JP2001166410A - Photosensitive silver halide emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion having high sensitivity and improved illuminance failure characteristics or heat fog resistance, and to provide a photographic sensitive material using the emulsion. SOLUTION: Relating to the photosensitive silver halide emulsion, normal crystalline silver halide grains having >=50% proportion of (100) faces and dislocation lines occupy >=50% of the total projected area and 10-8-10-4 mol one or more polyvalent metal ions based on 1 mol grain silver are contained in the silver halide grains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a light-sensitive silver halide emulsion containing normal-crystal silver halide grains (hereinafter also referred to as normal crystals or normal-crystal grains) and a silver halide photographic light-sensitive material having the emulsion. The present invention relates to a silver halide photographic material having high sensitivity and improved illuminance failure characteristics or heat fogging using normal-crystal silver halide grains.

[0002]

2. Description of the Related Art In recent years, demands for photographic silver halide emulsions have become more and more severe. In particular, extremely high levels of performance, such as high sensitivity, small illuminance failure, and excellent storage stability, have been demanded.

US Pat. No. 4,434,226 discloses a method for increasing the sensitivity of a silver halide emulsion, particularly using tabular silver halide grains.
Nos. 4,439,520 and 4,414,310
Nos. 4,433,048 and 4,414,306
No. 4,459,353, JP-A-58-11193.
No. 5, No. 58-111936, No. 58-111937
And Nos. 58-113927 and 59-99433. As a method for further increasing the sensitivity and granularity of a silver halide emulsion, a technique of introducing dislocation lines is generally known, and a technique of introducing dislocation lines into tabular silver halide grains is disclosed in US Pat. No. 4,956. , 269
Issue.

Although the above-described tabular grain technique is useful in achieving high sensitivity of silver halide grains, dislocation to silver halide grains having a high aspect ratio is required to take advantage of the properties of tabular grains. It has become evident that the use of lines can have adverse effects, such as rather degrading other photographic performance, for example, gradation and pressure resistance.

JP-A-5-107670, 4-317
No. 050, 5-53232, 4-372943
No. 4,362,628 discloses a technique for introducing dislocation lines into normal crystal grains. Also, Photo
ogr. Sci. Eng. 18 (1974) 215-2
25, JP-A-5-341417 and the like describe that cubic silver halide grains have low intrinsic desensitization and high contrast when a sensitizing dye is adsorbed.

However, in these techniques, sensitivity, gradation and pressure resistance are improved by introducing dislocation lines to normal crystal grains, but reciprocity failure characteristics are excellent and heat fog is remarkably improved. It has not been satisfactory as a silver halide emulsion that can withstand recent high demands.

On the other hand, a metal doping technique is known as a technique for controlling charge carriers (carriers) in silver halide grains such as free electrons and holes. For example, it has been reported by Leubner that the iridium complex doped with silver halide exhibits an electron trapping property (The Journal of Photo.
graphic Science Vol. 31,93
(1983)). Japanese Patent Application Laid-Open No. 6-175251 discloses a technique for achieving both sensitivity at 1/100 second exposure and reciprocity failure characteristics by using in-plane epitaxy type grains to which an iridium compound is added during a silver halide grain production process. It has been disclosed. JP-A-7-104406 discloses a technique in which silver halide fine particles are added in the presence of an iridium compound to improve reciprocity failure characteristics. However, when metal doping is performed, there is a disadvantage that fog, particularly heat-resistant fog, is deteriorated by metal ions present and adsorbed on the particle surface. JP-A-3-150
No. 40 discloses an iridium ion-containing emulsion in which iridium ions are not present on the grain surface and a method for producing the same. However, in this production method, metal ions adsorbed on the surface cannot be sufficiently removed, and no effect on heat resistance fog is described.

[0008] We have studied to further improve the photographic performance of a normal crystal emulsion in which dislocation lines have been introduced. As a result, it is possible to improve both sensitivity and reciprocity failure characteristics by performing metal doping. It has been found that normal crystals having dislocation lines have a remarkable effect as compared with particles having no dislocation lines. Further, heat fog was reduced by adding metal ions to silver halide fine particles in advance.

In addition, when the metal ion-containing fine particles are added, it is relatively easy to preferentially dissolve the fine particles in the twin bonding site to localize the metal in the twin crystal particles. In a normal crystal particle without a bonding site,
It is difficult to control the doping position of the metal in the grains. For this reason, the effect of improving the reciprocity failure property was smaller than that of twin grains. However, as a result of intensive studies, it is possible to adjust the doping position by adjusting the pBr and / or the pBr of the fine particles when they are dissolved. I made it.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide emulsion having high sensitivity and improved illuminance failure characteristics or improved heat fog, and a photographic material using the same.

[0011]

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

(1) 50% or more of the total projected area is (1)
00) Normal-crystal silver halide grains having a dislocation line with an area ratio of 50% or more, and a polyvalent of 10 ⁻⁸ mol or more and 10 ⁻⁴ mol or less per 1 mol of silver inside the normal-crystal silver halide grains. A photosensitive silver halide emulsion comprising at least one metal ion.

(2) 50% or more of the total projected area is (1)
00) An emulsion containing normal crystal silver halide grains having a dislocation line with an area ratio of 50% or more, wherein the normal crystal silver halide grains contain fine particles having a particle diameter of 0.1 μm or less containing polyvalent metal ions. 0.05 to 3.0 with respect to the silver content of the grain emulsion.
% Photosensitive silver halide emulsion characterized by being prepared by a solid solution method.

(3) 50% or more of the total projected area is (1)
00) Normal crystal silver halide grains having a dislocation line with an area ratio of 50% or more, and 10 ^-8 mol or more and 10 ^-4 mol per 1 mol of silver of the grain emulsion inside the normal crystal silver halide grains.
A photosensitive silver halide emulsion comprising at least one kind of polyvalent metal ion of at most 1 mol, and at least 60 mol% of the polyvalent metal ion is localized near the vertexes and / or ridges of the grains.

(4) 50% or more of the total projected area is (1)
00) A normal crystal silver halide grain having a dislocation line with an area ratio of 50% or more, wherein the normal crystal silver halide grain contains an emulsion containing fine particles having a particle diameter of 0.1 μm or less containing a polyvalent metal ion. Wherein the pBr is 2.3 to 3.8 during the dissolution ripening after the fine grain emulsion is added to the host grain emulsion.

(5) 50% or more of the total projected area is (1)
00) A normal crystal silver halide grain having a dislocation line with an area ratio of 50% or more, wherein the normal crystal silver halide grain contains an emulsion containing fine particles having a particle diameter of 0.1 μm or less containing a polyvalent metal ion. PB of the fine grain emulsion.
A photosensitive silver halide emulsion, wherein r is 2.0 or more and 4.0 or less.

(6) A high iodine localized region having a silver iodide content of 7 mol% or more is 0.1 to 50% or more of the total projected area.
Normal-crystal silver halide grains containing 5.0% by volume and having a (100) face ratio of 50% or more, and 10 ^-8 mol or more and 10 -10 mol or less per 1 mol of silver inside the normal-crystal silver halide grains.
A photosensitive silver halide emulsion containing at least one kind of polyvalent metal ion of ^-4 mol or less.

(7) 50% or more of the total projected area has a high iodine localization region having a silver iodide content of 7 mol% or more within 0.1 to 0.1%.
Normal crystal silver halide grains containing 5.0% by volume and having a (100) face ratio of 50% or more, wherein the normal crystal silver halide grains contain polyvalent metal ions and have a particle diameter of 0.1 μm or less. A photosensitive silver halide emulsion prepared by a method of forming a solid solution in grains.

(8) 50% or more of the total projected area has a high iodine-localized region having a silver iodide content of 7 mol% or more within 0.1 to 0.1%.
Normal-crystal silver halide grains containing 5.0% by volume and having a (100) face ratio of 50% or more, and 10 ^-8 mol or more and 10 -10 mol or less per 1 mol of silver inside the normal-crystal silver halide grains.
^-4 mol or less of a polyvalent metal ion, wherein at least 60 mol% of the polyvalent metal ion is localized near the apex and / or ridge line of the grain. .

(9) 50% or more of the total projected area has a high iodine localization region having a silver iodide content of 7 mol% or more of 0.1 to 0.1%.
Normal crystal silver halide grains containing 5.0% by volume and having a (100) face ratio of 50% or more, wherein the normal crystal silver halide grains contain fine particles having a particle diameter of 0.1 μm or less containing polyvalent metal ions. PB during dissolution ripening after adding the fine grain emulsion to host grains.
A photosensitive silver halide emulsion wherein r is 2.3 or more and 3.8 or less.

(10) 50% or more of the total projected area has a high iodine-localized region having a silver iodide content of 7 mol% or more within 0.1 to 0.1%.
Normal crystal silver halide grains containing 5.0% by volume and having a (100) face ratio of 50% or more, wherein the normal crystal silver halide grains contain fine particles having a particle diameter of 0.1 μm or less containing polyvalent metal ions. A light-sensitive silver halide emulsion prepared by a method of adding a silver halide emulsion, wherein the pBr of the fine grain emulsion is 2.0 or more and 4.0 or less.

(11) The method of any one of (1) to (10), wherein the polyvalent metal compound is a Group VIII metal compound.
The photosensitive silver halide emulsion as described in the above item.

(12) 50% or more of the total projected area is
(100) Normal-crystal silver halide grains having an area ratio of 50% or more, wherein a high silver iodide coating layer is temporarily formed on the surface of the silver halide grains during the growth of the silver halide emulsion. 12. The photosensitive silver halide photographic emulsion according to any one of 1 to 11.

(13) A silver halide photographic light-sensitive material, characterized in that at least one layer on a support contains the light-sensitive silver halide emulsion as described in any one of (1) to (12) above.

