JP2001092057A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material using a silver halide emulsion high in sensitivity and superior in resistance to deterioration of photographic performances due to pressure to be applied. SOLUTION: The silver halide photographic sensitive material is provided on a support with at least one photosensitive silver halide emulsion layer and this emulsion layer contains silver halide grains each having a projected grain diameter of >=2.0 μm occupying >=50% of the projection areas of the total silver halide grains, and this photosensitive material is characterized by the fact that >=80% of the silver halide grains having projected grain diameter of >=2.0 μm are not subjected to stress dislocation at the time of being applied to a specified pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material characterized by a silver halide photographic emulsion. More specifically, the present invention relates to a silver halide photographic material using a silver halide grain emulsion having high sensitivity and little change in photographic properties due to pressure load.

[0002]

2. Description of the Related Art Generally, various mechanical pressures are applied to a photographic material coated with a silver halide emulsion. For example, a negative film for general photography is entangled in a patrone, bent when loaded into a camera, or pulled for frame advance. Furthermore, the exposed negative film must pass through a processing step for development, and in that case, the emulsion surface may be pressed in a swollen state depending on the processing machine. As described above, when various pressures are applied to the photographic light-sensitive material, pressure is also applied to the silver halide particles using gelatin as a support (binder) of silver halide particles or a plastic film as a support as a medium. . It is known that when pressure is applied to silver halide grains, the photographic properties of the photographic material change. For example, KB Mothe
r, J. Opt. Soc. Am., 38, 1054 (1948), P. Faelens an
d P. de Smet, Sci. et Ind. Phot., 25, No. 5, 178 (195
4), P. Faelens, J. Phot. Sci., 2,103 (1954). Also, R. King and D. Ashling, J.
According to Phot. Sci., 33, (1985), electrons generated by pressure loading on silver halide grains are captured by the photosensitive center of the surface and become the development center and cover the grains, and plastic deformation due to pressure loading It is described in detail that internal structural defects caused by the above decrease surface sensitivity by capturing electrons.

When pressure is applied to a photographic light-sensitive material, that is, when pressure is applied to silver halide grains, the sensitivity of the photographic light-sensitive material is reduced by subsequent exposure and development processing or subsequent development processing. There is a case (pressure desensitization) and a case where the fogging occurs (pressure fogging). Various improvements have been made to these phenomena which are not preferable for photographic materials. For example, JP-A-50-116025, 5
JP-A-1-107129 discloses a method for improving pressure desensitization by adding an iridium salt or a thallium salt at the time of forming silver halide grains. JP-A-3-36032, JP-A-3-36033 and U.S. Pat.No. 5,061,616 add an iodide to a tabular host emulsion, and then define a pAg and a temperature to form a silver bromoiodide thin layer shell. Thus, a method for improving pressure desensitization is disclosed. JP-A-5-45756 discloses a method for improving pressure desensitization by reducing silver nuclei inside silver halide grains. At this time, a method of estimating the degree of pressure desensitization by an induced absorption peak intensity ratio before and after a pressure load in microwave photoconductivity measurement is also disclosed.

Japanese Patent Application Laid-Open No. 9-189974 discloses a method in which a peripheral portion of a silver halide host emulsion is dissolved and then a silver iodobromide layer is regenerated in the peripheral portion to obtain silver halide grains. A technique for improving the feeling is disclosed. U.S. Pat. No. 5,709,988 teaches that the pressure property is improved by reducing the ratio of dislocation lines in the central region to the ratio of dislocation lines in the peripheral region. Is not sufficiently improved. In particular, in the blue photosensitive layer, it is necessary to design silver halide grains having a high AgI content, and further improvement in pressure property is required.

[0005] As described above, the improvement of the photographic properties due to the pressure load of the photographic light-sensitive material is becoming more and more important as the photographic light-sensitive material advances day by day. Development of high-speed photographic emulsions is desired.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and provides a silver halide photograph using a silver halide emulsion having high sensitivity and excellent resistance to photographic deterioration due to pressure load. It is intended to provide a photosensitive material.

[0007]

The object of the present invention has been achieved by the following means.

(1) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, 50% or more of the projected area of all silver halide grains contained in the emulsion layer is not less than 50%. The projection area is occupied by silver halide grains having a diameter of 2.0 μm or more, and when a specific pressure is applied to the photosensitive material, 80% or more of the silver halide grains having a projection area of 2.0 μm or more ( (Grain number) does not include stress dislocations.

(2) 90% or more of the total projected area of the silver halide grains having a projected area diameter of 2 μm or more are tabular grains having an aspect ratio of 2 or more (1).
3. The silver halide photographic light-sensitive material described in 1. above.

(3) The halogen according to (1), wherein 90% or more of the total projected area of the silver halide grains having a projected area diameter of 2 μm or more are tabular grains having an aspect ratio of 10 or more. Silver halide photographic material.

(4) In the silver halide grains having a projected area diameter of 2 μm or more, grains having no dislocation line within 80% from the center of the main surface occupy 90% or more of the whole grains. The silver halide photographic material according to any one of (1) to (3).

(5) In the silver halide grains having a projected area diameter of 2 μm or more, 70% from the center of the grains.
The silver halide photographic light-sensitive material according to any one of (1) to (4), wherein the average AgI content within 5 mol% or more.

(6) In the silver halide grains having a projected area diameter of 2 μm or more, dislocations are localized in substantially only corner portions of the grains (1).
Or the silver halide photographic material according to any one of (5) to (5).

(7) In the silver halide grains having a projected area diameter of 2 μm or more, the grains take a form in which silver halide epitaxials are substantially bonded to silver halide base grains. Do (1) to (5)
5. The silver halide photographic material according to any one of the above.

(8) In the silver halide grains having a projected area diameter of 2 μm or more, at least 50% of the total silver amount
The above-described grain growth is performed by adding silver iodide fine particles formed outside the vessel in which the growth is being performed to the vessel in which the growth is being performed simultaneously with the addition of the silver salt aqueous solution and the halogen salt aqueous solution. (1) to (7)
5. The silver halide photographic material according to any one of the above.

(9) In the silver halide grains having a projected area diameter of 2 μm or more, at least 50% of the total silver amount
(1) to (7) wherein the grain growth is performed by adding silver iodobromide fine particles formed outside the growing vessel to the growing vessel. The silver halide photographic light-sensitive material as described in any one of 1) to 2) above.

(10) Any of (1) to (9), wherein the photosensitive silver halide emulsion layer is located farthest from the support among all the photosensitive silver halide emulsion layers. 2. The silver halide photographic light-sensitive material according to item 1.

[0018]

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

The silver halide emulsion in the present invention is preferably silver bromide, silver iodobromide, or silver iodochlorobromide. More preferably, the iodine content is 2 mol based on the total silver content of the grains.
silver iodobromide and silver iodochlorobromide in an amount of 1% to 20% by mol. The form of the silver halide grains may be a normal crystal such as octahedron, cubic, or tetradecahedron, but tabular grains are more preferred.

In the present invention, a tabular grain means a silver halide grain having two opposing parallel (111) main planes.
The tabular grains of the present invention have one twin plane or two or more parallel twin planes. The twin plane refers to the (111) plane when ions at all lattice points on both sides of the (111) plane are in a mirror image relationship.

When the tabular grains are viewed from above, the tabular grains have a triangular shape, a hexagonal shape, or a round shape in which these are rounded, and have outer surfaces parallel to each other.

The projected area diameter and thickness of the tabular grains are determined by taking a transmission electron micrograph by a replica method and determining the diameter (projected area diameter) and thickness of a circle having an area equal to the projected area of each grain. In this case, the thickness is calculated from the length of the shadow of the replica.

The silver halide grains in the present invention preferably have a projected area diameter of 2.0 μm or more and 20.0 μm or less.
It is more preferably from 3.0 μm to 10.0 μm. Silver halide grains having a projected area diameter of 2.0 μm or more preferably account for 50% or more of the total projected area of the silver halide grains present in the photosensitive layer containing the silver halide grains. The equivalent sphere diameter is preferably 1.0 μm or more and 5.0 μm or less, and 1.2 μm or less.
m or more and 3 μm or less is more preferable. The equivalent sphere diameter is the diameter of a sphere having a volume equal to the volume of an individual particle.
The aspect ratio is preferably 2 or more and 50 or less, and 1
0 or more and 30 or less are more preferable. The aspect ratio is a value obtained by dividing the projected area diameter of a particle by the thickness of the particle.

The emulsion of the present invention is preferably monodisperse. The coefficient of variation of the equivalent sphere diameter of all silver halide grains of the present invention is 30% or less, preferably 25% or less. Also,
In the case of tabular grains, the coefficient of variation of the projected area diameter is also important, and the variation coefficient of the projected area diameter of all silver halide grains of the present invention is preferably 30% or less, more preferably 25% or less. . The variation coefficient of the thickness of the tabular grains is preferably 30% or less, more preferably 20% or less. The coefficient of variation is the value obtained by dividing the standard deviation of the distribution of the equivalent diameter of individual silver halide grains by the average equivalent diameter, or the standard deviation of the distribution of the thickness of individual silver halide tabular grains is divided by the average thickness. Value.

The silver halide grains of the present invention have a projected area diameter of 2 μm or more, and when a specific pressure is applied to a light-sensitive material containing an emulsion layer containing the grains, the size of the large-size grains is reduced to 80 μm. % Of the large-sized grains when a specific pressure is applied to a photosensitive material containing an emulsion layer containing the grains. % Or more does not contain stress dislocations "means that after applying a specific pressure to a photosensitive material containing an emulsion layer containing the grains, care must be taken not to cause dislocations in the grains, and the halogenated material is used for the halogenation. When a silver particle is taken out and observed with an electron microscope, a stress dislocation caused by a pressure load inside the particle (a dislocation that can be clearly identified as a dislocation caused by a pressure load by observing the particles before and after the pressure load with a transmission electron microscope) )exist No particles is that 80% or more of the total particles. It is preferable that the number of grains having no stress dislocation is 80% or more of the whole grains.
More preferably, it is 0% or more.

Dislocation refers to a displacement of an atomic plane in a crystal lattice, and is a kind of lattice defect. Dislocations introduced into silver halide grains have a significant effect on photographic performance.
GC Farnell, RB Flint and JB Chanter, J. P
hot. Sci., 13, 25 (1965) shows that the location of latent image nuclei in large sized high aspect ratio tabular silver bromide grains is closely related to defects in the grains. Have been.

In this specification, a dislocation is defined as follows.

Dislocations generated due to lattice misalignment due to the incorporation of different types of halogen atoms during the formation of silver halide grains are called "growth dislocations". Dislocations that occur when a pressure is applied and that remain inside the grains after a pressure load are referred to as “stress dislocations”.

In the present invention, it has been confirmed that many of the grains having growth dislocations in the silver halide grains before the pressure load have many stress dislocations remaining after the pressure load. Generally, when a crystal is in an elastic deformation region when pressure is applied, dislocation does not occur. Dislocations occur when the crystal undergoes plastic deformation. When the dislocation generation density is low, the dislocations disappear during deformation because they do not interact with each other. On the other hand, if there are impurities or lattice defects (point defects, dislocations, plane defects, etc.) that hinder the movement of dislocations in the crystal, the dislocations generated by the deformation will not be able to move due to interaction with them and accumulate in the crystal. Will be done. Thus, it is considered that the presence of growth dislocations inside silver halide grains causes the dislocations to remain inside the grains because they interact with the dislocations generated by deformation.

Further, the support coated with the silver halide grains having the stress dislocation did not show an image in the surface development even after the exposure, in particular, the exposure to high illuminance. The number of growing dislocations was 1 or more and 30 or less per grain, but no pressure desensitization occurred before the pressure loading, but after the pressure loading, the dislocations became entangled enough to form a complex network inside. I was Observation of particles obtained by slightly developing the surface of the light-sensitive material to which a pressure was applied by a transmission electron microscope revealed that the particles in which dislocations formed a network inside were not surface-developed. From this, it is inferred that the particles in which network dislocations exist due to the pressure load cause pressure desensitization.

The specific pressure load and observation of stress dislocation according to the present invention will be described.

When any pressure is applied to the light-sensitive material having the emulsion layer coated on the support, pressure is also applied to the silver halide grains coated on the support.

