the sample 401).

As can be seen from Table 402, the use of the emulsion of the present invention showed an improvement in the performance of a full-color photographic light-sensitive material as well as a single-layer photographic light-sensitive material.

[0366]

[Table 12]

[0367]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/015 G03C 1/015 1/047 1/047

Claims (9)

[Claims] 1. The method according to claim 1, wherein the tabular grains satisfying the following (i) to (vi) occupy 50% or more of the total projected area, wherein the coefficient of variation of the equivalent circle diameter of all grains is 40% or less. Silver halide photographic emulsion. (I) Silver iodobromide or silver iodochlorobromide grains having a (111) plane as a main surface. (Ii) Circle-equivalent diameter of 1.0 μm or more and 0.1 μm or less. (Iii) Consisting of a core and a shell. One dislocation line per grain from the core-shell interface to the grain edge
(Iv) When the tabular grains are viewed from a direction perpendicular to the main surface, the shell-constituting region is an annular region having a length of 10% or more from the side to the center of the tabular grains. (V) The average silver iodide content of all grains is I mol% (0.3 <
I <20), the silver iodide content is in the range of 0.7I to 1.3I. (Vi) The equivalent sphere diameter is 0.5 μm or more. 2. The silver halide photographic emulsion according to claim 1, wherein the number of dislocation lines in (iii) is 20 or more. 3. The silver halide photographic emulsion according to claim 1, wherein the coefficient of variation of the equivalent circle diameter of all grains is 25% or less. 4. The silver halide photographic emulsion according to claim 1, wherein the coefficient of variation of the equivalent circle diameter of all grains is 15% or less. 5. The method for producing a silver halide photographic emulsion according to claim 1, wherein a shell containing dislocations is grown in the presence of a crystal habit controlling agent. 6. The method for producing a silver halide photographic emulsion according to claim 5, wherein a high molecular weight gelatin containing 30% or more of a component having a molecular weight of 280,000 or more in a molecular weight distribution measured by a PAGI method is used. . 7. The method for producing a silver halide photographic emulsion according to claim 5, wherein a tabular grain formed by adding a silver halide fine grain emulsion is used as a core. 8. A silver halide photographic material comprising the silver halide photographic emulsion according to claim 1. Description: 9. A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion prepared by the production method according to any one of claims 5 to 7.