(14) A color reversal photographic light-sensitive material, characterized in that at least one layer on a support contains the light-sensitive silver halide emulsion as described in any one of (1) to (12) above.

Hereinafter, the present invention will be described in more detail. The dislocation lines of the silver halide grains of the present invention are described, for example, in J. Am. F. Ha
Milton, Photo. Sci. Eng. 11
(1967), p. 57; Shiozawa, J.M.
Soc. Photo. Sci. Japan 35 (197
2) It can be observed by the method described on page 213, that is, a method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for an electron microscope so as to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, the use of a high-pressure electron microscope (200 kV for a thickness of 0.25 μm) enables more clear observation. In the case of normal crystal silver halide grains, it is often difficult to observe the transmission of an electron beam due to the grain thickness. In this case, as shown in FIG. While paying careful attention not to apply pressure, 0.2 parallel to the (100) plane.
By cutting out a slice of 5 μm or less and observing the slice, the presence or absence of dislocation lines can be confirmed.

The intergranular variation coefficient of the number of dislocation lines of the normal crystal grains of the present invention is preferably 25% or less, more preferably 20% or less.

The number of dislocation lines per normal crystal grain of the present invention is preferably 20 or more, more preferably 30 or more. The number of dislocation lines per normal crystal grain referred to here means that a flake having a thickness of 0.2 ± 0.05 μm including one (100) surface per cubic particle is cut out as shown in FIG. It is defined as the number of dislocation lines when the slice is observed from the (100) direction. The number of particles for counting dislocation lines is 300 or more.

The standard deviation of the number of dislocation lines is σ and the average is α.
In this case, the interparticle variation coefficient K (%) is represented by the following equation. K (%) = [σ / α] × 100 The pAg at the time of dislocation line introduction is preferably less than 7.8 from the viewpoint of uniformity of the number of dislocation lines. In order to uniformly introduce dislocation lines, it is preferable that the crystal habit of the particles is uniform.
00) The coefficient of variation of the surface ratio is preferably 20% or less.

The start time of dislocation line introduction is 30 to 90% of the amount of silver consumed for grain growth before the introduction of dislocation lines.
Is preferable, and more preferably 40 to 70%.

The method of introducing dislocation lines according to the present invention is not particularly limited. A high silver iodide-containing layer is formed on the host grains at the position where the dislocation lines are introduced, and the layer is formed outside the layer relative to the layer. It is preferable to form a silver halide layer having a low silver iodide content, that is, a method of introducing dislocations using a gap in a silver halide lattice constant caused by a so-called steep halogen composition difference. As a method for forming a high silver iodide layer at a dislocation line introduction start position, a method of adding an aqueous solution of iodide ion such as an aqueous solution of potassium iodide and a solution of a water-soluble silver salt by double jet, a method of adding silver iodide fine particles A method using only an aqueous solution of iodide ion, a method using an iodide ion releasing agent, and the like. A method using silver iodide fine particles, a method using an iodide ion releasing agent is preferable, and fine silver iodide particles are added. The method is most preferred.

When dislocation lines are introduced, the average silver iodide content on the outer side including the dislocation line region is preferably at most 10 mol%, more preferably at most 5 mol%.

The outside including the dislocation line region is a region defined as follows. That is, as described above, when a slice having a thickness of 0.25 μm or less is cut out from a normal crystal grain, the silver halide grains of the present invention have dislocation lines normal to the surface from the grain center toward the surface. Although observed, it refers to the region on the particle surface side from the boundary line formed by connecting the starting point of the group of dislocation lines on the particle center side to the adjacent dislocation lines. Further, in the grains containing dislocation lines, a high iodine-containing phase having a halide composition different from that of the region clearly in contact with the starting point on the grain center side of the dislocation lines is observed in the transmission electron microscope image. Is associated with the dislocation line forming operation, and is defined as being included in the region “outside the dislocation line region” in the present invention. FIG. 2 shows a schematic diagram of a cubic particle. (A) shows the case where the dislocation line exists on the entire surface, and (b) shows the case where the dislocation line exists only on a part of the surface. A region covered by hatching indicates “inside the dislocation line region” in the present invention, and the other region indicates “outside including the dislocation line region”.

The silver halide emulsion of the present invention preferably has a silver chloride content of 5 mol% or less, and a silver iodide content of 0.5 mol% or more. More preferably, the silver iodide content is 1 to 5
Mol%.

The silver halide grains preferably have a particle diameter of 0.1 to 1.2 μm, more preferably 0.15 to 0.7 μm, in the length of one side of a cube having the same volume.
The size distribution of the silver halide grains is the same volume of cube 1
The variation coefficient of the side length is preferably 15% or less, but does not necessarily need to be a so-called monodisperse emulsion.

The intergranular distribution of the silver iodide content of the tabular grains of the present invention is obtained by dividing the coefficient of variation of the silver iodide content (the standard deviation of the silver iodide content intergranular distribution by the average silver iodide content). Is preferably 20% or less, more preferably 10% or less. The average silver iodide content of each silver halide grain can be measured by a method using an X-ray microanalyzer as described in JP-A-60-254032.

The silver iodide content on the surface of the silver halide grains of the present invention is preferably from 0 to 15 mol%, more preferably from 0.1 to 10 mol%. The silver iodide content on the grain surface as referred to in the present invention is described in JP-A-8-171157.
It is a numerical value measured by the XPS method described in the item.

The "coefficient of variation of (100) plane ratio between grains" of silver halide grains is determined by the following method.

The (100) plane ratio of each silver halide grain is determined by depositing a metal from the oblique direction of the grain (shadowing treatment), and then performing SEM (Scanning Electron).
Observation is performed by using an nMicroscope (scanning electron microscope) and image processing is performed on the observed image.

The present inventors have performed a shadowing treatment on the particles, and when the particles are observed from directly above by SEM using the shadow caused by the difference in the amount of adhering metal, the (100) plane and the non- (100) ) Succeeded in distinguishing faces. The shadowing process is described in “Electron Microscope Sample Techniques”, Seibundo Shinkosha, 1
23, (1970), a method which has been conventionally used for shading silver halide grains in replica observation of the grains.

The procedure for measuring the (100) plane ratio is specifically as follows. In order to remove silver halide grains from the silver halide emulsion used for the measurement, a method is generally employed in which gelatin, which is a dispersion medium, is decomposed with a protease under safelight, and the supernatant is removed by centrifugation and washed with distilled water. Used. When silver halide particles are present in a coating film containing gelatin as a main binder, the gelatin may be similarly decomposed by a protease and the particles may be taken out, and when a polymer other than gelatin is contained. In this case, the polymer may be dissolved and removed using an appropriate organic solvent. When a dye, a sensitizing dye, or the like is adsorbed on the particle surface, an alkaline aqueous solution,
These can be removed by using an alcohol or the like as appropriate to obtain a clean silver halide grain surface. The particles dispersed in water are applied to a conductive substrate, dried and used for measurement, but it is preferable to arrange the particles on the substrate without agglomeration, and a series of procedures using an optical microscope or SEM It is preferable to observe and confirm the sample obtained in the above. A dispersing aid may be used to prevent aggregation of the particles. Further, after decomposing with a protease, a dispersion diluted with distilled water may be applied on a conductive substrate. further,
In order to arrange the particles without aggregating on the substrate, a spin coater, a vacuum freeze dryer, or the like may be appropriately used. The conductive substrate is preferably smooth, and a mirror-polished low-resistance silicon single crystal wafer having a resistivity of 1.0 ohm · cm or less is preferably sufficiently washed and used. Further, a thin polyethylene terephthalate base obtained by thinly depositing carbon to impart conductivity may be used.

On the silver halide particles thus dispersed on the substrate, a metal was vapor-deposited from a direction of 45 ° with respect to the substrate. The metal to be deposited is generally Cr, Pt-Pd, or the like, but platinum carbon is preferred because of the granularity of the deposited film and the straightness in the deposition direction. If the metal deposition thickness is small, the contrast difference required for discriminating the (100) plane and the non- (100) plane of the particles cannot be obtained in SEM observation. On the other hand, when the thickness is large, the measurement error increases, so that about 20 nm is preferable. The SEM used for observation is to improve the measurement accuracy,
It is preferred to use as high a resolution device as possible. The accelerating voltage of the electron beam is pointing upward in later image processing (100)
Observation was performed at 1.8 kV, at which a contrast difference that allows easy identification of the surface, the outer shape of the particles, and the substrate was obtained. In the observation, the particles were observed from directly above without tilting the sample.

After the observation image is taken on a polaroid or negative film, the image may be taken into a computer for image processing by a scanner. However, in order to suppress image deterioration at the time of taking the image, the SEM and the computer for image processing are connected, and the image is taken online. Preferably, it is stored as a digital image.

The captured image is processed by image processing software.
Impulse noise of the image was removed by a median filter. Then, the (100) face facing upward, and
The outline of each particle was binarized using a threshold value at which an image could be extracted, a number was assigned to each particle, and the area of each was measured. The measured area of the (100) plane and the area within the contour of the particle were input to spreadsheet software in ASCII format, and the (100) plane ratio of each particle was calculated.

The standard deviation of the (100) plane ratio is given by σ (10
Assuming that the average value of the (0)% and (100) plane ratios is α (100)%, the interparticle variation coefficient K (%) is expressed by the following equation. K (%) = [σ (100) / α (100)] × 100 In particular, in the normal-crystal silver halide grains containing dislocation lines of the present invention, the coefficient of variation of the (100) plane occupancy should be reduced. Is preferably, and particularly preferably 15% or less,
10% or less is more preferable.

The (100) plane occupancy is 50% or more, but is more preferably 60 to 95% in terms of production stability.