Pressure is applied to a photographic material in various cases. For example, it is considered that pressure is applied when the film is wound into a patrone, when the film is loaded into the camera, when the frame is fed in the camera, or when the film is processed by the developing processor. The pressure load referred to in the present invention is also assumed to be a pressure load under these various conditions. For the sake of simplicity, a pressure load test method has been proposed, such as a bending test and a scratch test with a fine needle. In the present invention, silver halide grains are taken out of the light-sensitive material after applying a specific pressure to the light-sensitive material so that dislocations do not occur, and the inside of the grains is observed with an electron microscope. In the present invention, "specific pressure" refers to a sample (photosensitive material)
Is adjusted to 25 ° C. and 55%, and a load of 4 g is applied to a fine needle having a diameter of 50 μm to scratch the emulsion surface in a certain direction.
When the specific pressure is applied to the photosensitive material containing an emulsion layer containing large-size silver halide grains having a projected area diameter of 2 μm or more according to the present invention, 80% or more of the large-size grains contain no stress dislocation. The material performed well in the other pressure loading tests described above and also under good pressure loading under various practical conditions as described above.

Only the layer where the silver halide grains are to be observed, so that the sample scratched at the above-mentioned specific pressure should not be subjected to such a pressure that new dislocation lines are generated on the coated silver halide grains. The silver halide grains are taken out of the sample, placed on a mesh for an electron microscope, and observed by a transmission method in a state where the sample is cooled with liquid nitrogen so as to prevent damage by an electron beam. At this time, the larger the particle size or the greater the thickness of the tabular particles, the more difficult it is for an electron beam to pass through. Therefore, a higher-voltage electron microscope can be used for clearer observation. Observation of the grains before pressure application is also performed only from the layer where the silver halide grains are to be observed, taking care not to apply enough pressure to newly generate dislocation lines on the coated silver halide grains. The silver halide grains are taken out, placed on a mesh for an electron microscope, and observed by a transmission method in a state where the sample is cooled with liquid nitrogen so as to prevent damage by an electron beam.

In the present invention, when determining the ratio of silver halide grains containing dislocation lines before and after pressure loading, it is preferable to directly observe at least 100 grains, more preferably 200 grains or more, particularly preferably 3 grains or more.
More than 00 particles.

Next, observation of dislocation lines before and after pressure loading will be described.

The dislocation lines of tabular grains are described, for example, in JF Hamilt
on, Phot. Sci. Eng., 11, 57 (1967) and T. Shiozawa, J.
Sci. Pci. Sci. Japan, 35, 213 (1972) can be observed by a direct method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out with care not to apply enough pressure to generate dislocation lines from the emulsion are placed on a mesh for electron microscopic observation,
Observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (eg, printout) due to an electron beam. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

"Growth dislocations" are often linear or curved, and their number can be counted. Even if dislocation lines cross each other, the approximate number can be counted. In the present invention, the projected area diameter is 2.0
In silver halide grains having a size of at least μm, grains having no growth dislocation within 80% of the area from the center of the main plane of the grains are preferably 90% or more, more preferably 95%, of the grains. That is all. The center of the main plane means the position of the center of gravity of the main plane.

"Stress dislocation" observed after pressure loading
Are often curved, and the dislocation lines are often observed densely or intersecting with each other, but in this case also, the approximate number can be counted. In the present invention, the number of grains having five or more stress dislocations after pressure loading is preferably 80% or more, more preferably 90% or more of the number of grains having a projected area diameter of 2.0 μm or more.

In the silver halide grains of the present invention, the content of AgI with respect to the silver content in the three-dimensional region up to 70% in terms of silver from the center of the grains is 5%.
Or more, more preferably 7% or more. Here, the center of the particle means the position of the center of gravity of the particle.

In the present invention, the silver halide grains have an area of 20% or less, preferably 1% or less, from the outer periphery of the grain projection portion.
It is preferable that dislocation lines exist in a portion within 0%. The dislocation line may exist near the outer peripheral part along the outer peripheral part, or may be localized near the corner part. The vicinity of the corner portion is defined as two perpendicular lines when two perpendicular lines are dropped to two sides forming a corner from the position of x% from the particle center on a straight line connecting the center of the particle and the corner on the main plane of the particle. It is a three-dimensional area surrounded by sides. The value of x is preferably 50 or more and less than 100, more preferably 7
5 or more and less than 100. The average number of dislocation lines present is preferably 10 or more per particle. More preferably, the average is 20 or more per particle.

The silver halide grains in the present invention may have a silver halide crystal part (that is, an epitaxial part) bonded to the silver halide grains in addition to the silver halide grains. The ratio of the bonded silver halide crystal part (epitaxial part) to the total silver amount of the grain including the epitaxial part is preferably 2% to 30%, and more preferably 5% to 15%.
% Or less is more preferable. The epitaxial portion may be present in any portion of the grain body, but is preferably a grain main surface portion, a grain edge portion, or a grain corner portion. The composition of the epitaxial part is AgCl, AgBrCl, AgBrCl.
I, AgBrI, AgI, AgSCN are preferred,
gCl, AgBrCl, AgBrClI are preferred.

Next, a method for preparing silver halide grains will be described.

As a method for preparing a silver halide emulsion, a method of forming silver halide nuclei and then growing silver halide grains to obtain grains of a desired size is generally used. There is no difference. The formation of tabular grains includes at least the steps of nucleation, ripening, and growth. This process is described in U.S. Pat.
It is described in detail in the issue. In the growing step, a step of adding a silver salt aqueous solution and a halogen salt solution to a reaction vessel by a double jet method to grow silver halide grain nuclei is preferable.
In the growth by the double jet method, a method of controlling pAg in the reaction solution can also be used.

Next, the method for preparing the silver halide emulsion of the present invention will be described in detail.

The preparation step of the present invention comprises (a) a base particle forming step and a subsequent particle forming step ((b) step). Basically, only the step (a) may be used,
It is more preferable to perform the step (b) subsequent to the step (a). The step (b) includes (b1) a dislocation introduction step, and (b2)
Either the corner dislocation limited introduction step or the (b3) epitaxial bonding step may be used, and at least one may be used, or two or more may be combined.

First, the (a) base particle forming step will be described. The base portion is preferably at least 50%, more preferably at least 70%, even more preferably at least 80%, based on the total silver used for grain formation. The average iodine content relative to the silver content of the base is 0 mol% or more.
It may be 0% mol or less, preferably 5 mol% or more and 25 mol% or less, more preferably 7 mol% or more and 20 mol% or less. . The base may have a core-shell structure as needed. At this time, the core portion of the base portion is preferably 50% or more and 70% or less based on the total silver content of the base portion, and the average iodine composition of the core portion is 0 mol% or more and 30 mo or less.
It may be 1% or less, preferably 5 mol% or more and 25 mol% or less, more preferably 7 mol% or more and 20 mol% or less. The iodine composition of the shell is preferably from 0 mol% to 3 mol%. The growth of the base may be performed by a double jet method in which an aqueous solution of a silver salt and an aqueous solution of a halogen salt are simultaneously added. Alternatively, it is preferable to dilute the concentration of the added solution. Also, pAg at the time of growth
Is also preferably increased. At this time, the pAg is preferably 7.0 or more, and more preferably 7.4 or more.

It is more preferable to add the AgI fine grain emulsion prepared outside the reaction vessel simultaneously with the addition of the silver salt aqueous solution and the halogen salt aqueous solution. At this time, the growth temperature is preferably from 50 ° C. to 90 ° C., more preferably from 60 ° C. to 85 ° C. The AgI fine grain emulsion to be added may be prepared in advance or may be added while being continuously prepared. The preparation method at this time is described in JP-A-10-4357.
No. 0 can be referred to.

The average grain size of the AgI emulsion to be added is 0.
The thickness is from 01 μm to 0.1 μm, preferably from 0.02 μm to 0.08 μm. The iodine composition of the base particles is
It can be changed by the amount of the AgI emulsion to be added.

In place of the addition of the aqueous silver salt solution and the aqueous halide salt solution, fine particles of silver iodobromide may be added. At this time, base particles having a desired iodine composition can be obtained by making the iodine amount of the fine particles equal to the iodine amount of the desired base particles. Although silver iodobromide fine particles may be prepared in advance, it is preferable to add them while continuously preparing them. The silver iodobromide fine particle size to be added is 0.005μ.
m or more and 0.05 μm or less, preferably 0.01 μm or more and 0.03 μm or less. Temperature during growth is 60 ° C or more and 9
The temperature is 0 ° C or lower, preferably 70 ° C or higher and 85 ° C or lower.

Next, the step (b) will be described.

First, the step (b1) will be described.
The step (b1) includes a first shell step and a second shell step. A first shell is provided on the base described above. The ratio of the first shell is preferably from 1 mol% to 10 mol% based on the total silver amount, and the average silver iodide content is from 20 mol% to 100 mol%. More preferably, the ratio of the first shell is from 1 mol% to 5 mol% based on the total silver amount, and the average silver iodide content is from 25 mol% to 100 mol%.
It is as follows. For the growth of the first shell on the substrate, basically, an aqueous solution of silver nitrate and an aqueous solution of halogen containing iodide and bromide are added by a double jet method. Alternatively, a silver nitrate aqueous solution and a halogen aqueous solution containing iodide are added by a double jet method. Alternatively, an aqueous halogen solution containing iodide is added by a single jet method.

Any of the above methods or a combination thereof may be used. As is apparent from the average silver iodide content of the first shell, silver iodide can be precipitated in addition to the silver iodobromide mixed crystal during the formation of the first shell. In any case, the silver iodide usually disappears during the next formation of the second shell, and all of the silver iodide is changed to a silver iodobromide mixed crystal.

As a preferred method for forming the first shell, there is a method in which a silver iodobromide or silver iodide fine grain emulsion is added, ripened and dissolved. Further, as a preferred method, there is a method of adding a silver iodide fine grain emulsion and then adding an aqueous solution of silver nitrate or an aqueous solution of silver nitrate and an aqueous solution of halogen. In this case, the dissolution of the silver iodide fine grain emulsion is promoted by the addition of an aqueous solution of silver nitrate.
Mol%. Then, the calculated silver nitrate aqueous solution is used as the second shell. The silver iodide fine grain emulsion is preferably added rapidly.

When the silver iodide fine grain emulsion is rapidly added,
Preferably, the silver iodide fine grain emulsion is added within 10 minutes. More preferably, it is added within 7 minutes. These conditions can vary depending on the temperature of the system to be added, pBr, pH, the type and concentration of the protective colloid agent such as gelatin, the presence or absence of the silver halide solvent, the type and the concentration, etc., but the shorter is preferable as described above. It is preferable that the addition of an aqueous solution of silver salt such as silver nitrate is not substantially performed during the addition.
The temperature of the system at the time of addition is preferably from 40 ° C to 90 ° C,
A temperature of 50 ° C or higher and 80 ° C or lower is particularly preferred.

The silver iodide fine grain emulsion only needs to be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. Preferably 100%
It is silver iodide. Silver iodide has β-form and γ-form in its crystal structure.
There may be isomers as well as α-isomer or α-isomer-like structures as described in US Pat. No. 4,672,026. In the present invention, the crystal structure is not particularly limited,
A mixture of β-form and γ-form, more preferably β-form is used. A silver iodide fine grain emulsion is disclosed in US Pat. No. 5,004,679.
May be formed immediately before the addition described in the number, etc.,
Any of those which have undergone a normal washing step may be used, but those which have undergone a normal washing step are preferably used in the present invention. A silver iodide fine grain emulsion is disclosed in U.S. Pat.
It can be easily formed by the method described in US Pat. No. 2,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the grains are formed with a constant pI value during grain formation, is preferred. Where pI is the logarithm of the reciprocal of the I ^- ion concentration of the system. The temperature, pI, pH, type and concentration of protective colloid such as gelatin, the presence or absence of silver halide solvent, type, concentration, etc. are not particularly limited, but the grain size is 0.1 μm or less, more preferably 0.07 μm. The following are convenient for the present invention.
Although the particle shape cannot be completely specified because of the fine particles, the variation coefficient of the particle size distribution is preferably 25% or less.
In particular, when the content is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are determined by placing silver iodide fine grains on a mesh for observation with an electron microscope and observing them directly by a transmission method instead of a carbon replica method. This is because the observation error by the carbon replica method becomes large due to the small particle size.

The grain size is defined as the diameter of a circle having a projected area equal to the observed grain. The particle size distribution is also determined using the same projected area circle diameter.
The most effective silver iodide fine grains in the present invention have a grain size of 0.06 μm or less and 0.02 μm or more, and a variation coefficient of grain size distribution is 18% or less.