The method for producing the halogenated particles of the present invention includes:
Any method known in the art can be appropriately combined. For example, JP-A-61-6643 and JP-A-61-146.
No. 305, No. 62-157024, No. 62-1855
No. 6, No. 63-92942, No. 63-151618
Nos. 63-163451 and 63-220238
And JP-A-63-31244 can be referred to. For example, a double jet method, a double jet method, a so-called controlled double jet method which maintains a constant pAg in a liquid phase in which silver halide is formed, which is a type of the double jet method, and a soluble silver halide having a different composition, respectively. A triple jet method, which is independently added, can also be used. A forward mixing method can be used, and a so-called reverse mixing method in which grains are formed in excess of silver ions can also be used. It is preferable to control pAg (the logarithm of the reciprocal of silver ion concentration) in the liquid phase in which silver halide grains are formed in accordance with the growth rate of silver halide grains, in order to obtain highly monodispersed grains. .
In determining the addition rate, refer to JP-A-54-48521.
And No. 58-49938.

Further, a silver halide solvent can be used if necessary. Silver halide solvents often used include ammonia, thioethers and thioureas. Regarding thioethers, US Pat. Nos. 3,271,157 and 3,790,387
No. 3,574,628 and the like. The mixing method is not particularly limited, and a neutral method using no ammonia, an ammonia method, an acidic method, or the like can be used. However, in order to reduce fog of silver halide grains, a pH (hydrogen ion concentration (The logarithmic value of the reciprocal of the above) is preferably 5.5 or less, more preferably 4.5 or less.

The silver halide grains of the present invention have a (100)
In order to reduce the variation coefficient of the intergranular distribution of the surface occupancy, iodide ions are preferably supplied to the mixed solution using silver iodide fine particles or using an iodide ion releasing agent. Examples of iodide ion releasing agents that can be used for the preparation of silver halide grains are shown below, but are not limited thereto.

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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In the silver halide grains of the present invention, the region having a silver iodide content of 7 mol% or more is 0.1 to 5.
It is preferably contained at 0%, more preferably 0.1 to 0.1%.
1.0%.

The region having a silver iodide content of 7 mol% or more of the present invention is preferably present at a depth of 60% or less in terms of silver amount on the outer side of the grains. This means the position at which the cells have been grown. It is preferably at a position of 60% to 90% in terms of the amount of silver on the outer side of the grains.
More preferably, it is 5% to 80%. Further, the silver iodide content is more preferably at least 10 mol%. The region having a silver iodide content of 7 mol% or more can be measured by the EPMA method with a sufficiently narrowed measurement beam diameter.

The method for forming the region having a silver iodide content of 7 mol% or more is not particularly limited. As in the case of dislocation line introduction, a high silver iodide-containing layer is formed on the host grain, and the layer is further formed outside the layer. A method of forming a silver halide layer having a low silver iodide content relative to the layer, that is, a method of introducing dislocations using a gap of a silver halide lattice constant caused by a so-called steep halogen composition difference is preferable. . As a method for forming a high silver iodide layer at a dislocation line introduction start position, a method of adding an aqueous solution of iodide ion such as an aqueous solution of potassium iodide and a solution of a water-soluble silver salt by double jet, a method of adding silver iodide fine particles A method of adding only an aqueous solution of iodine ion,
And the like, a method using silver iodide fine particles, a method using an iodide ion releasing agent are preferable, and a method using silver iodide fine particles is most preferable.

It is preferable to form a band-like high iodine profile inside the grains by making the high silver iodide-containing layer of the present invention more localized. The high iodine profile can be observed using a transmission electron microscope at a low temperature in the same manner as the dislocation line observation described above. The observed high iodine profile is shown in FIG. The high iodine profile is preferably present in 50% by number or more of all grains, more preferably 60% by number or more.

The method for forming a high iodine profile according to the present invention is not particularly limited. In addition to the above-described method for forming a region having a silver iodide content of 7 mol% or more, controlling the environment during the formation is more effective. It is preferable to localize the layer containing high silver iodide. For example, it is preferable to reduce the temperature during the formation, shorten the formation time, or increase the crystal growth rate immediately after the formation.

The silver halide grains of the present invention are produced in the presence of a dispersion medium. Here, "in the presence of a dispersion medium" means that the protective colloid is formed in a mixed solution in which the protective colloid grows particles by gelatin or another substance capable of constituting a hydrophilic colloid, and preferably the presence of colloidal protective gelatin. Do it below.

In the practice of the present invention, when gelatin is used as the above protective colloid, the gelatin may be either lime-treated or acid-treated. The details of the method for producing gelatin are described in Arthur Guice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

Examples of hydrophilic colloids other than gelatin that can be used as the protective colloid include gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
There are various kinds of synthetic hydrophilic polymer substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole. For gelatin,
It is preferable to use one having a jelly strength of 200 or more in the puggy method.

The silver halide grains of the present invention contain at least one or more polyvalent metal ions. Here, the terms are defined, but "doping" or "doping"
This means that a substance other than silver ions or halide ions is contained in silver halide grains. The term "dopant" refers to compounds that dope the silver halide grains.
The term "metal dopant" refers to a polyvalent metal compound that is doped into silver halide grains.

As the metal dopant, Mg, Al,
Ca, Sc, Ti, V, Cr, Mn, Fe, Co, C
u, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo,
Tc, Ru, Rh, Pd, Cd, Sn, Ba, Ce, E
u, W, Re, Os, Ir, Pt, Hg, Tl, Pb,
Metal compounds such as Bi and In are preferably used.

The metal compound to be doped is preferably selected from a single salt or a metal complex. When selecting from metal complexes, 6-coordinate, 5-coordinate, 4-coordinate and 2-coordinate complexes are preferred, and octahedral 6-coordinate and planar 4-coordinate complexes are more preferred.
Further, the complex may be a mononuclear complex or a polynuclear complex. The ligands constituting the complex include CN ⁻ , C
O, NO ₂ ^-, 1,10-phenanthroline, 2,2'-
Bipyridine, SO ₃ ^2-, ethylenediamine, NH _{3, ^{pyridine, H 2 O, NCS -,}} CO -, NO 3 -, SO 4 2-, OH
_{^{-, N 3 -, S 2-}} , F -, Cl -, Br -, I - and the like can be used. Particularly preferred metal dopants include K
₄ Fe (CN) ₆ , K ₃ Fe (CN) ₆ , K ₄ Ru (C
N) ₆ , K ₃ Ru (CN) ₆ , Pb (NO ₃ ) ₂ , K ₂ IrC
_{l 6, K 3 IrCl 6,} K 2 IrBr 6, InCl 3 and the like.

The concentration distribution of the metal dopant in the silver halide grains can be determined by dissolving the grains little by little from the surface to the inside and measuring the dopant content of each part. Specific examples include the method described below.

Prior to metal determination, the silver halide emulsion is pretreated as follows. First, 50 ml of a 0.2% actinase aqueous solution is added to about 30 ml of the emulsion, and the mixture is stirred at 40 ° C. for 30 minutes to perform gelatin decomposition. This operation is repeated five times. After centrifugation, 5 times with 50 ml of methanol, 1
The washing was repeated twice with 50 ml of N nitric acid and five times with ultrapure water,
Centrifugation is performed again to separate only silver halide.

The surface portion of the obtained silver halide grains is dissolved with an aqueous ammonia solution or with a pH-adjusted ammonia solution (the ammonia concentration and pH are changed according to the type and amount of silver halide to be dissolved). As a method for dissolving the extreme surface of silver bromide grains of silver halide, about 3% of the silver halide grains can be dissolved by using about 10% aqueous ammonia solution 20 ml per 2 g of silver halide grains.
At this time, the amount of silver halide dissolved was determined by centrifuging the aqueous ammonia solution after dissolving the silver halide and the silver halide, and determining the amount of silver present in the obtained supernatant by a high frequency induction plasma mass spectrometer. (ICP-MS), high frequency induction plasma emission spectrometry (ICP-AES), or atomic absorption spectrometry.

From the difference between the amount of metal contained in the silver halide after surface dissolution and the amount of metal of all silver halide not dissolved, the amount of metal per mol of silver halide existing at about 3% of the grain surface is determined. be able to. Metals can be quantified by dissolving them in an aqueous solution of ammonium thiosulfate, an aqueous solution of sodium thiosulfate, or an aqueous solution of potassium cyanide, and performing a matrix-matched ICP-MS method.
The CP-AES method or the atomic absorption method can be used. Among them, potassium cyanide as a solvent and IC as an analyzer
P-MS (FISON Elemental Anal)
ysis Co., Ltd.), a silver halide of about 40 m
g was dissolved in 5 ml of 0.2N potassium cyanide.
The internal standard element Cs solution was added to ppb, and the volume was adjusted to 100 ml with ultrapure water to obtain a measurement sample. Then, the metal in the measurement sample is quantified by ICP-MS using a calibration curve obtained by combining a matrix using metal-free silver halide. At this time, the exact amount of silver in the measurement sample was determined by diluting the measurement sample 100 times with ultrapure water by ICP-
It can be quantified by AES or atomic absorption. After such dissolution of the grain surface, the silver halide grains were washed with ultrapure water, and the dissolution of the grain surface was repeated in the same manner as described above, whereby the metal in the silver halide grain internal direction was removed. The quantity can be determined.

The metal dopa of the silver halide grains of the present invention
The preferred content of the silver salt is 1 to 1 mole of silver halide.
× 10^-6~ 1 × 10^-FourMole, more preferably 1 ×
10 ^-6~ 1 × 10^-FiveIs a mole.

The metal dopant is preferably localized near the apex and / or ridge. The vertex in the present invention refers to a point where three (100) planes of a cube intersect perpendicularly. In the case of a tetradecahedron, a (111) plane appears at the vertex, and this (111) plane is also defined as a vertex here. The vicinity of the vertex appears at the vertex or the vertex portion (1
11) Point within 20 nm below the surface. Further, the ridge line in the present invention refers to a line where two (100) planes of a cube intersect perpendicularly. Although the (110) plane may appear at the ridge, this (110) plane is also defined as a ridge. The vicinity of the ridge refers to an area within 20 nm below the surface of the (110) plane appearing on the ridge or the ridge. The measuring method is to cut out the slices having a size of 20 nm or less parallel to the (111) plane at the apex and / or the (110) plane at the ridge line, and measure the slices by the metal determination method described above. Of the metal localized at the apex and / or the ridge line can be determined.

In the silver halide grains of the present invention, the ratio of the amount of the metal dopant localized at the apex and / or the ridgeline to the amount of the metal dopant contained in the whole grains is 6%.
0% or more, preferably 70% or more, more preferably 80% or more.

The effect of the metal dopant can be effectively exhibited by adding the metal dopant to the base grains in a state of being doped in the silver halide fine grain emulsion in advance. At this time, the concentration of the metal dopant per mole of the silver halide fine particles was 1
× 10 ^-1 to 1 × 10 ^-7 mol is preferred, and 1 × 10 ^-3 to 1
× 10 ^-5 mol is more preferred.

As a method of previously doping the silver halide fine particles with the metal dopant, it is preferable to form the silver halide fine particles in a state where the metal dopant is dissolved in a halide solution.

The halogen composition of the silver halide fine grains may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. It is preferable that

The silver halide fine particles containing the metal dopant may be deposited on the base grains at any time between the formation of the base grains and before the start of chemical sensitization. The period before the start is particularly preferable. By adding the fine grain emulsion in a state where the salt concentration of the base emulsion is low, the silver halide fine grains are deposited together with the metal dopant in the portion where the activity of the base grains is highest.
That is, it can be efficiently deposited and localized on the vertices and / or ridges of the present invention. Aging p when depositing
Br is preferably from 2.3 to 3.8, more preferably from 2.8 to 3.4. The pBr of the silver halide fine particles containing a metal dopant is preferably adjusted in advance to 2.0 to 4.0, more preferably 2.5 to 3.5. In addition to controlling pBr at the time of deposition, as a means for localizing a metal dopant at a vertex and / or a ridge, a silver halide containing a metal dopant after adsorbing a compound (dye) having (100) face selectivity may be used. There is a method of adding and depositing fine particles.

As a method for confirming the efficient deposition on the apex and / or the ridge line, there is a method for cutting out the above-mentioned thin slices and quantifying the localized metal. When the silver halide grains have different halogen compositions, the deposited portion can be specified by measuring the halogen composition. For example, (10
0) A slice having a thickness of 20 nm or less parallel to the plane is cut out, and positions having different halogen compositions are specified by the EPMA method in which the measurement beam diameter is sufficiently narrowed.

The term “depositing” means that the silver halide fine particles are not aggregated and adsorbed on the base particles as they are, but are dissolved in the reaction system in which the silver halide fine particles and the base particles coexist and the silver halide fine particles are dissolved. Regenerating as silver halide on grains. That is, when a part of the emulsion obtained by the above method is taken out and observed with an electron microscope, no silver halide fine particles are observed, and no epitaxial projection is observed on the surface of the base particle. .

The silver halide fine particles to be added are preferably added in an amount of 1 × 10 ^{−7 to} 0.5 mol of silver per mol of base grains, preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol. More preferably, an amount is added.

Physical ripening conditions for depositing silver halide fine grains can be arbitrarily selected within a range of 30 to 70 ° C. for 10 to 60 minutes.

The silver halide grains may be those obtained by removing unnecessary soluble salts after grain growth, or may be those containing them. Also, Japanese Patent Application Laid-Open
As in the method described in 138538, desalting can be performed at any point during silver halide growth. When removing the salts, a research disclosure (Re
Search Disclosure (hereinafter abbreviated as RD) No. 17643 No. II. Specifically, in order to remove the soluble salt from the emulsion after the formation of the precipitate or after the physical ripening, a Nudel washing method may be used in which gelatin is gelled, and inorganic salts, anionic surfactants, anionic surfactants A precipitation method using a hydrophilic polymer (eg, polystyrene sulfonic acid) or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin) may be used. Further, salt removal using an ultrafiltration membrane as described in JP-A-8-228468 can also be performed.

The silver halide emulsion of the present invention may be subjected to reduction sensitization. Reduction sensitization is performed by adding a reducing agent to a silver halide emulsion or a mixed solution for grain growth. Alternatively, a silver halide emulsion or a mixed solution for grain growth is prepared under a low pAg of pAg7 or less, or at pH7.
It is carried out by ripening or growing particles under the above high pH conditions. These methods may be combined.

Further, as shown in JP-A-7-219093 and JP-A-7-225438, reduction sensitization may be performed before or after the chemical sensitization step.

The reduction sensitization may be performed in the presence of the following oxidizing agents. In particular, compounds [III] to
It is preferable to perform reduction sensitization in the presence of [V].

As a preferable reducing agent, titanium dioxide
Urea, ascorbic acid and its derivatives, stannous salts
I can do it. Other suitable reducing agents include borane compounds,
Hydrazine derivatives, formamidinesulfinic acid, sila
Compounds, amines and polyamines, sulfites, etc.
I can do it. The addition amount is 10 per mole of silver halide. ^-2
-10^-8Molar is preferred.

To carry out low pAg ripening, a silver salt can be added, but a water-soluble silver salt is preferred. Silver nitrate is preferred as the water-soluble silver salt. The pAg at the time of aging is suitably 7 or less, preferably 6 or less, and more preferably 1 to 1.
3 (where pAg = -log [Ag ⁺ ]).

High pH ripening is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As the alkaline compound, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used. In the method of adding ammoniacal silver nitrate to silver halide formation, an alkaline compound other than ammonia is preferably used because the effect of ammonia is reduced.

As a method of adding a silver salt or an alkaline compound for reduction sensitization, rush addition or addition over a certain period of time may be used. In this case, the addition may be performed at a constant flow rate, or may be performed by changing the flow rate like a function. Further, the required amount may be added several times. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed in a soluble halide solution and added together with the halide. Further, it may be added separately from the soluble silver salt and the soluble halide.

In the silver halide emulsion of the present invention, an oxidizing agent for silver may be added during the production process. The oxidizing agent for silver refers to a compound having an effect of acting on metallic silver to convert it into silver ions. In particular, a compound which converts silver atoms by-produced in the process of forming silver halide grains into silver ions is effective. Here, the generated silver ion may form a water-soluble silver salt such as silver halide, silver sulfide, or silver selenide, or may form a water-soluble silver salt such as silver nitrate. You may.

The oxidizing agent for silver is inorganic,
It may be an organic substance. As the inorganic oxidizing agent, ozone, hydrogen peroxide and its adduct (for example, NaBO _{2.
H 2 O 2 · 3H 2 0,2NaCO} 3 · 3H 2 O 2, Na 4 P 2 O
_{7 · 2H 2 O 2, 2Na} 2 SO 4 · H 2 O 2 · H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2 O 6, K 4 P
₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti
_{(O 2) C 2 O 4} ] · 3H 2 O, 4K 2 SO 4 · Ti (O 2)
_{OH · SO 4 · 2H 2 O} , Na 3 [VO (O 2) (C 2 O 4)
₂ · 6H ₂ O]), permanganate (e.g. KMn
O _4), an oxyacid salt such as chromate (e.g., K ₂ Cr ₂ O _7), a halogen element such as iodine and bromine, perhalogenate (e.g., potassium periodate), the high-valence metal Salts (eg, potassium hexacyanoferrate) and thiosulfonates. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and the like.
Compounds that release an active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B) are mentioned.

Preferred oxidizing agents are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates and quinones. Particularly preferred are the following formulas [III] to [V].
And most preferably a compound represented by the formula [III].

[0095] (III) R'SO in ₂ S-M (IV) R'SO ₂ S-R ¹⁰ [V] _{R'SO 2 S-L m -SSO 2} -R 11 Formula, R ', R ¹⁰ and R ¹¹ may be the same or different,
Represents an aliphatic group, an aromatic group or a heterocyclic group, M represents a cation, L represents a divalent linking group, and m is 0 or 1.

The oxidizing agent is added in an amount of 10 ^-7 to 1 mol per mol of silver.
It is about 10 ^-1 mol, preferably 10 ^-6 to 10 ^-2 mol, and more preferably 10 ^-5 to 10 ^-3 mol. The oxidizing agent is preferably added during grain formation, or before or during formation of a structure due to a difference in halogen composition. As the addition method,
The usual method of adding an additive to a photographic emulsion, for example,
A water-soluble compound is an aqueous solution having an appropriate concentration, and a compound that is insoluble or hardly soluble in water is selected from among organic solvents (alcohols, glycols, ketones, esters, amides, etc.) that are miscible with water. Alternatively, a method of dissolving in a material that does not adversely affect the photographic characteristics and adding it as a solution can be adopted.

The silver halide grains can be subjected to chemical sensitization by a conventional method. That is, a chalcogen sensitization method using a compound having a chalcogen such as S, Se, Te, or a noble metal sensitization method using gold or another noble metal compound can be used alone or in combination. The tabular grains of the present invention are preferably subjected to selenium sensitization. Preferred selenium sensitizers include those described in JP-A-9-265145.

The addition amount of the selenium compound depends on the compound used.
Products, types of silver halide photographic emulsions, conditions of chemical ripening, etc.
Therefore, it is not uniform, but usually 1 mole of silver halide
R10 ^-8-10^-3Moles of silver halide
5 × 10 per le^-8~ 1 × 10 ^-FourMole range
Is preferred. The method of addition depends on the properties of the selenium compound used.
Depending on the situation, water or methanol, ethanol, ethyl acetate, etc.
A method of dissolving in an organic solvent alone or in a mixed solvent, or
A method of premixing and adding with a gelatin solution,
Organic solvent soluble as disclosed in US Pat.
During chemical sensitization in the form of an emulsified dispersion of a mixed solution with a polymer
Is added.