The silver iodide fine grain emulsion is preferably formed by the above-mentioned grain formation and then preferably washed with ordinary water described in US Pat. No. 2,614,929 or the like, and adjusted with a protective colloid such as pH, pI, gelatin and the like. The concentration of silver halide is adjusted. The pH is preferably 5 or more and 7 or less. The pI value is a pI value at which the solubility of silver iodide is the lowest or a pI value higher than the pI value.
It is preferable to set the I value. As the protective colloid, ordinary gelatin having an average molecular weight of about 100,000 is preferably used. Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. It is sometimes convenient to use a mixture of gelatins having different molecular weights. Emulsion 1k
The amount of gelatin per g is preferably 10 g or more and 100 g or more.
It is as follows. More preferably, it is 20 g or more and 80 g or less. The silver amount in terms of silver atoms per kg of the emulsion is preferably from 10 g to 100 g. More preferably 20g
Not less than 80 g. The amount of gelatin and / or silver is preferably selected to a value suitable for rapidly adding a silver iodide fine grain emulsion.

The silver iodide fine grain emulsion is usually dissolved and added in advance, but at the time of addition, it is necessary to sufficiently increase the stirring efficiency of the system. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective to prevent the generation of foam during stirring. Specifically, U.S. Pat.
The antifoaming agents described in the examples of 275,929 and the like are used.

As a more preferred method of forming the first shell, US Pat. No. 5,496,6 replaces the conventional iodide ion supply method (a method of adding free iodide ions).
Using the iodide ion releasing agent described in No. 94, a silver halide phase containing silver iodide can be formed while rapidly generating iodide ions.

The iodide ion-releasing agent releases iodide ions by reaction with an iodide ion-releasing regulator (base and / or nucleophile). Seeds. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinates, carboxylates, ammonia, amines, Examples include alcohols, ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines, and sulfides.

The release rate and timing of iodide ions can be controlled by controlling the concentrations of bases and nucleophiles, the method of addition, and the temperature of the reaction solution. The base is preferably an alkali hydroxide.

The preferred concentration range of the iodide ion releasing agent and the iodide ion release controlling agent used for rapidly generating iodide ions is 1 × 10 ^{−7 to} 20 M, more preferably 1 × 10 ⁻⁵ to 20 μM. 10M, more preferably 1 × 1
It is 0 ^{-4 to} 5M, particularly preferably 1 × 10 ^{-3 to} 2M.

If the concentration exceeds 20 M, the amount of the iodide ion releasing agent having a large molecular weight and the amount of the iodide ion releasing agent to be added become too large with respect to the capacity of the particle forming container.

If the concentration is lower than 1 × 10 ⁻⁷ M, the reaction rate of iodide ion release reaction becomes slow, and it is difficult to rapidly generate an iodide ion releasing agent, which is not preferable.

A preferred temperature range is 30 to 80 ° C.
More preferably 35 to 75 ° C, particularly preferably 35 to 6 ° C.
0 ° C.

If the temperature is higher than 80 ° C., the reaction rate of iodide ion release generally becomes extremely high, and if the temperature is lower than 30 ° C., the reaction rate of iodide ion release is generally extremely low. Absent.

When a base is used for releasing iodide ions, a change in the pH of the solution may be used. At this time, the preferable pH range for controlling the release rate and timing of iodide ions is 2 to 12, more preferably 3 to 12.
11, particularly preferably 5 to 10, and most preferably the adjusted pH is 7.5 to 10.0. Even under neutral conditions at pH 7, hydroxide ions determined by the ionic product of water act as regulators.

A nucleophile and a base may be used in combination.
Also at this time, the release rate and timing of iodide ions may be controlled by controlling the pH within the above range.

When iodine atoms are released from the iodide ion releasing agent in the form of iodide ions, all iodine atoms may be released, or a part of the iodine atoms may remain without being decomposed.

A second shell is provided on the tabular grains having the above-described base and the first shell. The ratio of the second shell is preferably from 10 mol% to 40 mol% based on the total silver amount, and the average silver iodide content is from 0 mol% to 5 mol%. More preferably, the ratio of the second shell is from 15 mol% to 30 mol% based on the total silver amount, and the average silver iodide content is from 0 mol% to 3 mol%. Second on tabular grains with base and first shell
The growth of the shell may be in the direction of increasing or decreasing the aspect ratio of the tabular grains. Basically, the second shell is grown by adding a silver nitrate aqueous solution and a bromide-containing halogen aqueous solution by a double jet method. Alternatively, after adding an aqueous halogen solution containing bromide, an aqueous silver nitrate solution may be added by a single jet method. System temperature,
The pH, the type and concentration of the protective colloid agent such as gelatin, the presence or absence of the silver halide solvent, the type, the concentration, and the like can vary widely. Regarding pBr, in the present invention, it is preferable that pBr at the end of the formation of the layer be higher than pBr at the beginning of the formation of the layer. Preferably, pBr in the initial stage of formation of the layer
Is 2.9 or less, and pBr at the end of the formation of the layer is 1.7.
That is all. More preferably, pBr in the initial stage of the formation of the layer
Is 2.5 or less, and pBr at the end of the formation of the layer is 1.9.
That is all. Most preferably, pBr in the initial stage of the formation of the layer is 2.3 or less and 1 or more. Most preferably, the pBr at the end of the layer is 2.1 or more and 4.5 or less.

It is preferable that dislocation lines exist in the step (b1). The dislocation lines are preferably present near the edge of the tabular grains. The vicinity of the edge portion refers to an outer peripheral portion (edge portion) of six sides of the tabular grain and an inner portion thereof, that is, a portion grown in the step (b1). It is preferable that the average number of dislocation lines per grain is 10 or more. More preferably, the average is 20 or more per particle.
When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, approximately 10, 20
It is possible to count as many as 30 or 30 books, which can be clearly distinguished from the case where only a few are present. The average number of dislocation lines per particle is determined as a number average by counting the number of dislocation lines for 100 particles or more.

The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% (number) of all grains, more preferably 100 to 70%, particularly preferably 100 to 100%. Or 90%.

If the ratio is less than 50%, it is not preferable from the viewpoint of homogeneity between particles.

In the present invention, when the ratio of the particles containing dislocation lines and the number of dislocation lines are obtained, it is preferable to directly obtain the dislocation lines for at least 100 particles.
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

Next, the step (b2) will be described.

The first mode is a method in which only the vicinity of the corner is dissolved by iodide ions. The second mode is a method in which a silver salt solution and an iodide salt solution are simultaneously added. As a mode, there is a method of substantially dissolving only the vicinity of the corner portion using a silver halide solvent, and as a fourth mode, there is a method via halogen conversion.

The method of dissolving with iodide ions, which is the first embodiment, will be described.

By adding iodide ions to the base particles, the vicinity of each corner of the base particles is melted and rounded. Subsequently, when a silver nitrate solution and a bromide solution, or a mixed solution of a silver nitrate solution, a bromide solution, and an iodide solution are simultaneously added, the grains further grow and dislocations are introduced near the corners. This method is disclosed in Japanese Patent Laid-Open No. 4-149541.
And JP-A-9-189974 can be referred to.

The total amount of iodide ions added in this embodiment is defined as I ₂ (mol%) obtained by multiplying the value obtained by dividing the total mole number of the iodide ions by the total mole number of silver of the base grains and multiplying by 100. Then, it is preferable that (I ₂ −I ₁ ) satisfies 0 or more and 8 or less with respect to the silver iodide content I ₁ (mol%) of the base grains in order to obtain an effective dissolution according to the present invention, More preferably, it is 0 or more and 4 or less.

In the present embodiment, the concentration of the iodide ion added is preferably low, and specifically, the concentration is not more than 0.2 mol / liter (hereinafter, liter is also referred to as “L”). Preferably, more preferably, 0.1 mol / L.

The pAg at the time of adding iodide ions is preferably 8.0 or more, more preferably 8.5 or more.

Following dissolution of the corners of the base particles by addition of iodide ions to the base particles, a silver nitrate solution alone was added, or a silver nitrate solution and a bromide solution, or a silver nitrate solution, a bromide solution, and a iodide solution were mixed. The liquid is added simultaneously to further grow the grains and introduce dislocations near the corners.

The second embodiment, a method of simultaneous addition of a silver salt solution and an iodide salt solution, will be described. By rapidly adding the silver salt solution and the iodide salt solution to the base grains, silver iodide or silver halide having a high silver iodide content can be epitaxially generated at the corners of the grains. At this time, the addition rate of the silver salt solution and the iodide salt solution is preferably 0.2 to 0.5 minutes, more preferably 0.5 to 2 minutes. This method is described in detail in JP-A-4-149541 and can be referred to. .

Following the dissolution of the corners of the base particles by the addition of iodide ions to the base particles, a silver nitrate solution alone was added, or a silver nitrate solution and a bromide solution, or a silver nitrate solution, a bromide solution, and a iodide solution were mixed. The liquid is added simultaneously to further grow the grains and introduce dislocations near the corners.

The third embodiment, a method using a silver halide solvent will be described.

When a silver halide solvent is added to the dispersion medium containing the base grains and then a silver salt solution and an iodide salt solution are simultaneously added, silver iodide or iodide is added to the corners of the base grains dissolved by the silver halide solvent. Silver halide having a high silver halide content grows preferentially. At this time, it is not necessary to rapidly add the silver salt solution and the iodide salt solution. This method is described in detail in JP-A-4-149541, which can be referred to.

Following the dissolution of the corners of the base particles by adding iodide ions to the base particles, a silver nitrate solution was added alone, or a silver nitrate solution and a bromide solution, or a silver nitrate solution, a bromide solution, and a iodide solution were mixed. The liquid is added simultaneously to further grow the grains and introduce dislocations near the corners.

Next, a method via halogen conversion, which is the fourth embodiment, will be described.

An epitaxial growth site support (hereinafter referred to as a site director) is added to the base particles, for example,
No. 8-108526, a silver chloride epitaxial is formed at the corners of the base grains by adding a water-soluble iodide and then silver iodide or silver iodide is added by adding iodide ions. This is a method of performing halogen conversion to silver halide having a high silver halide content. The site director may be a sensitizing dye or a water-soluble thiocyanate ion, but a water-soluble iodide ion is preferred. The iodide ion used is 0.0005 to
1 mol%, preferably 0.001 to 0.5 mol%. After the addition of the iodide ion, the silver chloride solution and the chloride salt solution are added simultaneously, whereby silver chloride epitaxial can be formed at the corners of the base grains.

The halogen conversion of silver chloride by iodide ions will be described. Highly soluble silver halide is converted to less soluble silver halide by adding halide ions that can form less soluble silver halide. This process is called halogen conversion and is described, for example, in US Pat. No. 4,142,900. In the present invention, silver chloride epitaxially grown at the corners of the substrate is selectively halogen-converted by iodide ions, thereby forming a silver iodide phase at the corners of the substrate grains. Details are described in JP-A-4-149541.

Silver halide epitaxially grown at the corners of the base grains was converted into a silver iodide phase by adding iodide ions, followed by a single addition of a silver nitrate solution.
Alternatively, a silver nitrate solution and a bromide solution, or a mixed solution of a silver nitrate solution, a bromide solution, and an iodide solution are simultaneously added to further grow the grains and introduce dislocations near the corners.

It is preferable that dislocation lines exist in the step (b2). Preferably, the dislocation lines exist substantially near the corners of the tabular grains. The vicinity of a corner is defined as two perpendiculars when two perpendiculars are respectively dropped to two sides forming a corner from the position of x% from the center of the particle on a straight line connecting the center of the particle and the corner on the main plane of the particle. It is a three-dimensional area surrounded by two sides. The value of x is preferably 50 or more and less than 100, and more preferably 75 or more and less than 100. It is preferable that the average number of dislocation lines per grain is 10 or more. More preferably, the average is 20 or more per particle. When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where only a few pieces exist. The average number of dislocation lines per particle is determined as a number average by counting the number of dislocation lines for 100 particles or more.

The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% (number) of all grains, more preferably 100 to 70%, particularly preferably 100 to 100%. Or 90%.

[0095] If the amount is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when calculating the ratio of the particles containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles.
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

Next, the step (b3) will be described.

Regarding the epitaxial formation of silver halide on the base grains, as described in US Pat. No. 4,435,501, an iodide ion, aminoazaindene or a spectral sensitizing dye adsorbed on the surface of the base grains is used. It has been shown that silver halide epitaxy can be formed at selected sites, such as edges or corners of substrate grains, by a site director. Further, Japanese Patent Laid-Open No. 8-
No. 69069 discloses that a silver salt epitaxial is formed at a selected site on the basis of an ultrathin tabular grain, and the epitaxial phase is optimally chemically sensitized to achieve high sensitization.

In the present invention, it is very preferable to use these methods to sensitize the base particles of the present invention.
The site director may use an aminoazaindene or a spectral sensitizing dye, but it is more preferable to use an iodide ion or a thiocyanate ion.