The value of pAg (the logarithm of the reciprocal of silver ion concentration) at the time of selenium sensitization is preferably 6.0 to 10.0, more preferably 6.5 to 9.5. The pH is preferably between 4 and 9, more preferably between 4.0 and 6.5.
It is. The temperature is preferably between 40 and 90C, more preferably between 45 and 85C.

For selenium sensitization, a sulfur sensitizer, a gold sensitizer, or both may be used in combination.

As sulfur sensitizers, US Pat. No. 1,57
4,944, 2,410,689, 2,27
8,947, 2,728,668, 3,50
1,313, 3,656,955, West German Application Publication (OLS) No. 1,422,869, JP-A-55-45
016, 56-24937, JP-A-5-1651
Sulfur sensitizers described in No. 35 or the like can be used, and thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, and rhodanine Preferred examples include derivatives, dithiacarbamic acids, organic polysulfide compounds, and sulfur alone. The amount of the sulfur sensitizer to be added is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is from 1 × 10 ^-4 to 1 × 10 ^-9 mol per mol of silver halide. It is preferred that
More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

Examples of the gold sensitizer include chloroauric acid, gold thiosulfate, gold thiocyanate and the like, as well as thioureas, rhodanines, and gold complexes of other various compounds. The addition amount of the gold sensitizer is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but is from 1 × 10 ^-4 to 1 × 10 ^-9 mol per mol of silver halide. It is preferred that More preferably, 1 × 10 ⁻⁵ to 1 × 10
^-8 mol.

Other chemical sensitizers that can be used in combination are, for example, US Pat. Nos. 2,448,060 and 2,56.
No. 6,245, No. 2,566,263 and the like, and salts of noble metals such as platinum, palladium, and rhodium.

These sensitizations can also be carried out in the presence of a silver halide solvent such as thiocyanate (such as ammonium thiocyanate or potassium thiocyanate) or tetrasubstituted thiourea (such as tetramethylthiourea).

The silver halide grains of the present invention may be of the surface latent image type or of the internal latent image type. The particles may be shallow internal latent image type particles as described in JP-A-9-222684.

In the present invention, the silver halide emulsion is prepared by using Research Disclosure 308119 (hereinafter referred to as RD308).
119). The places to be described are shown below.

[Item] [Page of RD308119] Iodine structure 993 IA Section Manufacturing method 993 IA and 994 E Crystal habit (normal crystal) 993 IA Section Crystal habit (twin crystal) 993 IA Item Epitaxial 993 IA Item Halogen composition (uniform) 993 IB Item Halogen composition (not uniform) 999 IB Item Halogen conversion 994 IC Item Halogen substitution 994 IC Item Metal-containing 994 ID Item Monodispersion 995 I-F Solvent addition 995 I-F Latent image forming position (surface) 995 I-G Latent image forming position (internal) 995 I-G Applicable photosensitive material (negative) 995 I-H Applicable light-sensitive material (positive) Section 995 IH Use the emulsion as a mixture Section 995 IJ Desalting Section 995 II-A The silver halide emulsion of the present invention has physical ripening, chemical ripening and spectral sensitization. Can be used. Additives used in such a process are described in Research Disclosure No. 17643, no. 18716 and no.
308119 (hereinafter referred to as RD17643, RD1
8716 and RD308119).

The following shows the places to be described. (Items) (RD308119 page) (RD17643) (RD18716) Chemical sensitizer 996 III-A section 23 648 Spectral sensitizer 996 IV-AA, B, C, D, H, I, J sections 23 to 24 648 To 9 supersensitizer 996 IV-AE, Section J 23 to 24 648 to 9 Antifoggant 998 IV 24 to 25 649 Stabilizer 998 IV 24 to 25 649 Known photographic additives that can be used in the present invention are also described above. It is described in Risaari Disclosure. The relevant sections are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIIIC 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubrication Agent 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) Item 1011 XXB Various couplers can be used in the present invention. Are described in the above research disclosure. The relevant sections are shown below.

[Item] [Page of RD308119] [RD17643] Yellow-coupler 1001 VII-D VIIC-G Magenta coupler 1001 VII-D VIIC-G Cyan coupler 1001 VII-D VIIC-G Colored coupler 1002 VII-G VIIG DIR coupler 1001 VII-F VIIF BAR coupler 1002 VII-F Other useful residues Release coupler 1001 VII-F Alkali-soluble coupler 1001 VII-E Addition used in the present invention The agent can be added by a dispersion method described in RD308119XIV or the like.

In the present invention, the aforementioned RD17643
28 pages, RD18716 pages 647-8 and RD308
The support described in XIX 119 can be used.

The light-sensitive material of the present invention includes RD3081 described above.
An auxiliary layer such as a filter layer or an intermediate layer described in the item 19VII-K can be provided.

The light-sensitive material of the present invention is obtained by using the above-mentioned RD30811.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 9VII-K can be employed.

The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. .

The light-sensitive material of the present invention is the same as that of RD17643.
Pages 28-29, RD18716 647 and RD30
The development can be performed by the usual method described in XIX of No. 8119.

The emulsion of the present invention is described in JP-A-8-171157.
It is preferable to contain a compound of the general formula [I] or [II] or [III] described in the above item.

Examples of the light-sensitive material of the present invention include, for example, the type and serial number of a photographic light-sensitive material, the name of a manufacturer, the emulsion No. Various information on photographic materials such as, for example, shooting date and time,
Aperture, exposure time, lighting conditions, filters used, weather,
Various information when shooting the camera, such as the size of the shooting frame, the model of the camera, the use of anamorphic lenses, etc., such as the number of prints, selection of filters, customer's color preference, the size of the trimming frame, etc. A magnetic recording layer may be provided for inputting various kinds of necessary information, similar various kinds of information obtained at the time of printing, and other customer information.

In the present invention, the magnetic recording layer is preferably coated on the opposite side of the support from the photographic component layer. The undercoat layer, the antistatic layer (conductive layer), It is preferable that a magnetic recording layer and a slip layer are formed.

As the magnetic fine powder used for the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder and the like can be used. . Methods for producing these magnetic powders are known, and they can be produced according to known methods.

The optical density of the magnetic recording layer is preferably small in consideration of the influence on a photographic image, and is 1.5 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less. The optical density is measured by Konica Sakura Densitometer P
Using DA-65, using a filter that transmits blue light, light having a wavelength of 436 nm is vertically incident on the coating film,
According to a method of calculating light absorption by the coating film.

It is preferable that the amount of magnetization of the magnetic recording layer per 1 m ² of the photosensitive material is 3 × 10 ^-2 emu or more. The amount of magnetization was measured by using an external magnetic field of 1000 in a coating direction of a coating film having a fixed volume using a sample vibration magnetometer (VSM-3) manufactured by Toei Industry.
The magnetic flux density (residual magnetic flux density) when the external magnetic field is reduced to 0 after saturation with Oe once is measured, and this is converted into the volume of the transparent magnetic layer contained per 1 m ² of the photographic light-sensitive material. You can ask. If the amount of magnetization per unit area of the transparent magnetic layer is smaller than 3 × 10 ⁻² emu, input / output of magnetic recording is hindered.

The thickness of the magnetic recording layer is 0.01 to 20 μm
It is preferably from 0.05 to 15 μm, more preferably from 0.1 to 10 μm.

As the binder constituting the magnetic recording layer, vinyl resins, cellulose ester resins, urethane resins, polyester resins and the like are preferably used. It is also preferable to form a binder by aqueous coating using an aqueous emulsion resin without using an organic solvent. Further, it is necessary to adjust physical properties of these binders by curing with a curing agent, heat curing, electron beam curing, and the like. In particular, curing by adding a polyisocyanate-type curing agent is preferable.

It is necessary to add an abrasive to the magnetic recording layer in order to prevent clogging of the magnetic head, and it is preferable to add nonmagnetic metal oxide particles, particularly alumina fine particles.

Examples of the support for the photosensitive material include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cellulose triacetate film, cellulose diacetate film, polycarbonate film, polystyrene film, polyolefin film and the like. it can.
In particular, JP-A-1-244446 and JP-A-1-291248.
No. 1-298350 No. 2-89045 No. 2
-93641, 2-181749, 2-214
When a polyester having a high water content as shown in JP-A Nos. 852 and 2-291135 is used, even if the support is thinned, the curl recovery property after the development processing is excellent.

In the present invention, the supports preferably used are PET and PEN. When these are used, the thickness is preferably 50 to 100 μm, particularly preferably 60 to 90 μm.

The light-sensitive material of the present invention comprises ZnO, V ₂ O ₅ , T
iO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
It is preferable to have a conductive layer containing metal oxide particles such as O, BaO, and MoO ₃ , wherein the metal oxide particles contain oxygen vacancies and foreign atoms that form donors for the metal oxide used. Is generally preferred because of its high conductivity, and the latter is particularly preferred because it does not give fog to the silver halide emulsion.

As the binder for the conductive layer or the undercoat layer, the same binder as that for the magnetic recording layer can be used.

It is preferable to coat a higher fatty acid ester, a higher fatty acid amide, a polyorganosiloxane, a liquid paraffin, a wax or the like as a sliding layer on the magnetic recording layer.