By changing the amount of iodide ion or thiocyanate ion added, the silver salt epitaxial formation site can be limited to the edge or corner of the base grain.

The amount of iodide ion to be added is 0.0005 to 1.0 mol%, preferably 0.001 to 0.5 mol%, based on the silver amount of the base particles. The amount of thiocyanate ion is 0.01 to the amount of silver in the base particles.
-0.2 mol%, preferably 0.02-0.1 mol%
It is.

After the addition of these site directors, a silver salt solution and a chloride salt solution are added to form silver chloride epitaxial. At this time, the temperature is preferably from 40 to 70 ° C, more preferably from 45 to 60 ° C. In this case, pA
g is preferably 7.5 or less, more preferably 6.5 or less. By using the site director, a silver chloride epitaxial is formed at a corner portion or an edge portion of the base grain. The emulsion thus obtained was prepared according to the method described in JP-A-8-690.
As in the case of No. 69, the epitaxial phase may be selectively subjected to chemical sensitization for sensitization, but subsequent to the silver chloride epitaxial formation, a silver salt solution and a halogen salt solution may be added simultaneously to further grow. It was found that the sensitivity was further increased. The halogen salt aqueous solution to be added at this time is a bromide salt solution or a mixture of a bromide salt solution and an iodide salt solution. Further, the temperature at this time is preferably from 40 to 80 ° C, more preferably from 45 to 70 ° C. In this case, pA
g is preferably 5.5 or more and 9.5 or less, and 6.0 or more and 9.5 or less.
0 or less is preferable.

The epitaxial formed in the step (b3) is basically characterized in that a halogen composition different from that of the base grains is formed outside the base grains formed in the step (a). The composition of the epitaxial is AgC
1, AgBrCl or AgBrClI is preferred. It is further preferable to introduce a “dopant (metal complex)” into the epitaxial layer as described in JP-A-8-69069. The position of the epitaxial growth may be at least a part of the corner portion, the edge portion, or the main plane portion of the base particle, or may extend over a plurality of portions. It is preferable to take the form of only a corner portion, only an edge portion, or a corner portion and an edge portion.

Although the dislocation line may not exist in the step (b3), it is more preferable that the dislocation line exists. The dislocation lines are preferably present at the junction between the base particles and the epitaxially grown part or at the epitaxial part. It is preferable that the average number of dislocation lines present in the junction or the epitaxial portion is 10 or more per grain. More preferably, the average is 20 or more per particle. When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where only a few pieces exist. The average number of dislocation lines per particle is determined as a number average by counting the number of dislocation lines for 100 particles or more.

The tabular grains of the present invention desirably have a uniform distribution of dislocation dose between grains. In the emulsion of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% (number) of all grains, more preferably 100 to 70%, particularly preferably 100 to 100%. Or 90%.

If it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when determining the ratio of the particles containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles.
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

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

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

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci.
Photo. Japan. No. 16. P30 (196
Enzyme-treated gelatin as described in 6) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used.

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

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain and a method of doping only the core portion, only the shell portion, or only the epitaxial portion of the grain can be selected. For example,
Mg, Ca, Sr, Ba, Al, Sc, Y, La, C
r, Mn, Fe, Co, Ni, Cu, Zn, Ga, R
u, Rh, Pd, Re, Os, Ir, Pt, Au, C
d, Hg, Tl, In, Sn, Pb, and Bi can be used. These metals include ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, and hexacoordinated complexes,
It can be added in the form of a salt that can be dissolved at the time of particle formation, such as a coordination complex salt. For example, CdBr ₂ , CdC
l ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ C
OO) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe
(CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ RhCl ₆ , K
₄ Ru (CN) ₆ . The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These are metal compounds
Only the types may be used, or two or more types may be used in combination.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding an aqueous solution of hydrogen halide (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be used. If necessary, an acid or alkali may be added. The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles. Further, a water-soluble silver salt (for example, AgNO ₃ ) or an aqueous alkali halide solution (for example, NaCl, K
(Br, KI) can be added continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

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

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

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

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

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

The emulsion of the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-7 mol, per mol of silver halide. The preferred range of the palladium compound is 1 per mole of silver halide.
It is from × 10 ⁻³ to 5 × 10 ⁻⁷ mol. The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² to 1 × 10 ⁻⁶ mol per mol of silver halide.

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

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

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, reduction sensitization refers to a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a pAg1 to 7 low pAg atmosphere called silver ripening, or a pH 8 to 11 called high pH ripening. Any method of growing or maturing in a high pH atmosphere can be selected. Also, two or more methods can be used in combination.

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

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

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

During the production process of the emulsion of the present invention, an acid for silver is used.
It is preferable to use an agent. The oxidizing agent for silver is
It acts on metallic silver to convert it to silver ions.
Refers to a compound having Especially the formation process of silver halide grains
And very fine silver by-produced during chemical sensitization
A compound that converts particles into silver ions is effective.
The silver ions generated here are silver halide, silver sulfide,
It may form a silver salt that is hardly soluble in water like silver lenide,
Further, a silver salt easily soluble in water such as silver nitrate may be formed.
The oxidizing agent for silver may be inorganic or organic.
You may. Ozone and hydrogen peroxide as inorganic oxidants
And its additives (eg, NaBO_Two・ H_TwoO_Two・ 3H_Two
O, 2NaCO_Three・ 3H_TwoO_Two, Na_FourP_TwoO₇・ 2H_TwoO_Two,
2Na_TwoSO_Four・ H_TwoO_Two・ 2H_TwoO), peroxy acid salt
(Eg K_TwoS_TwoO₈, K_TwoC_TwoO₆, K_TwoP_TwoO₈), Peru
Xy complex compounds (for example, K_Two[Ti (O_Two) C_TwoO_Four]
3H_TwoO, 4K_TwoSO_Four・ Ti (O_Two) OH ・ SO_Four2H
_TwoO, Na_Three[VO (O_Two) (C_TwoH _Four)_Two・ 6H_TwoO), excessive
Manganates (eg, KMnO_Four), Chromate (example)
For example, K_TwoCr_TwoO₇) Like oxyacid salts, iodine and bromine
Such halogen elements, perhalates (eg, periodic acid
Potassium), high valent metal salts (eg, hexacia
Potassium ferric acid), and thiosulfonates
There is.

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

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

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

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

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

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

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

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

The amount of addition was 4 × / mol of silver halide.
It can be used at 10 ^-6 to 8 × 10 ^-3 mol.

The light-sensitive material produced by using the silver halide emulsion obtained in the present invention may comprise a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. It is sufficient that at least one layer is provided, and there is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one color-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, a unit photosensitive layer is generally used. The sequence of the red-sensitive layer in order from the support side,
A green color sensitive layer and a blue color sensitive layer are provided in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

The silver halide emulsion having excellent pressure resistance as defined in this specification can be used in at least one of the light-sensitive layers, but is preferably used in the emulsion layer located farthest from the support. Is preferable in that the effects of the present invention can be achieved.

A non-light-sensitive layer such as an intermediate layer of each layer may be provided between the above-mentioned silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

As the intermediate layer, JP-A-61-43748 was used.
No. 59-113438, No. 59-113440
Couplers and DIR compounds as described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer structure of an emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, 62-200350
As described in JP-A-62-206541 and JP-A-62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
For example, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / a high-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL) or BH / BL / GL / GH / R
H / RL, or BH / BL / GH / GL / RL /
They can be installed in the order of RH.

As described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of JP-A No. 6, a blue-sensitive layer / GL / RL / GH / RH can be provided in this order from the farthest side from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a lower sensitivity than the middle layer. Further, there is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-speed emulsion layer / They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. Also, 4
The arrangement may be changed as described above even in the case of more than layers. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The above-mentioned various additives are used in the light-sensitive material according to the present invention, but other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (1978).
Item 18716 (January 1979)
Jan.) and Item 308119 (December 1989), and the relevant portions are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column-996 right-998 right Super strong Sensitizer 649 right column 4 Brightener 4 page 647 right column 998 right 5 Antifoggant, 24-25 page 649 right column 998 right-1000 right and stabilizer 6 light absorber, 25-26 649 Page right column to 1003 left to 1003 right Filter dye, page 650 Left column UV absorber 7 Stain inhibitor page 25 right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardener 26 page 651 Page left column 1004 right to 1005 left 10 Binder page 26 Same as above 1003 right to 1004 right 11 Plasticizer, lubricant 27 page 650 Page right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 Same as above 1005 left to 1006 left Surfactant 13 static page 27 Same as above 1006 right to 1007 left inhibitor 14 matting agent 1008 left to 1009 left.

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in JP-A No. 7 or 4,435,503 to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-CG and N
o. 307105, VII-CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in EP 249,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
No. 35730, No. 55-118034, No. 60-18
No. 5,951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO 88/04795 are particularly preferred.

Examples of the cyan coupler include phenol-based and naphthol-based couplers.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622, and 4,333,999.
No. 4,775,616, No. 4,451,55
No. 9, No. 4,427,767, No. 4,690, 8
No. 89, No. 4,254,212, No. 4,296,
199 and JP-A-61-42658 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137 and European Patent 341,188A.
No.

Examples of couplers in which a coloring dye has an appropriate diffusivity include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

The colored coupler for correcting the unnecessary absorption of the coloring dye is described in Research Disclosure No.
No. 17643, section VII-G; VII of 307105-
Section G, U.S. Pat. No. 4,163,670, JP-B-57-
39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, British Patent 1,146,368.
Those described in the above item are preferred. Also, U.S. Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 4,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in U.S. Pat. No. 4,777,120 as a leaving group.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, VII-F and the same No. 307105, VII-
Patent described in section F, JP-A-57-151944,
Preferred are those described in JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350 and U.S. Pat. Nos. 4,248,962 and 4,782,012.

As a coupler which releases a nucleating agent or a development accelerator in an image-like manner at the time of development, UK Patent No. 2,099
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in US Pat.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950 and JP-A-62-24252.
R redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, couplers capable of releasing dyes which discolor after release as described in EP 173,302A and EP 313,308A , RD. No. 1
Bleaching accelerator releasing couplers described in US Pat. Nos. 4,5, 1449, 24241, and JP-A-61-201247.
55,477, etc., couplers releasing leuco dyes described in JP-A-63-75747, and couplers releasing fluorescent dyes described in U.S. Pat. No. 4,774,181. .

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027.

Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). , Decyl phthalate, bis (2,4-di-ter
t-amylphenyl) phthalate, bis (2,4-di-
tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); esters of phosphoric acid or phosphonic acid (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, Tri-2-ethylhexyl phosphate,
Tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate); benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate); amides ( For example, N, N-diethyldodecaneamide, N, N-diethyllauramide,
N-tetradecylpyrrolidone); alcohols or phenols (eg, isostearyl alcohol, 2,
4-di-tert-amylphenol); aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl)
Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octyl aniline); hydrocarbons (eg, Paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, the boiling point is about 30 ° C.
As described above, an organic solvent having a temperature of preferably 50 ° C. or more and about 160 ° C. or less can be used, and typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide. Can be

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described, for example, in US Pat.
9,363, West German Patent Application (OLS) No. 2,541,
274 and 2,541,230.

When the light-sensitive material of the present invention is applied as a color light-sensitive material, phenethyl alcohol or JP-A-63-2
57747, 62-272248 and JP-A-1-80941, for example, 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3, 5-dimethylphenol, 2-phenoxyethanol, 2- (4
It is preferred to add various preservatives or fungicides such as-(thiazolyl) benzimidazole.

The present invention can be applied to various black-and-white and color photographic materials. For example, black and white film, black and white photographic paper, color negative film for general or movie use,
Typical examples include color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention
It can be particularly preferably used for a film for color duplication.

Suitable supports that can be used in the present invention are described, for example, in RD. No. No. 17643, page 28;
No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness here means the film thickness measured under humidity control at 25 ° C. and 55% relative humidity (2 days). Further, the film swelling rate T _1/2 can be measured according to a method known in the art, and is described, for example, by A. Green et al. In Photographic Science and Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129 can be used for measurement. In addition, T _1/2 is 30 in the color developing solution.
℃, the maximum swelling film thickness of 9 reached when treated for 3 minutes 15 seconds
0% is defined as the saturated film thickness, and defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating.

The light-sensitive material of the present invention has a total dry film thickness of 2 μm to 2 μm on the side opposite to the support having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) of 0 μm. The back layer preferably contains, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. . The swelling ratio of the back layer is preferably from 150 to 500%.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. No. 17643, pages 28 to 29;
No. 18716, page 651, left column to right column; 30
The development can be carried out by a usual method described on pages 880 to 881 of No. 7105.