When the light-sensitive material of the present invention is used as a color light-sensitive material for roll-shaped photographing, not only can the size of the camera and the patrone be reduced, but also resources can be saved and the storage space for the developed negative film can be saved. , The film width is about 20 to 35 mm, preferably 20 to 35 mm.
３０30 mm. Shooting screen area is also 300-700mm
If it is in the range of about ² and preferably in the range of 400 to 600 mm ^2, the small format can be realized without deteriorating the image quality of the final photographic print, and the size of the patrone and the size of the camera can be reduced more than before. In addition, the aspect ratio of the shooting screen is not limited, and is not limited to the conventional 12 aspect ratio.
6 size 1: 1, half size 1: 1.4,135
It can be used for various types such as (standard) size 1: 1.5, high-vision type 1: 1.8, panorama type 1: 3.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that the light-sensitive material is housed in a cartridge. The most common cartridge is the current 135 format patrone. In addition, JP-A-58-67329, JP-A-58-195236, JP-A-58-181535, JP-A-58-182634,
U.S. Pat. No. 4,221,479, JP-A-1-23104
No. 5, 2-170156, 2-199451,
2-124564, 2-201441, 2-
No. 205843, No. 2-210346, No. 2-211
No. 443, No. 2-214853, No. 2-264248
Nos. 3-37645 and 3-37646; U.S. Pat. Nos. 4,846,418 and 4,848,693;
The cartridges proposed in JP-A-4,832,275 and the like can also be used. Further, the present invention can be applied to "Small photographic roll film cartridge and film camera" in JP-A-5-210201.

The silver halide photographic emulsion of the present invention is particularly effective in the development processing for reversal films.

[0133]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 << Preparation of Seed Emulsion N-1 >> 250 ml of a 4N silver nitrate aqueous solution and KBr were added to 500 ml of a 2.0% aqueous gelatin solution at a temperature of 40 ° C. in accordance with the method described in JP-A-50-45437.
-KI (KBr: KI molar ratio = 98: 2) aqueous solution 250
ml of pAg by the controlled double jet method.
Was added over a period of 35 minutes while controlling the pH at 9.0 and the pH at 2.0. The pH of the aqueous gelatin solution containing the obtained silver halide particles was adjusted to 5.5 with an aqueous calcium carbonate solution, and a 5% aqueous solution 36 of Demol N manufactured by Kao Atlas was used as a precipitant.
After adding 4 ml and 244 ml of a 20% aqueous solution of magnesium sulfate as a polyvalent ion to cause coagulation, sedimentation by standing and decanting the supernatant, 1400 ml of distilled water was added and dispersed again. 3% 20% aqueous solution of magnesium sulfate
6.4 ml was added and the mixture was coagulated again. The sedimented supernatant was decanted, the total amount was made 425 ml with an aqueous solution containing 28 g of ossein gelatin, and the mixture was dispersed at 40 ° C. for 40 minutes to obtain seed emulsion N-1. As a result of observation with an electron microscope, this seed emulsion was a monodisperse emulsion having an average particle size of 0.093 μm.

<< Preparation of Silver Iodide Fine Particle Emulsion N-2 >> 0.0
To 5000 ml of a 6.0 mass% gelatin solution containing 6 mol of potassium iodide, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide
Was added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the fine particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg.

As a result of observation with an electron microscope, the average particle size of the AgI fine particles was about 0.05 μm. << Preparation of Emulsion Em-1 >> Emulsion E-1 was prepared using the following solution.
m-1 was prepared. (Solution Gr-1) 161.1 g of ossein gelatin 10% by mass methanol solution of surfactant (EO-1) 3.0 ml Seed emulsion N-1 97.7 ml Finished to 4.2 L with distilled water EO-1: HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) (B-1) 3524.9 g of silver nitrate 5.928 L with distilled water (B-2) Potassium bromide 2798.9 g Potassium iodide 162.7 g Finish to 7.0 L with distilled water (B-3) Potassium bromide 2915.5 g Finish to 7.0 L with distilled water (B-4) 37) g of silver iodide fine grain emulsion N-2 376.1 g (B-5) 25% NaCl solution containing 1.5 × 10 ^-6 mol of K ₂ IrCl ₆ per mol of silver of solution B-1 Amount described in Table 1 70 Solution Gr- stirred at ℃ In one, solution B-
1 and B-2 by controlled double jet method
While maintaining the pAg at 8.1 with a 1.75 N KBr solution and the pH at 4.0 with an aqueous acetic acid solution, the mixture was supplied at an addition rate at which no new small particles were generated in the mixed solution. 2. Solution B-1
When 869 L was added, the addition of the solution B-1 and the solution B-2 was interrupted, and the mixture was stirred for 1 minute, and then the solution B-4 was added at a constant rate of 2 minutes. Then, after stirring for 2 minutes, addition of the solutions B-1 and B-3 was started. Until the addition of the solution B-1 is completed, the pAg is maintained at 7.7 with a 1.75 N KBr solution and the pH is maintained at 4.0 with an aqueous acetic acid solution at an addition rate at which no new small particles are generated in the mixed solution. Supplied. During the addition of the solutions B-1 and B-3, 90
At the time the% was added, solution B-5 was added. Solution B-1
After the addition was completed, a 3.5N KBr solution was added to adjust the pAg to 9.1, followed by stirring for 2 minutes.
According to the method described in -72658, desalination treatment is performed,
Thereafter, gelatin was added and dispersed, and the pH was adjusted to 40 at 40 ° C.
80, pAg was adjusted to 8.06. The emulsion thus obtained is designated as Em-1.

From the electron micrograph of the obtained silver halide grains, Em-1 was found to have an average cubic side length of 0.42 μm,
The particles were slightly tetrahedral particles having a coefficient of variation of 18% for one side length of the cube.

<< Preparation of Emulsion Em-2 >> In the preparation method of Emulsion Em-1, the point that pAg in grain growth until the addition of Solution B-4 was changed to 7.3, and that Solution B-5 was added Emulsion Em-2 was prepared in the same manner except that no emulsion was present. Emulsion Em-2 has an average cubic side length of 0.42 μm.
m, cubic particles having a cubic side length of 13% and a coefficient of variation of 13%.

<< Preparation of Emulsion Em-3 >> In the method of preparing Emulsion Em-1, the solution B-1 was changed to B-6.
Emulsion Em-3 was prepared in the same manner except that the pAg in the grain growth until the addition of the solution B-4 was changed to 7.3, and that the solution B-4 was not added. Emulsion Em-
Sample No. 3 was a cubic particle having a cubic side length average value of 0.42 μm and a cubic side length variation coefficient of 15%. (B-6) Silver nitrate 3560.5 g Finish up to 5.988 L with distilled water.

<< Preparation of Emulsion Em-4 >> In the preparation method of Emulsion Em-1, pAg in the grain growth until the addition of Solution B-4 was changed to 7.3. Emulsion Em-4 was prepared in the same manner except that the composition was changed to 7. Emulsion Em-4 has a cubic average length of one side of 0.42 μm.
m, cubic particles having a cubic side length of 14%. (B-7) 25% NaCl solution containing 1.0 × 10 ^-7 mol of K ₂ IrCl ₆ per mol of silver of the solution B-1 Table 1 Amount described in Table 1 << Preparation of emulsion Em-5 >> In the preparation method, pA in particle growth until solution B-4 was added
Emulsion Em-5 except that g was changed to 7.3.
Was prepared. Emulsion Em-5 had a cubic average length of one side of 0.4.
The particles were cubic particles having a size of 2 μm and a coefficient of variation of one side of a cube of 13%.

<< Preparation of Emulsion Em-6 >> Emulsion Em-6 was prepared in the same manner as in the method of preparing Emulsion Em-5, except that Solution B-5 was changed to B-8. Emulsion Em-6 was cubic shaped grains having a cubic side length average value of 0.42 μm and a cubic side length variation coefficient of 16%. (B-8) K ₄ Ru (CN) ₆ was added in an amount of 1.5 per mole of silver in the solution B-1.
25% NaCl solution containing × 10 ^-6 mol << Preparation of emulsion Em-7 >> Emulsion Em-7 was prepared in the same manner as in the preparation method of emulsion Em-5 except that solution B-5 was changed to B-9. did. Emulsion Em-7 was cubic shaped grains having a cubic side length average value of 0.42 μm and a cubic side length variation coefficient of 15%. (B-9) A 25% NaCl solution containing 1.5 × 10 ^-6 mol of K ₄ Fe (CN) ₆ per mol of silver of the solution B-1 Emulsion Em according to the method described in this specification When the number ratio of dislocation lines of silver halide grains of Nos. -1 to 7 and the number of grains having a high iodine profile were measured, 60% or more of the grains other than Em-3 showed dislocation lines and high iodine content. Had a degree contour. When the silver iodide content of the high iodine contour portion was measured, each of the layers was a high silver iodide-containing layer containing 7 mol% or more of iodine, and the volume thereof was 0.5 to 1.
It was 0%. Neither the dislocation line nor the high iodine profile was observed in Em-3. When the (100) plane ratio was measured, the (100) plane ratio of Em-1 was 45%, and the other particles were all 60% or more.

Next, the following sensitizing dyes S-1 and S-2, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and triphenylphosphine selenide were added to the emulsions Em-1 to Em-7. The emulsion was subjected to chemical sensitization so as to optimize the fog-sensitivity relationship, and the following stabilizer ST-1 and antifoggants AF-1 and AF-2 were added to each emulsion in an amount of 1 g per mol of silver halide. , 3mg, 20mg
added. A dispersion of the following coupler C-1 was added to each of the obtained emulsions, and a general photographic additive such as a spreading agent and a hardening agent was further added to prepare a coating solution. Sample 1 by applying and drying on a support by a conventional method
01 to 107 were produced. ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene AF-1: 1-phenyl-5-mercaptotetrazole AF-2: 1- (4-carboxy) phenyl-5-mercaptotetrazole

[0143]

Embedded image

These samples were passed through a Toshiba glass filter O-56 using a light source at 5400 ° K.
Wedge exposure was performed at exposure times of / 100 seconds and 8 seconds, and development processing was performed according to the following processing steps, and sensitivity and high illuminance failure characteristics were evaluated. The sensitivity is obtained from the reciprocal of the exposure amount that gives a density at which the color density becomes 1.0 in 1/100 second exposure, and is a relative value when the sensitivity of the sample 102 is 1. The high illuminance failure property ΔS is the reciprocal of the exposure amount that gives a density of 1.0 at 1/100 second exposure and the exposure amount that gives a density of 1.0 at 8 second exposure. It is the ratio to the reciprocal. It is shown that ΔS is closer to 1 so that high illuminance failure is smaller and preferable.

<< Development Step >> Processing Step Processing Time Processing Temperature First Development 4 minutes 38 ° C. Rinse 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color Development 6 minutes 38 ° C. Adjustment 2 minutes 38 ° C. Bleaching 6 minutes 38 C. Fixing 4 minutes 38.degree. C. Washing with water 4 minutes 38.degree. C. Stabilizing 1 minute Room temperature Drying The treatment liquid composition used in the above treatment step is as follows. First developer Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added to make up to 1000 ml. (PH 9.60) Reversal solution Nitrilotrimethylenephosphonic acid hexasodium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to make up to 1000 ml. (PH 5.75) Color developing solution Sodium tetrapolyphosphate 3 g Sodium sulfite 7 g Sodium tertiary phosphate (dihydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1 g Water was added to make up to 1000 ml. (PH 11.70) Conditioner Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water was added to complete 1000 ml. (PH 6.15) Bleaching solution Sodium ethylenediaminetetraacetate (dihydrate) 2 g Iron (III) ammonium ethylenediaminetetraacetate (dihydrate) 120 g Ammonium bromide 100 g Water was added to make up to 1000 ml. (PH 5.56) Fixing solution 80 g ammonium thiosulfate 5 g sodium sulfite 5 g sodium bisulfite 5 g Water was added to make up to 1000 ml. (PH 6.60) Stabilizing solution Formalin (37% by mass) 5 ml KONIDAX (manufactured by Konica Corporation) 5 ml Water was added to make up to 1000 ml. (PH 7.00) The results are shown in Table 1.

[0146]

[Table 1]

As shown in Table 1, the emulsion of the present invention has improved illuminance failure without significant desensitization.

Example 2 << Preparation of Iridium-Containing Silver Bromide Fine Particle Emulsion N-3 >>
5000 ml of a 6.0% by weight gelatin solution containing 06 mol of potassium bromide, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate, 7.06 mol of potassium bromide and 4.4 × 10 ^-3 mol of K Aqueous solution 200 containing ₂ IrCl ₆
0 ml was added over 10 minutes. P during fine particle formation
H was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C.
After the formation of the fine particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg and the finished pBr was 1.8. As a result of electron microscope observation,
The average particle size of the fine particles was about 0.05 μm.

<< Preparation of Emulsion Em-8 >> In the method of preparing Emulsion Em-2, when desalting was performed and gelatin was added and dispersed, solution B-10 was added until the fine particles were dissolved. Emulsion Em-8 was prepared in the same manner except that ripening was performed. The pBr was kept at 2.1 during the aging of the microparticles. Emulsion Em-8 has a cubic average length of one side of 0.42 μm.
m, cubic particles having a cubic side length of 14%. (B-10) 89.5 g of iridium-containing silver bromide fine grain emulsion N-3.

<< Preparation of Emulsion Em-9 >> An emulsion Em-9 was prepared in the same manner as in the method of preparing the emulsion Em-8, except that the solution B-10 was changed to B-11. Emulsion Em-9
Were cubic shaped particles having a cubic side length average of 0.42 μm and a cubic side length variation coefficient of 13%. (B-11) 596.9 g of an iridium-containing silver bromide fine grain emulsion N-3.

<< Preparation of Emulsion Em-10 >> In the method of preparing Emulsion Em-9, the solution B-
1. Emulsion Em-10 was prepared in the same manner except that the addition time of B-3 was doubled. Emulsion Em-10 has an average cubic side length of 0.42 μm, and a coefficient of variation of cubic side length of 17%.
Of cubic particles.

According to the method described in this specification, the emulsion Em-
When the dislocation lines of silver halide grains of 5, 8, 9, and 10 and the number ratio of grains having a high iodine profile were measured, Em was measured.
In all of the grains other than -10, 60% or more of the grains had a dislocation line and a high iodine profile. When the silver iodide content of the high iodine contour portion was measured, all were 7 mol%.
It was a high silver iodide-containing layer containing the above-mentioned iodine, and its volume was 0.5 to 1.0% of the whole grains. Em-10 had no dislocation line, but had 62% by number of grains having a high iodine profile. When the (100) plane ratio was measured, all the particles were 60% or more.

Next, the above-mentioned sensitizing dyes S-1, S-2, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and triphenylphosphine selenide were added to the emulsions Em-1 to Em-7. The emulsion was subjected to chemical sensitization so as to optimize the fog-sensitivity relationship, and the above-mentioned stabilizer ST-1 and antifoggants AF-1 and AF-2 were added to each emulsion in an amount of 1 g per mol of silver halide. , 3mg, 20mg
added. To each of the obtained emulsions, a dispersion of the above-mentioned coupler C-1 was added, and a general photographic additive such as a spreading agent and a hardener was further added to prepare a coating solution. Sample 2 after coating and drying on a support by a conventional method
01 to 204 were produced.

These samples were evaluated for sensitivity and high illuminance failure characteristics in the same manner as in Example 1. In addition, 23 ° C and humidity 5
The sample was sealed at 5% and 55%
The composition was forcibly deteriorated at 3 ° C. for 3 days to evaluate heat resistance fog. The heat resistance fog characteristic ΔD is a rise value of the fog density due to forced deterioration, and the closer to zero, the better and preferable the heat resistance storage stability. Table 2 shows the results.

[0155]

[Table 2]

As shown in Table 2, the emulsion of the present invention has improved illuminance failure without significant desensitization. When doping is carried out by adding metal ion-containing fine particles, the effect becomes even more remarkable, and heat fog is significantly reduced.

Example 3 << Preparation of Emulsion Em-11 >> In the method of preparing Emulsion Em-9, the sensitizing dye S described below was added before adding the solution B-11.
Emulsion Em-1 in the same manner as above except that -1 and S-2 were added.
1 was prepared. Emulsion Em-11 was cubic shaped grains having an average cubic side length of 0.42 μm and a coefficient of variation of cubic side length of 15%.

According to the method described in this specification, the emulsion Em-
When the number ratios of the dislocation lines and the high iodine contours of the silver halide grains 9 and 11 were measured, 60% or more of the grains had a dislocation line and a high iodine contour. When the silver iodide content of the high iodine contour portion was measured, each was a high silver iodide-containing layer containing 7 mol% or more of iodine, and the volume thereof was 0.5 to 1.0% of the whole grain.
Met. Table 3 shows the results of quantifying the ratio of metal ions localized within 20 nm below the surface of the vertices and ridges of the particles by the method described in this specification.

Then, the above-mentioned sensitizing dyes S-1, S-2, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and triphenylphosphine selenide were added to the emulsions Em-9 and 11, and the emulsion was emulsified in a conventional manner. The emulsion was chemically sensitized so that the fog-sensitivity relationship was optimized, and the above-mentioned stabilizer ST-1 and antifoggants AF-1 and AF-2 were added to each emulsion.
1 g, 3 mg, 20 m
g was added. To each of the obtained emulsions, a dispersion of the above-mentioned coupler C-1 was added, and a general photographic additive such as a spreading agent and a hardener was further added to prepare a coating solution. Samples 301 and 302 were prepared by coating and drying on a support by a conventional method.

The samples were evaluated for sensitivity and high illuminance failure characteristics in the same manner as in Example 1. Table 3 shows the results.

[0161]

[Table 3]

As shown in Table 3, the emulsion of the present invention has improved illuminance failure without desensitization. In addition, metal ions are placed below the surface of the (111) and (110) planes.
The effect becomes even more pronounced when localized within nm.

Example 4 << Preparation of Iridium-Containing Silver Bromide Fine Grain Emulsion N-4 >>
5000 ml of a 6.0% by weight gelatin solution containing 06 mol of potassium bromide, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate, 6.70 mol of potassium bromide and 4.4 × 10 ⁻³ mol of K Aqueous solution 200 containing ₂ IrCl ₆
0 ml was added over 10 minutes. P during fine particle formation
H was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C.
After the formation of the fine particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg and the finished pBr was 2.7. As a result of electron microscope observation,
The average particle size of the fine particles was about 0.05 μm.

<< Iridium-Containing Silver Bromide Fine Particle Emulsion N-5
Preparation> 5000 ml of a 6.0 mass% gelatin solution containing 0.06 mol of potassium bromide, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate, 6.00 mol of potassium bromide and 4.4 × 10 5 2000 ml of an aqueous solution containing ^-3 mol of K ₂ IrCl ₆ was added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the fine particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. Finish is 12.53k
g, the finished pBr was 4.2. As a result of observation with an electron microscope, the average particle size of the fine particles was about 0.05 μm.

<< Preparation of Emulsion Em-12 >> Emulsion Em-12 was prepared in the same manner as in the method of preparing Emulsion Em-9, except that Solution B-11 was changed to B-12. The pBr was kept at 2.6 during the aging of the microparticles. Emulsion Em-1
Sample No. 2 was a cubic particle having an average cubic side length of 0.42 μm and a cubic side length variation coefficient of 15%. (B-12) Iridium-containing silver bromide fine grain emulsion N-4 596.9 g Adjusted to pBr2.1 with an aqueous potassium bromide solution.

<< Preparation of Emulsion Em-13 >> Emulsion Em-13 was prepared in the same manner as in the method of preparing Emulsion Em-9, except that Solution B-11 was changed to B-13. The pBr was kept at 3.0 during the aging of the microparticles. Emulsion Em-1
Sample No. 3 was a cubic particle having a cubic side length average value of 0.42 μm and a cubic side length variation coefficient of 14%. (B-13) 596.9 g of an iridium-containing silver bromide fine grain emulsion N-4.