The color developing solution used for developing the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, in particular, 3-methyl-4-
Sulfates of amino-N-ethyl-N-β-hydroxyethylaniline are preferred. These compounds are used depending on the purpose.
More than one species may be used in combination.

The color developing solution may be, for example, a pH buffer such as an alkali metal carbonate, borate or phosphate,
It generally contains a development inhibitor or antifoggant such as chloride, bromide, iodide, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine and catecholsulfonic acid; ethylene glycol; Organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines; dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos Various chelating agents such as carboxylic acids can be used. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-
Representative examples include diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. be able to.

When the reversal process is performed, color development is usually performed after black-and-white development. The black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, for example, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-
Known black and white developing agents of aminophenols such as p-aminophenol can be used alone or in combination. The p of these color developing solutions and black-and-white developing solutions
H is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 L or less per square meter of the light-sensitive material. 500 ml ( Hereinafter, it is also referred to as “mL”.) When the replenishment amount is reduced, it is preferable to prevent the evaporation and air oxidation of the processing liquid by reducing the contact area of the processing liquid with air.

The contact area between the photographic processing solution and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [capacity of treatment liquid (cm / ³ )].

The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05.
As a method of reducing the aperture ratio in this way, in addition to a method of providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a movable lid described in JP-A-1-82033 is used. And a slit developing method described in JP-A-63-216050. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps of bleaching, bleach-fixing, fixing, washing and stabilization. Further, by using means for suppressing the accumulation of bromide ions in the developer, the replenishing amount can be reduced.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent. .

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Furthermore, processing in two continuous bleach-fix baths, fixing before bleach-fix processing,
Alternatively, bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids (particularly, sodium persulfate is suitable for a color negative film for movies), quinones, and nitro compounds are used. Representative bleaching agents include organic complex salts of iron (III), for example, ethylenediaminetetraacetic acid,
Complex salts with aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or, for example, citric acid, tartaric acid, malic acid Can be used. Of these, iron (III) aminopolycarboxylate complexes, including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate,
It is preferable from the viewpoint of rapid processing and prevention of environmental pollution. further,
The aminoboric acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: for example, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95731, No. 53-
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-18426, Research Disclosure No. 17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A-51-140129; thiazolidine derivatives described in JP-A-51-140129; Japanese Patent Publication No. 45-8506;
Nos. 832 and 53-32735, U.S. Pat.
No. 6,561, the thiourea derivative described in West German Patent 1,
127,715; JP-A-58-16235; West German Patent Nos. 966,410 and 2,741
8,430; polyamine compounds described in JP-B-45-8836; and JP-A-49-40943 and JP-A-49-59644.
Nos. 53-94927, 54-35727, 55
Compounds described in -26506 and 58-163940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat.
No. 58, West German Patent No. 1,290,812,
Compounds described in -95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,884 are also preferable. These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain, in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specific examples include acetic acid, propionic acid, and hydroxyacetic acid.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Of these, use of thiosulfates is common, and in particular, ammonium thiosulfate can be used most widely. Also, thiosulfate and, for example, thiocyanate,
A combination use of a thioether compound and thiourea is also preferable. Examples of the preservatives of the fixing solution and the bleach-fixing solution include sulfites, bisulfites, carbonyl bisulfite adducts and European Patent No. 2
Sulfinic acid compounds described in No. 94,769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methyl for adjusting pH. It is preferable to add imidazoles such as imidazole in an amount of 0.1 to 10 mol / L.

It is preferable that the total time of the desilvering step is shorter as long as defective desilvering does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method for enhancing the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method described in JP-A-62-183461, using a rotating means. There is a method to improve the effect. In addition, the photosensitive material is moved while the wiper blade provided in the solution is in contact with the emulsion surface, and the turbulence of the emulsion surface is used to improve the stirring effect, and the circulation flow rate of the entire processing solution is increased. There is a method to make it. Such an agitation improving means is effective for any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, thereby increasing the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibition effect by the bleaching accelerator.

The automatic developing machine used for developing the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-19.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 1258 and 60-191259. Japanese Patent Laid-Open No. Sho 6
As described in Japanese Patent Application No. 0-191257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective in shortening the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of water to be washed in the water washing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use,
Further, for example, the washing water temperature, the number of washing tanks (the number of stages),
It can be set in a wide range according to a replenishment method such as countercurrent or forward flow, and other various conditions. Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is shown in Journal of
the Society of Motion Pi
cure and Television Engi
neers, vol. 64, p. 248-253 (1955)
May issue).

According to the multi-stage counter-current method described in the above document,
Although the amount of washing water can be greatly reduced, there is a problem that bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also described in JP-A-57-8542, for example, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and others, such as benzotriazole, by Hiroshi Horiguchi "The Chemistry of Bactericidal and Fungicides" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Techniques" (1982) Industrial Technology Association, Japan Bactericidal and Fungicide Society, Ed. A fungicide described in "A fungus encyclopedia" (1986) can also be used.

The washing water p in the processing of the photosensitive material of the present invention.
H is 4-9, preferably 5-8. The washing water temperature and washing time can also be variously set depending on, for example, the characteristics and use of the photosensitive material, but are generally at 15 to 45 ° C. for 20 seconds to 1 hour.
A range of 0 minutes, preferably 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Patent Application Laid-Open No. 57-8543
, 58-14834 and 60-220345 can all be used.

Further, a stabilization treatment may be further performed after the water washing treatment. An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

For example, in a process using an automatic developing machine,
When each of the above-mentioned treatment liquids is concentrated by evaporation, it is preferable to add water to correct the concentration.

In the silver halide color photographic light-sensitive material to which the present invention is applied, a color developing agent may be incorporated for the purpose of simplifying and speeding up the processing. In order to incorporate them, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in US Pat. No. 3,342,597, for example, US Pat. No. 3,342,599,
Research Disclosure No. 14, 850 and the same No. Nos. 15, 15 and 159; 13,924, the metal salt complex described in U.S. Pat. No. 3,719,492, and the urethane-based compound described in JP-A-53-135628.

The silver halide color light-sensitive material to which the present invention is applied may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are described, for example, in JP-A-56-6433.
No. 9, No. 57-144547 and No. 58-115
No. 438.

Various processing solutions in the present invention may be used at a temperature of 10 ° C. to 5 ° C.
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide photographic light-sensitive material of the present invention is disclosed in US Pat. No. 4,500,626 and JP-A-60-1.
No. 33449, No. 59-218443, No. 61-23
No. 8056, European Patent No. 210,660A2, and the like.

Further, silver halide color photographic light-sensitive materials to which the present invention is applied are described in JP-B-2-32615 and JP-B-2-3615.
In the case where the present invention is applied to a film unit with a lens described in, for example, US Pat.

[0195]

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.

(Example 1) Silver halide emulsions A-1 to A-10 were prepared by the following production method.

(Production Method of Emulsion A-1) Phthalated low molecular weight gelatin having a molecular weight of 15,000 and a phthalation rate of 97% 3
42.2 L of an aqueous solution containing 1.7 g and 31.7 g of KBr was kept at 35 ° C. and stirred vigorously. AgNO ₃ 316.7 g
Was added to the aqueous solution containing 1583 mL of an aqueous solution containing 152.7 mL of KBr, 221.5 g of KBr, and 52.7 g of low-molecular-weight gelatin having a molecular weight of 15,000 over 1 minute by a double jet method. Immediately after the addition is completed, 52.8 g of KBr is added,
2485 mL of an aqueous solution containing 398.2 g of AgNO ₃ and K
2581 mL of an aqueous solution containing 291.1 g of Br was added over 2 minutes by the double jet method. Immediately after the addition, 47.8 g of KBr was added. Thereafter, the temperature was raised to 40 ° C. and the product was aged sufficiently. After ripening, 923 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000 and K
After adding 79.2 g of Br, 15947 mL of an aqueous solution containing 5103 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over a period of 12 minutes while accelerating the flow so that the final flow was 1.4 times the initial flow. At this time, the silver potential was kept at -60 mV with respect to the saturated calomel electrode. After washing with water, gelatin was added, pH 5.7, pAg 8.8, emulsion 1
The seed emulsion was adjusted to a weight of 131.8 g in terms of silver and a weight of 64.1 g of gelatin per kg. 97% phthalation rate
1211 mL of an aqueous solution containing 46 g of phthalated gelatin and 1.7 g of KBr was kept at 75 ° C. and stirred vigorously. After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Ltd.) was added.
Was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and K were added.
The Br aqueous solution was added over a period of 6 minutes by a double jet method at a flow rate accelerated so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was set to -20 with respect to the saturated calomel electrode.
mV. Sodium benzenethiosulfonate 2m
After addition of g and thiourea dioxide 2 mg, AgNO ₃ 1
Aqueous solution containing 44.5g, 410mL and KI 7mol
% Of a mixed aqueous solution of KBr and KI was added by a double jet method over a period of 56 minutes while the flow rate was accelerated so that the final flow rate was 3.7 times the initial flow rate. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode. AgNO ₃ 4
121.3 mL of an aqueous solution containing 5.6 g and an aqueous KBr solution were added by a double jet method over 22 minutes. At this time,
The silver potential was kept at +20 mV with respect to the saturated calomel electrode. The temperature was raised to 82 ° C., and KBr was added to bring the silver potential to −80.
After adjusting to mV, Ag with a particle size of 0.037 μm
6.33 g of I fine grain emulsion was added in terms of KI weight. Immediately after the addition was completed, 206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. During the initial 5 minutes of the addition, the silver potential was kept at -80 mV with an aqueous KBr solution.
After washing with water, gelatin was added, and pH 5.8, p
Ag was adjusted to 8.7. After adding compounds 11 and 12, the temperature was raised to 60 ° C. After the addition of sensitizing dyes 11 and 12, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. At the end of the chemical sensitization, Compound 13 and Compound 14 were added. Here, the optimal chemical sensitization means that the sensitizing dye and each compound are mixed with 1 mol of silver halide.
It means that it was selected from the added amount range of 10 ^-1 to 10 ^-8 mol per ¹ .

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[0199]

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[0202]

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As a result of observing the obtained particles with a transmission electron microscope while cooling them with liquid nitrogen, it was found that about 90% of all particles had one or more dislocations within 80% of the projected area from the center of the particles. Eight dislocation lines were present per grain having one or more dislocation lines. In addition, an average of 12 dislocation lines per grain were observed in a grain peripheral portion having a projected area of 20% from the grain peripheral portion.

(Emulsion A-2) 9.9 g of the aforementioned seed emulsion
After the addition, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , 7.0 g of AgNO ₃
And a KBr aqueous solution were added over a period of 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. Sodium benzenethiosulfonate 2mg and thiourea dioxide 2m
g, and 381 mL of an aqueous solution containing 134.4 g of AgNO ₃ and an aqueous solution of KBr are accelerated by a double jet method so that the final flow rate is 3.7 times the initial flow rate, and 5
Added over 6 minutes. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was added to a silver iodide content of 7 mol.
% While simultaneously accelerating the flow rate and adding the silver potential to -30 mV with respect to the saturated calomel electrode. Ag
121.3 mL of an aqueous solution containing 45.6 g of NO ₃ and KBr
The aqueous solution was added by the double jet method over 22 minutes.
At this time, the silver potential was +20 mV with respect to the saturated calomel electrode.
Kept. The temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −80 mV, and then 6.33 g of an AgI fine grain emulsion having a grain size of 0.037 μm was added in terms of KI weight. Immediately after the addition was completed, 206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. During the initial 5 minutes of the addition, the silver potential was kept at -80 mV with an aqueous KBr solution. After washing with water, gelatin was added, and pH 5.
8, pAg was adjusted to 8.7. Subsequent steps were performed for Emulsion A-
The same processing as in Example 1 was performed.

As a result of observing the obtained particles with a transmission electron microscope while cooling the particles with liquid nitrogen, it was found that about 98% of all particles having no dislocation existed within 80% of the projected area from the center of the particles.
%Met. On the other hand, 13 dislocation lines per grain were observed on average from the grain periphery to the grain periphery having a projected area of 20%.