<< Preparation of Emulsion Em-14 >> Emulsion Em-13
Except that B-14 was used instead of solution B-2 added before addition of solution B-4, and that solution B-2 was used instead of solution B-3 added after addition of solution B-4. Prepared emulsion Em-14 in the same manner. Emulsion Em
-14 was cubic particles having a cubic side length average value of 0.42 μm and a cubic side length variation coefficient of 14%. (B-14) Potassium bromide 2857.2 g Potassium iodide 81.3 g Finish up to 7.0 L with distilled water.

<< Preparation of Emulsion Em-15 >> Emulsion Em-15 was prepared in the same manner as in the method of preparing Emulsion Em-9, except that Solution B-11 was changed to B-15. Solution B-
After the addition of 15, the pBr was adjusted with an aqueous potassium bromide solution, and the pBr was kept at 3.0 during the aging of the fine particles. Emulsion E
m-15 is the average length of one side of the cube 0.42 μm,
The particles were cubic particles having a side length variation coefficient of 15%. (B-15) Iridium-containing silver bromide fine grain emulsion N-5 596.9 g.

<< Preparation of Emulsion Em-16 >> An emulsion Em-16 was prepared in the same manner as in the method of preparing the emulsion Em-9, except that the solution B-11 was changed to B-15. The pBr was kept at 4.0 during the aging of the microparticles. Emulsion Em-1
No. 6 was cubic particles having a cubic side length average value of 0.42 μm and a cubic side length variation coefficient of 16%.

According to the method described in this specification, the emulsion Em-
When the number ratios of dislocation lines and high iodine contours of silver halide grains of 9, 12 to 16 were measured, 60% or more of the grains had dislocation lines and high iodide contours. Was. When the silver iodide content of the high iodine contour portion was measured, each of the layers was a high silver iodide-containing layer containing 7 mol% or more of iodine, and the volume thereof was 0.5 to 1.
It was 0%. Table 4 shows the results of quantifying the ratio of metal ions localized within 20 nm below the surface of the vertices and ridges of the particles by the method described in this specification.

Next, the above-mentioned sensitizing dyes S-1, S-2, potassium thiocyanate, potassium chloroaurate, sodium thiosulfate and triphenylphosphine selenide were added to the emulsions Em-9 and 12 to 16, respectively. According to a conventional method, chemical sensitization was performed so that the fog-sensitivity relationship was optimized, and the above-mentioned stabilizer ST-1 and antifoggant AF-1 were added to each emulsion.
AF-2 was used in an amount of 1 g, 3 m per mol of silver halide.
g and 20 mg were added. To each of the obtained emulsions, a dispersion of the above-mentioned coupler C-1 was added, and a general photographic additive such as a spreading agent and a hardener was further added to prepare a coating solution. Samples 401 to 406 were prepared by coating and drying on a support in a conventional manner.

The samples were evaluated for sensitivity and high illuminance failure characteristics in the same manner as in Example 1. In addition, 23 ° C and humidity 5
The sample was sealed at 5% and 55%
The composition was forcibly deteriorated at 3 ° C. for 3 days to evaluate heat resistance fog. The heat resistance fog characteristic ΔD is a rise value of the fog density due to forced deterioration, and the closer to zero, the better and preferable the heat resistance storage stability. Table 4 shows the results.

[0173]

[Table 4]

As shown in Table 4, the emulsion of the present invention has improved illuminance failure without significant desensitization.
Further, when the pBr of the metal ion-containing fine particles or the pBr at the time of aging and depositing the metal ion-containing fine particles is adjusted,
Metal ions are localized in the vicinity of the (111) plane and the (110) plane, and the effect becomes more remarkable, and heat fog is also significantly reduced.

[0175]

According to the present invention, a silver halide emulsion having high sensitivity and improved illuminance failure characteristics or improved heat fogging and a photographic material using the same can be provided.

The silver halide photographic emulsion of the present invention and the photographic material using the same have high sensitivity, improved illuminance failure characteristics, and reduced heat fog.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing the direction in which a normal crystal silver halide grain of the present invention is cut into thin slices for observing the number of dislocation lines in the electron microscope.

FIG. 2 is a schematic diagram showing a dislocation line image when the cubic silver halide grains of the present invention are observed with an electron microscope.

FIG. 3 is an example showing a high iodine profile in the silver halide emulsion of the present invention observed using a transmission electron microscope.

[Explanation of symbols]

 1 Dislocation line image 2 Boundary line connecting the origins of dislocation lines on the particle center side

Claims (14)

[Claims] (1) At least 50% of the total projected area is (100)
Normal crystal silver halide grains having a dislocation line with an area ratio of 50% or more, and a silver content of 1 in the normal crystal silver halide grains.
A photosensitive silver halide emulsion containing at least one kind of polyvalent metal ion in an amount of 10 ^-8 mol or more and 10 ^-4 mol or less per mol. 2. At least 50% of the total projected area is (100)
A host grain emulsion comprising normal crystal silver halide grains having a dislocation line with an area ratio of 50% or more, wherein the normal crystal silver halide grains contain fine particles having a particle diameter of 0.1 μm or less containing polyvalent metal ions. A photosensitive silver halide emulsion prepared by a method of dissolving 0.05 to 3.0% with respect to the amount of silver of the photosensitive silver halide. (3) at least 50% of the total projected area is (100)
Normal crystal silver halide grains having a dislocation line with an area ratio of 50% or more, and 10 ^-8 mol or more and 10 ^-4 mol of 1 mol of silver in the grain emulsion inside the normal crystal silver halide grains.
A photosensitive silver halide emulsion containing at least one or more of the following polyvalent metal ions, wherein at least 60 mol% of the polyvalent metal ions are localized near the vertices and / or ridges of grains. 4. At least 50% of the total projected area is (100)
A method of adding an emulsion containing normal crystal silver halide grains having a dislocation line with an area ratio of 50% or more, wherein the normal crystal silver halide grains contain fine particles having a particle diameter of 0.1 μm or less containing polyvalent metal ions. Wherein the pBr is 2.3 to 3.8 during dissolution ripening after the fine grain emulsion is added to the host grain emulsion. 5. At least 50% of the total projected area is (100)
A method of adding an emulsion containing normal crystal silver halide grains having a dislocation line with an area ratio of 50% or more, wherein the normal crystal silver halide grains contain fine particles having a particle diameter of 0.1 μm or less containing polyvalent metal ions. Wherein the fine grain emulsion has a pBr of 2.0 or more and 4.0 or less. 6. A (100) plane ratio of 50% or more, wherein 50% or more of the total projected area contains 0.1 to 5.0% by volume of a high iodine localized region having a silver iodide content of 7 mol% or more. Normal-crystal silver halide grains, and 10 ^-8 mol or more and 10 ^-4 mol of 1 mol of silver in the normal-crystal silver halide grains.
A photosensitive silver halide emulsion containing at least one or more of the following polyvalent metal ions. 7. A 50% or more (100) plane ratio of at least 50% of the total projected area contains 0.1 to 5.0% by volume of a high iodine localized region having a silver iodide content of 7 mol% or more. A photosensitive silver halide grain, wherein the normal crystalline silver halide grain is produced by a method in which fine particles having a particle diameter of 0.1 μm or less containing polyvalent metal ions are dissolved in host particles. Silver halide emulsion. 8. A (100) plane ratio of 50% or more, wherein 50% or more of the total projected area contains 0.1 to 5.0% by volume of a high iodine localized region having a silver iodide content of 7 mol% or more. Normal-crystal silver halide grains, and 10 ^-8 mol or more and 10 ^-4 mol of 1 mol of silver in the normal-crystal silver halide grains.
A photosensitive silver halide emulsion containing at least one or more of the following polyvalent metal ions, wherein at least 60 mol% of the polyvalent metal ions are localized near the vertices and / or ridges of grains. 9. At least 50% of the total projected area contains 0.1 to 5.0% by volume of a high iodine-localized region having a silver iodide content of 7 mol% or more, and a (100) plane ratio of 50% or more. Normal-crystal silver halide grains, wherein the normal-crystal silver halide grains are prepared by adding an emulsion containing fine particles having a particle diameter of 0.1 μm or less containing polyvalent metal ions, and the fine-grain emulsion is used as host grains. PBr during dissolution ripening after addition to
A light-sensitive silver halide emulsion having a ratio of 3 or more and 3.8 or less. 10. A high iodine-localized region having a silver iodide content of 7 mol% or more accounts for 0.1 to 5.0% of the total projected area.
An emulsion containing normal-crystal silver halide grains having a (100) face ratio of 50% or more containing at least 50% by volume, wherein the normal-crystal silver halide grains contain fine particles having a particle diameter of 0.1 μm or less containing polyvalent metal ions. A light-sensitive silver halide emulsion prepared by the method of adding, wherein the fine grain emulsion has a pBr of 2.0 or more and 4.0 or less. 11. The photosensitive silver halide emulsion according to claim 1, wherein the polyvalent metal compound is a Group VIII metal compound. 12. At least 50% of the total projected area is (10
0) normal crystal silver halide grains having an area ratio of 50% or more;
The photosensitive silver halide photographic emulsion according to any one of claims 1 to 11, wherein a high silver iodide coating layer is temporarily formed on the surface of the silver halide grains during the growth of the silver halide emulsion. . 13. The method according to claim 1, wherein at least one layer on the support is provided.
13. A silver halide photographic light-sensitive material comprising the light-sensitive silver halide emulsion according to any one of items 1 to 12. 14. The method according to claim 1, wherein at least one layer on the support is provided.
13. A color reversal photographic light-sensitive material, comprising the light-sensitive silver halide emulsion according to any one of items 1 to 12.