(Emulsion A-3) 9.9 g of the aforementioned seed emulsion
After the addition, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , 7.0 g of AgNO ₃
And a KBr aqueous solution were added over a period of 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. Sodium benzenethiosulfonate 2mg and thiourea dioxide 2m
g, and 284 mL of an aqueous solution containing 100.2 g of AgNO ₃ and an aqueous solution of KBr are accelerated by a double jet method so that the final flow rate is 3.7 times the initial flow rate.
Added over 5 minutes. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was added to a silver iodide content of 7 mol.
% While simultaneously accelerating the flow rate and adding the silver potential to -30 mV with respect to the saturated calomel electrode. Ag
121.3 mL of an aqueous solution containing 45.6 g of NO ₃ and KBr
The aqueous solution was added by the double jet method over 22 minutes.
At this time, the silver potential was +20 mV with respect to the saturated calomel electrode.
Kept. After the temperature was raised to 82 ° C. and KBr was added to adjust the silver potential to −80 mV, 9.57 g of an AgI fine grain emulsion having a grain size of 0.037 μm was added in terms of KI weight. Immediately after completion of the addition, 310.5 mL of an aqueous solution containing 100.0 g of AgNO ₃ was added over 24 minutes. During the initial 7.5 minutes of the addition, the silver potential was -80 m with an aqueous KBr solution.
Kept at V. After washing with water, add gelatin and add
H5.8 and pAg8.7 were adjusted. In the subsequent steps, the same processing as in emulsion A-1 was performed.

As a result of observing the obtained particles with a transmission electron microscope while cooling them with liquid nitrogen, it was found that about 95% of all particles had one or more dislocations within 80% of the projected area from the center of the particles. Approximately 12 lines were observed per particle. In addition, about 12 dislocation lines per grain were observed from the grain periphery to the grain periphery having a projected area of 20%.

(Emulsion A-4) 9.9 g of the aforementioned seed emulsion
After the addition, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , 7.0 g of AgNO ₃
And a KBr aqueous solution were added over a period of 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. Sodium benzenethiosulfonate 2mg and thiourea dioxide 2m
g, and 381 mL of an aqueous solution containing 134.4 g of AgNO ₃ and an aqueous solution of KBr are accelerated by a double jet method so that the final flow rate is 3.7 times the initial flow rate, and 5
Added over 6 minutes. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was mixed with a silver iodide content of 3 mol.
% While simultaneously accelerating the flow rate and adding the silver potential to -30 mV with respect to the saturated calomel electrode. Ag
121.3 mL of an aqueous solution containing 45.6 g of NO ₃ and KBr
The aqueous solution was added by the double jet method over 22 minutes.
At this time, the silver potential was +20 mV with respect to the saturated calomel electrode.
Kept. The temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −80 mV, and then 6.33 g of an AgI fine grain emulsion having a grain size of 0.037 μm was added in terms of KI weight. Immediately after the addition was completed, 206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. During the initial 5 minutes of the addition, the silver potential was kept at -80 mV with an aqueous KBr solution. After washing with water, gelatin was added, and pH 5.
8, pAg was adjusted to 8.7. Subsequent steps were performed for Emulsion A-
The same processing as in Example 1 was performed.

As a result of observing the obtained particles with a transmission electron microscope while cooling them with liquid nitrogen, it was found that about 98% of the particles having no dislocation existed within 80% of the projected area from the center of the particles.
%Met. On the other hand, 13 dislocation lines per grain were observed on average from the grain periphery to the grain periphery having a projected area of 20%.

(Emulsion A-5) 9.9 g of the aforementioned seed emulsion
After the addition, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , 7.0 g of AgNO ₃
And a KBr aqueous solution were added over a period of 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. Sodium benzenethiosulfonate 2mg and thiourea dioxide 2m
g, and 381 mL of an aqueous solution containing 134.4 g of AgNO ₃ and an aqueous solution of KBr are accelerated by a double jet method so that the final flow rate is 3.7 times the initial flow rate, and 5
Added over 6 minutes. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was added to a silver iodide content of 7 mol.
% At the same time, and the silver potential was kept at -30 mV with respect to the saturated calomel electrode. Ag
121.3 mL of an aqueous solution containing 45.6 g of NO ₃ and KBr
The aqueous solution was added by the double jet method over 22 minutes.
At this time, the silver potential was +20 mV with respect to the saturated calomel electrode.
Kept. The temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −80 mV, and after the addition was completed, 317 cc of a 1% KI aqueous solution was added. Immediately, 66.4 g of AgNO ₃
206.2 mL of an aqueous solution containing was added over 16 minutes. During the initial 5 minutes of the addition, the silver potential was raised to −80 with an aqueous KBr solution.
mV. After washing with water, gelatin was added to adjust the pH to 5.8 and the pAg to 8.7 at 40 ° C. In the subsequent steps, the same processing as in emulsion A-1 was performed.

As a result of observing the obtained particles with a transmission electron microscope while cooling them with liquid nitrogen, it was found that particles having no dislocations within 80% of the projected area from the center of the particles accounted for about 98% of the total number.
Were present. In addition, an average of 12 dislocation lines per grain were observed in a grain peripheral portion having a projected area of 20% from the grain peripheral portion. At this time, the dislocations existing in the outer peripheral portion were localized near the corners of the tabular grains.

(Emulsion A-6) 9.9 g of the aforementioned seed emulsion
After the addition, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , 7.0 g of AgNO ₃
And a KBr aqueous solution were added over a period of 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. Sodium benzenethiosulfonate 2mg and thiourea dioxide 2m
g, and 381 mL of an aqueous solution containing 134.4 g of AgNO ₃ and an aqueous solution of KBr are accelerated by a double jet method so that the final flow rate becomes 3.7 times the initial flow rate, and 5
Added over 6 minutes. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was added to a silver iodide content of 7 mol.
% While simultaneously accelerating the flow rate and adding the silver potential to -30 mV with respect to the saturated calomel electrode. Ag
121.3 mL of an aqueous solution containing 45.6 g of NO ₃ and KBr
The aqueous solution was added by the double jet method over 22 minutes.
At this time, the silver potential is set to 10
The minutes were kept at +20 mV and the remaining 12 minutes at 120 mV. After cooling to 50 ° C., 55% of 0.3% KI aqueous solution
L was added over 10 minutes. Immediately thereafter, AgNO ₃
100 mL of an aqueous solution containing 14.2 g and 5.5 of NaCl
g of an aqueous solution containing 120 g was added by double jet. Immediately thereafter, an aqueous solution 12 containing 56.8 g of AgNO ₃
0 mL and an aqueous solution of KBr were added by the double jet method over 50 minutes. At this time, the silver potential was kept at +100 mV. At this time, 9.4 × 10 ⁻⁴ mol of K ₄ [Ru (CN) ₆ ] was present per 1 mol of AgNO ₃ added. After washing with water, gelatin was added, and pH 5.
8, pAg was adjusted to 8.7. Subsequent steps were performed for Emulsion A-
The same processing as in Example 1 was performed.

Observation of the obtained particles with a transmission electron microscope while cooling them with liquid nitrogen revealed that particles having no dislocations within 80% of the projected area from the center of the particles accounted for about 98% of the total number.
Were present. On the other hand, an average of 10 dislocation lines per grain were observed from the outer periphery of the grain to 20% of the projected area of the grain. When the obtained particles were observed with a scanning electron microscope, an epitaxial layer was deposited on the main plane of the tabular particles.

(Emulsion A-7) 9.9 g of the aforementioned seed emulsion
After the addition, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , 7.0 g of AgNO ₃
And a KBr aqueous solution were added over a period of 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. Sodium benzenethiosulfonate 2mg and thiourea dioxide 2m
g, and 381 mL of an aqueous solution containing 134.4 g of AgNO ₃ and an aqueous solution of KBr are accelerated by a double jet method so that the final flow rate becomes 3.7 times the initial flow rate, and 5
Added over 6 minutes. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was added to a silver iodide content of 7 mol.
% While simultaneously accelerating the flow rate and adding the silver potential to -30 mV with respect to the saturated calomel electrode. Ag
330.8 mL of an aqueous solution containing 102.4 g of NO ₃ and KB
The r aqueous solution was added by the double jet method over 60 minutes. At this time, the silver potential was set to +20 mV with respect to the saturated calomel electrode for the first 50 minutes, and 120 mV for the remaining 10 minutes.
Kept. After cooling to 50 ° C., a 0.3% KI aqueous solution 5
5 mL was added over 10 minutes. Immediately thereafter, AgN
100 mL of an aqueous solution containing 14.2 g of O ₃ and NaCl 2.
120 ml of an aqueous solution containing 1 g and 4.17 g of KBr and AgI
A solution containing 0.0133 mol of fine particles was added at the same time. At this time, 9.4 × 10 ⁻⁴ mol of K ₄ [RuCN ₆ ] was present per 1 mol of AgNO ₃ added.
Thereafter, a sensitizing dye was added (for epitaxial stabilization). After washing with water, add gelatin and add
H5.8 and pAg8.7 were adjusted. In the subsequent steps, the same processing as in emulsion A-1 was performed.

Observation of the obtained particles with a scanning electron microscope revealed that an epitaxial layer had adhered to the corners of the tabular particles.

(Emulsion A-8) 9.9 g of the aforementioned seed emulsion
After the addition, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , 7.0 g of AgNO ₃
And a KBr aqueous solution were added over a period of 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. Sodium benzenethiosulfonate 2mg and thiourea dioxide 2m
g was added, and A was added to a stirring device installed outside the reaction vessel.
762 mL of an aqueous solution containing 134.4 g of gNO ₃ and KBr
90.1 g with KI 9.46 g and molecular weight 20,000
AgBrI fine grain emulsion (average size: 0.015 μm) containing 7 mol% of silver iodide by simultaneously adding 762 mL of an aqueous solution containing 38.1 g of the above gelatin was added to the reaction vessel over 90 minutes. did. At this time, the silver potential was set to -30 with respect to the saturated calomel electrode.
mV. Aqueous solution 12 containing 45.6 g of AgNO ₃
1.3 mL and KBr aqueous solution were added by a double jet method over 22 minutes. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. The temperature was raised to 82 ° C and KBr
Was added to adjust the silver potential to -80 mV, and then 0.03
6.33 g of an AgI fine grain emulsion having a grain size of 7 μm was added in terms of KI weight. Immediately after the addition is completed, AgNO
206.2 mL of an aqueous solution containing 66.4 g of ₃ was added over 16 minutes. During the initial 5 minutes of the addition, the silver potential was kept at -80 mV with an aqueous KBr solution. After washing with water, gelatin was added to adjust the pH to 5.8 and the pAg to 8.7 at 40 ° C. In the subsequent steps, the same processing as in emulsion A-1 was performed.

As a result of observing the obtained particles with a transmission electron microscope while cooling them with liquid nitrogen, 99.8% of all particles having no dislocations within 80% of the projected area from the center of the particles.
%Were present. In addition, an average of 12 dislocation lines per grain were observed in a grain peripheral portion having a projected area of 20% from the grain peripheral portion.

(Emulsion A-9) Emulsion A-9 was prepared by changing the amount of seed emulsion, the flow rate of addition and the like in the preparation of Emulsion A-1.
Was prepared.

(Emulsion A-10) Emulsion A-2 was prepared by changing the amount of seed emulsion, the flow rate of addition and the like in the preparation of emulsion A-2.
10 was prepared.

(Preparation of Emulsion B (Em-B)) (Emulsion for Low-Sensitivity Blue-Sensitive Layer) 1192 mL of an aqueous solution containing 0.96 g of low-molecular-weight gelatin and 0.9 g of KBr was maintained at 40 ° C. and stirred vigorously.
37.5 mL of an aqueous solution containing 1.49 g of AgNO ₃ and KB
37.5 mL of an aqueous solution containing 1.5 g of r was added over 30 seconds by the double jet method. After adding 1.2 g of KBr, the temperature was raised to 75 ° C. to ripen. After aging sufficiently, the amino group is chemically modified with trimellitic acid, and has a molecular weight of 10,000.
30 g of trimellitated gelatin at pH 0 and pH 7
Was adjusted. 6 mg of thiourea dioxide were added. AgN
116 mL of an aqueous solution containing 29 g of O ₃ and an aqueous KBr solution were added by double jet method at an accelerated flow rate such that the final flow rate was three times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. AgNO ₃ 11
440.6 mL of an aqueous solution containing 0.2 g and an aqueous KBr solution were added by a double jet method over a period of 30 minutes by accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the AgI fine grain emulsion used in the preparation of Em-1 was simultaneously added at an accelerated flow rate so that the silver iodide content became 15.8 mol%, and the silver potential was kept at 0 mV with respect to the saturated calomel electrode. Was. 96.5 mL of an aqueous solution containing 24.1 g of AgNO ₃ and an aqueous KBr solution were added over 3 minutes by a double jet method. At this time, the silver potential was kept at 0 mV.
After adding 26 mg of sodium ethylthiosulfonate, the temperature was lowered to 55 ° C., and an aqueous KBr solution was added to lower the silver potential to −.
Adjusted to 90 mV. The AgI fine grain emulsion described above was used for KI
8.5 g was added in terms of weight. Immediately after addition is complete, Ag
228 mL of an aqueous solution containing 57 g of NO ₃ was added over 5 minutes. At this time, it was adjusted with an aqueous KBr solution so that the potential at the end of the addition was +20 mV. It was washed with water and chemically sensitized almost in the same manner as Em-1.

(Preparation of Emulsion C (Em-C)) (Emulsion for low-sensitivity blue-sensitive layer) 1.02 g of phthalated gelatin containing 35 μmol of methionine per gram and having a molecular weight of 100,000 and a phthalation rate of 97%, and KBr of 0.97 g Aqueous solution containing 1192m
L was kept at 35 ° C. and stirred vigorously. AgNO ₃ 4.4
42 mL of an aqueous solution containing 7 g and 42 mL of an aqueous solution containing 3.16 g of KBr were added by a double jet method over 9 seconds. After adding 2.6 g of KBr, the temperature was raised to 66 ° C., and the mixture was sufficiently aged. After aging, 41.2 g of trimellitated gelatin having a molecular weight of 100,000 used in the preparation of Em-B
And 18.5 g of NaCl were added. After adjusting the pH to 7.2, 8 mg of dimethylamine borane was added. A
203 mL of an aqueous solution containing 26 g of gNO ₃ and an aqueous KBr solution were added by a double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode. AgNO ₃ 110.2
g of an aqueous solution containing 44 g and a KBr aqueous solution were added over 24 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, Em
AgI fine grain emulsion used in the preparation of -1 was simultaneously added at an accelerated flow rate such that the silver iodide content was 2.3 mol%, and the silver potential was -20 m with respect to the saturated calomel electrode.
Kept at V. 9. 1N aqueous potassium thiocyanate solution
After adding 7 mL, 153.5 mL of an aqueous solution containing 24.1 g of AgNO ₃ and an aqueous KBr solution were added over 2 minutes and 30 seconds by a double jet method. At this time, the silver potential was 10 m
Kept at V. An aqueous KBr solution was added to reduce the silver potential to -70 m.
Adjusted to V. 6.4 g of the above-mentioned AgI fine grain emulsion was added in terms of KI weight. Immediately after the addition, AgNO ₃
404 mL of an aqueous solution containing 57 g was added over 45 minutes. At this time, it was adjusted with an aqueous KBr solution so that the potential at the end of the addition was -30 mV. It was washed with water and chemically sensitized almost in the same manner as Em-1.

(Preparation of Emulsion D (Em-D)) (Emulsion of low-sensitivity blue-sensitive layer) In the preparation of Em-C, the amount of AgNO ₃ added during nucleation was changed to 2.0 times. And the final AgNO ₃ 57g
Potential at the end of addition of 404 mL of an aqueous solution containing
V was changed to be adjusted with an aqueous KBr solution. Except for this, it was prepared in substantially the same manner as in Em-C.

(Preparation of Emulsion E (Em-E)) (Magenta color-forming layer having a spectral sensitivity peak at 480 to 550 nm) (Layer giving a multilayer effect to red-sensitive layer) 0.71 g of low molecular weight gelatin having a molecular weight of 15,000, KBr 0.92 g, E
1200 mL of an aqueous solution containing 0.2 g of the modified silicone oil used in the preparation of m-1 was kept at 39 ° C., and the pH was 1.8.
And stirred vigorously. An aqueous solution containing 0.45 g of AgNO ₃ and an aqueous KBr solution containing 1.5 mol% of KI were added by a double jet method over 17 seconds. At this time, K
The excess concentration of Br was kept constant. The temperature was raised to 56 ° C. and ripened. After ripening sufficiently, phthalation rate 97% with molecular weight 100,000 containing 35 μmol methionine per gram
Of phthalated gelatin was added. After adjusting the pH to 5.9, 2.9 g of KBr was added. AgNO ₃ 2
288 mL of an aqueous solution containing 8.8 g and an aqueous KBr solution were added over 53 minutes by a double jet method. At this time, Em
AgI fine grain emulsion used in the preparation of -1 was simultaneously added so that the silver iodide content became 4.1 mol%, and the silver potential was kept at -60 mV with respect to the saturated calomel electrode.
After adding 2.5 g of KBr, the aqueous solution containing 87.7 g of AgNO ₃ and the aqueous KBr solution were accelerated by a double jet method so that the final flow rate was 1.2 times the initial flow rate, and 63%.
Added over minutes. At this time, the above AgI fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content became 10.5 mol%, and the silver potential was kept at -70 mV. After adding 1 mg of thiourea dioxide, AgNO ₃ 4
132 mL of an aqueous solution containing 1.8 g and an aqueous KBr solution were added over 25 minutes by a double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After adding 2 mg of sodium benzenethiosulfonate, the pH was adjusted to 7.3. After KBr was added to adjust the silver potential to -70 mV, 5.73 g of the above-mentioned AgI fine grain emulsion was added in terms of KI weight. Immediately after the completion of the addition, 609 m of an aqueous solution containing 66.4 g of AgNO ₃
L was added over 10 minutes. KB for 6 minutes at the beginning of addition
The silver potential was maintained at -70 mV with the r aqueous solution. After washing with water,
Gelatin was added to adjust the pH to 6.5 and the pAg to 8.2 at 40 ° C. After adding compounds 1 and 2, the temperature was raised to 56 ° C. After the above AgI fine grain emulsion was added in an amount of 0.0004 mol per 1 mol of silver, sensitizing dyes 13 and 14 were added. Potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Compound 13 at the end of chemical sensitization
And 14 were added.

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(Production Method of Emulsion F (Em-F)) (Emulsion for Mid-Sensitive Green-Sensitive Layer) Em-E was prepared except that the amount of AgNO ₃ added during nucleation was changed to 3.1 times in the preparation of Em-E. It was prepared in substantially the same manner as described above. However, the sensitizing dye of Em-E was replaced with sensitizing dyes 12, 1
Changed to 5, 16 and 17.

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[0229]

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(Production Method of Emulsion G (Em-G))
Emulsion for sensitive layer) 0.70 g of low molecular weight gelatin having a molecular weight of 15,000, KB
r 0.9 g, KI 0.175 g, used in the preparation of Em-1
Aqueous solution 120 containing 0.2 g of modified silicone oil used
Keep 0 mL at 33 ° C, adjust the pH to 1.8, and vigorously shake.
Stirred. AgNO_ThreeAn aqueous solution containing 1.8 g and 3.2 mo
9% aqueous KBr solution containing 1% KI by double jet method
Added over seconds. At this time, the excess concentration of KBr is kept constant.
Kept. The temperature was raised to 69 ° C. to ripen. After aging, 1g
Molecular weight 10 containing 35 μmol methionine per
0000 amino group chemically modified with trimellitic acid
27.8 g of remelted gelatin was added. pH
After adjusting to 6.3, 2.9 g of KBr was added. Ag
NO_Three270 mL of an aqueous solution containing 27.58 g and KBr water
The solution was added by the double jet method over 37 minutes. This
, A low molecular weight gelatin aqueous solution having a molecular weight of 15,000 and A
gNO_ThreeAn aqueous solution and a KI aqueous solution are disclosed in JP-A-10-43570.
Having a magnetic coupling induction stirrer as described in
Particle size prepared by mixing just before addition in the chamber
The silver iodide content of a 0.008μ AgI fine grain emulsion was
At the same time so as to be 4.1 mol%, and silver potential
Was kept at -60 mV with respect to the saturated calomel electrode. KB
After adding 2.6 g of AgNO, AgNO _ThreeIncluding 87.7g
The final flow rate of aqueous solution and KBr aqueous solution by double jet method
49 minutes by accelerating the flow rate to 3.1 times the initial flow rate
Was added. At this time, mix immediately before the above-mentioned addition and prepare.
The prepared AgI fine grain emulsion was adjusted to have a silver iodide content of 7.9 mol.
1% at the same time and accelerate the silver potential to -7.
It was kept at 0 mV. After adding 1 mg of thiourea dioxide,
AgNO_Three132 mL of an aqueous solution containing 41.8 g and KBr
The aqueous solution was added by the double jet method over 20 minutes.
KBr aqueous solution so that the potential at the end of the addition becomes +20 mV
The addition of the liquid was adjusted. Raise the temperature to 78 ° C and raise the pH to 9.1
After adjustment, KBr was added to bring the potential to -60 mV.
Was. The AgI fine grain emulsion used in the preparation of Em-1 was prepared using KI
5.73 g in terms of weight was added. Immediately after the addition,
gNO_Three321 mL of an aqueous solution containing 66.4 g in 4 minutes
Migrated. During the initial 2 minutes of the addition, use an aqueous KBr solution for silver electrolysis.
The position was kept at -60 mV. Rinse almost the same as Em-F
And chemically sensitized.

(Preparation of Emulsion H (Em-H)) (Emulsion for low-sensitivity green-sensitive layer) Ion-exchanged gelatin having a molecular weight of 100,000 and 17.8.
g, 6.2 g of KBr and 0.46 g of KI were kept at 45 ° C. and vigorously stirred. AgNO ₃ 11.85 g
And an aqueous solution containing 3.8 g of KBr were added over 47 seconds by the double jet method. After heating to 63 ° C,
Ion-exchanged gelatin having a molecular weight of 100,000 24.1
g was added and aged. After aging sufficiently, AgNO ₃ 1
An aqueous solution containing 33.4 g and an aqueous KBr solution were mixed by a double jet method so that the final flow rate was 2.6 times the initial flow rate.
Added over minutes. At this time, the silver potential was kept at +40 mV with respect to the saturated calomel electrode. Ten minutes after the start of the addition, 0.1 mg of K ₂ IrCl ₆ was added. NaCl 7
g of an aqueous solution containing 45.6 g of AgNO ₃ and K
The aqueous Br solution was added by the double jet method over 12 minutes. At this time, the silver potential was kept at +90 mV. An aqueous solution 1 containing 29 mg of yellow blood salt for 6 minutes from the start of addition.
00 mL was added. After adding 14.4 g of KBr,
6.3 g of the AgI fine grain emulsion used in the preparation of Em-1 was added in terms of KI weight. Immediately after the addition is completed, AgNO
_An aqueous solution containing 32.7 g of ₃ and an aqueous KBr solution were added by a double jet method over 11 minutes. At this time, the silver potential is increased by +
It was kept at 90 mV. It was washed with water and chemically sensitized almost in the same manner as Em-F.

(Preparation Method of Emulsion I (Em-I)) (Emulsion for Low-Sensitive Green-Sensitive Layer) The preparation was performed in substantially the same manner as in the preparation of Em-H except that the temperature during nucleation was changed to 38 ° C.

(Production Method of Emulsion J (Em-J)) (Emulsion for High-Sensitivity Red-Sensitive Layer) An aqueous solution 120 containing 0.38 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000 and 0.99 g of KBr
0 mL was kept at 60 ° C., the pH was adjusted to 2, and the mixture was stirred vigorously. Aqueous solution containing 1.96 g of AgNO ₃ and 1.9 KBr
An aqueous solution containing 7 g and 0.172 g of KI was added by a double jet method over 30 seconds. After ripening, molecular weight 1000 containing 35 μmol of methionine per 1 g
12.8 g of trimellitated gelatin obtained by chemically modifying the amino group of No. 00 with trimellitic acid was added. pH 5.9
2.99 g of KBr and 6.2 g of NaCl
Was added. Aqueous solution containing 27.3 g of AgNO ₃ 60.
7 mL and an aqueous KBr solution were added by the double jet method over 35 minutes. At this time, the silver potential was kept at -50 mV with respect to the saturated calomel electrode. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over a period of 37 minutes while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate. At this time, A used in the preparation of Em-1
The gI fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content was 6.5 mol%, and the silver potential was -5.
It was kept at 0 mV. After adding 1.5 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and K were added.
An aqueous Br solution was added over 13 minutes by the double jet method. KB so that the silver potential at the end of the addition becomes +40 mV.
The addition of the r aqueous solution was adjusted. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to -100 mV. The above AgI fine grain emulsion was added in an amount of 6.2 g in terms of KI weight. Immediately after the addition was completed, 300 mL of an aqueous solution containing 88.5 g of AgNO ₃ was added over 8 minutes. Adjustment was made by adding an aqueous KBr solution so that the potential at the end of the addition was +60 mV. After washing with water, gelatin was added to adjust the pH to 6.5 and the pAg to 8.2 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 61 ° C. After addition of sensitizing dye 18, 19, 20 and 21, K ₂ IrCl _6, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, it was optimally chemically sensitized by adding N- dimethylselenourea. At the end of chemical sensitization, compounds 13 and 14 were added.

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[0237]

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(Production Method of Emulsion K (Em-K))
Emulsion for sensitive layer) 4.9 g of low molecular weight gelatin having a molecular weight of 15,000, KBr
1200 mL of an aqueous solution containing 5.3 g was kept at 60 ° C and vigorously
Stirred well. AgNO_Three27m of aqueous solution containing 8.75g
36 mL of an aqueous solution containing L and 6.45 g of KBr in one minute
It was added by the migrating double jet method. Heated to 77 ° C
Later, AgNO_Three21 mL of an aqueous solution containing 6.9 g
Added over minutes. NH_FourNO_Three26g, 1N NaO
After successively adding 56 mL of H, the mixture was aged. After aging
The pH was adjusted to 4.8. AgNO _ThreeWater containing 141g
Aqueous solution 45 containing 438 mL of solution and 102.6 g of KBr
8mL by double jet method, final flow rate is 4 times of initial flow rate
Was added so that After cooling to 55 ° C, AgNO
_Three240 mL of an aqueous solution containing 7.1 g and 6.46 g of KI
And add the aqueous solution over 5 minutes by double jet method
Was. After adding 7.1 g of KBr, benzenethiosulfo
Sodium acid 4mg and K_TwoIrCl₆ 0.05mg
Added. AgNO_Three177 mL of an aqueous solution containing 57.2 g
223 mL of an aqueous solution containing 40.2 g of KBr in 8 minutes
Added over the double jet method. Almost same as Em-J
Washed in the same manner and chemically sensitized.

(Preparation of Emulsion L (Em-L)) (Emulsion for Medium-Sensitive Red-Sensitive Layer) The preparation was carried out in substantially the same manner as in the preparation of Em-K, except that the temperature during nucleation was changed to 42 ° C.

(Emulsions M, N, O (Em-M, -N,-
Production method of O)) (Emulsion for low-sensitivity red-sensitive layer) It was prepared in substantially the same manner as in Em-H or Em-I. However, the chemical sensitization was performed in substantially the same manner as in Em-J.

(Preparation of Emulsion P (Em-P)) (Emulsion for Highly Sensitive Green-Sensitive Layer) (Preparation of Seed Emulsion a) 0.017 g of KBr, average molecular weight 2
Aqueous solution 11 containing 0.4 g of 0000 oxidized gelatin
64 mL was kept at 60 ° C. and stirred. AgNO ₃ (1.6
g) An aqueous solution, an aqueous KBr solution, and an aqueous solution of oxidized gelatin (2.1 g) having an average molecular weight of 20,000 were added over 30 seconds by a triple jet method. At this time, the silver potential was kept at 13 mV with respect to the saturated calomel electrode. An aqueous KBr solution was added to adjust the silver potential to −66 mV, and then the temperature was raised to 60 ° C. 21 g of succinated gelatin having an average molecular weight of 100,000
Was added, and an aqueous solution of NaCl (5.1 g) was added. An aqueous solution of AgNO ₃ (206.3 g) and an aqueous solution of KBr were added over 61 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -44 mV with respect to the saturated calomel electrode. After desalting, the average molecular weight is 100
000 succinated gelatin and pH 5 at 40 ° C.
8, pAg was adjusted to 8.8, and seed emulsion a was prepared. This seed emulsion contains 1 mol of Ag and 80 g of gelatin per kg of emulsion, and is a tabular grain having an average equivalent circle diameter of 1.46 μm, a coefficient of variation of equivalent circle diameter of 28%, an average thickness of 0.046 μm, and an average aspect ratio of 45. there were.

(Formation of core) 134 g of the above seed emulsion a was prepared.
1200 mL of an aqueous solution containing 1.9 g of KBr and 22 g of succinated gelatin having an average molecular weight of 100,000 was stirred at 75 ° C. AgNO ₃ (43.9 g) aqueous solution and KBr
An aqueous solution and an aqueous solution of gelatin having a molecular weight of 20,000 are disclosed in
In a separate chamber having a magnetic coupling induction stirrer as described in U.S. Pat.
Added over minutes. At this time, the silver potential was kept at -40 mV with respect to the saturated calomel electrode.

(Formation of First Shell) After the formation of the core particles, an aqueous solution of AgNO ₃ (43.9 g), an aqueous solution of KBr, and an aqueous solution of gelatin having a molecular weight of 20,000 were mixed just before the addition in another chamber in the same manner as above to form a solution. Added over minutes. At this time, the silver potential was set to −40 with respect to the saturated calomel electrode.
mV.

(Formation of Second Shell) After the formation of the first shell, an aqueous solution of AgNO ₃ (42.6 g), an aqueous solution of KBr, and an aqueous solution of gelatin having a molecular weight of 20,000 were mixed immediately before addition in another chamber of the same type. Added over 17 minutes. At this time, the silver potential was set to -20 with respect to the saturated calomel electrode.
mV. Thereafter, the temperature was lowered to 55 ° C.

(Formation of Third Shell) After the formation of the second shell, the silver potential was adjusted to -55 mV, and AgNO ₃ (7.
1 g) aqueous solution, KI (6.9 g) aqueous solution and molecular weight 200
The gelatin aqueous solution of No. 00 was mixed immediately before the addition in another chamber as above and added over 5 minutes.

(Formation of Fourth Shell) After the formation of the third shell, an aqueous solution of AgNO ₃ (66.4 g) and an aqueous solution of KBr were added at a constant flow rate over 30 minutes by a double jet method. On the way, iridium potassium hexachloride and yellow blood salt were added. At this time, the silver potential is set at 30 with respect to the saturated calomel electrode.
mV. Perform normal water washing, add gelatin,
PH was adjusted to 5.8 and pAg to 8.8 at 40 ° C. This emulsion was designated as emulsion b. Emulsion b had an average equivalent circle diameter of 3.3 μm,
Coefficient of variation of equivalent circle diameter 21%, average thickness 0.090μm,
The tabular grains had an average aspect ratio of 37. Further, 70% or more of the total projected area has a circle equivalent diameter of 3.3 μ or more and a thickness of 0.3 μm.
Occupied by tabular grains of 090 μm or less.

Table 1 shows the properties of the silver halide emulsions A-1 to A-10 thus obtained, and Table 2 shows the properties of the silver halide emulsions A-1 to A-P.

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[Table 2]

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

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

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

3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were applied as a back layer to one surface of the support after the undercoat.

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

3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ²⁾ / G, major axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 emu
/ G, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06
g / m ² to diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out with an open kneader and a sand mill),
_{C 2 H 5 C (CH 2} OCONH-C 6 H 3 as a curing agent (C
0.3 g / m ² of H ₃ ) NCO) ₃ was applied with a bar coater using acetone, methyl ethyl ketone and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. 10 mg each of an abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as a matting agent / M
² was added. Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.).
° C). X- write saturation magnetization moment 4.2 emu / g to about 0.1, and the magnetic recording layer color density increment of D ^B of the magnetic recording layer in the (blue filter), the coercive force 7.3 ×
10 ⁴ A / m and the squareness ratio were 65%.

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

4) Coating of Photosensitive Layer Next, on the side opposite to the back layer obtained above, each layer having the following composition was applied in a multi-layered manner to prepare a sample 1 as a color negative photosensitive material.
01 was created. Further, Samples 102 to 110 were prepared by replacing the silver iodobromide emulsion A-1 in the fourteenth layer with the emulsions A-2 to A-10, respectively.

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

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.155 0.07μ Surface Fogged AgBrI (2) Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-30 002 Cpd-2 0.001 HBS-1 0.004 HBS-2 0.002.

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

Third layer (middle layer) AgBrI (2) 0.07μ 0.020 ExC-2 0.022 polyethyl acrylate latex 0.085 gelatin 0.294.

Fourth layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromochloride emulsion M silver 0.065 silver iodobromochloride emulsion N silver 0.100 silver iodobromochloride emulsion O silver 0.158 ExC-1 0.109 ExC-3 0.044 ExC-4 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.17 Gelatin 0.80.

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion K Silver 0.21 Silver Iodobromide Emulsion L Silver 0.62 ExC-1 0.14 ExC-2 0.026 ExC-30 0.020 ExC-4 0.12 ExC-5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18.

Sixth Layer (High Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromochloride Emulsion J Silver 1.67 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY- 5 0.008 Cpd-2 0.046 Cpd-4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12.

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

Eighth Layer (Multilayer Effect Donor Layer (Layer that Gives a Multilayer Effect to the Red Sensitive Layer)) Silver Iodobromide Emulsion 0.560 Cpd-4 0.030 ExM-2 0.096 ExM-30 028 ExY-1 0.031 ExG-1 0.006 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion G silver 0.39 silver iodobromochloride emulsion H silver 0.28 silver iodobromochloride emulsion I silver 0.35 ExM-2 0.36 ExM-3 0.045 ExG-1 0.005 HBS-1 0.28 HBS-3 0.01 HSB-4 0.27 Gelatin 1.39.

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion F 0.20 Silver Iodobromide Emulsion G Silver 0.25 ExC-6 0.009 ExM-2 0.031 ExM-30 0.029 ExY-1 0.006 ExM-4 0.028 ExG-1 0.005 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 gelatin 0.44.

Eleventh Layer (High Sensitive Green Sensitive Emulsion Layer) Silver Iodobromochloride Emulsion P Silver 1.200 ExC-6 0.004 ExM-1 0.016 ExM-3 0.036 ExM-4 0.020 ExM- 5 0.004 ExY-5 0.003 ExM-2 0.013 ExG-1 0.005 Cpd-4 0.007 HBS-1 0.18 Polyethyl acrylate latex 0.099 Gelatin 1.11.

Twelfth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.047 Cpd-1 0.16 Solid Disperse Dye ExF-5 0.010 Solid Disperse Dye ExF-6 0.010 HBS-1 0.082 Gelatin 1 0.057 thirteenth layer (low-sensitivity blue-sensitive emulsion layer) silver iodobromide emulsion B silver 0.18 silver iodobromochloride emulsion C silver 0.20 silver iodobromochloride emulsion D silver 0.07 ExC-1 0.041 ExC -8 0.012 ExY-1 0.035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0. 24 Gelatin 1.41.

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion A-1 silver 0.75 ExC-1 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd-2 0.075 Cpd-3 1.0 × 10 ⁻³ HBS-1 0.10 Gelatin 0.91.

Fifteenth layer (first protective layer) 0.07 μg of AgBrI (2) silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F- 18 0.009 F-19 0.005 F-20 0.005 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3.

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

Further, each layer may have a storability, a processing property, a pressure resistance, a fungicide / antibacterial property, B-4 to B-6, F-1 to F-18, and iron salts, lead salts, and gold salts. , Platinum salts, palladium salts, iridium salts, ruthenium salts and rhodium salts. The coating solution for the eighth layer was 8.5 × 10 ^-3 g per mol of silver halide, and the coating solution for the eleventh layer was 7.9 × 1-3.
0 ^-3 grams of calcium was added at calcium nitrate solution, to prepare a sample. Furthermore, at least one kind of W-1, W-6, W-7, and W-8 is contained for improving antistatic property, and at least one kind of W-2 and W-5 is provided for improving applicability. Contains.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-3 shown below was dispersed by the following method. That is, water 2
1.7 mL and 5 mL of 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonic acid 3 mL and 5 mL
A 0.5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) was placed in a 700 mL pot mill, and 5.0 g of the dye ExF-2 and 500 mL of zirconium oxide beads (1 mm in diameter) were added. Was dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersing, take out the contents,
It was added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.

Similarly, a solid dispersion of ExF-4 was obtained. The average particle size of the fine dye particles is 0.24 μm, respectively.
It was 0.45 μm and 0.52 μm. ExF-2 is a microprecipipi described in Example 1 of EP-A-549,489A.
station) and dispersed by a dispersion method. The average particle size was 0.06 μm.

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

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

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

[0281]

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[0282]

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[0283]

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[0284]

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[0285]

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[0286]

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[0287]

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[0288]

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[0289]

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[0290]

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[0291]

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[0292]

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[0293]

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[0294]

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[0295]

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The evaluation method of the sample is as follows. Exposure was performed for 1/100 second through a gelatin filter SC-39 (a long-wavelength light transmission filter having a cut-off wavelength of 390 nm) manufactured by FUJIFILM Corporation and a continuous wedge. The development was performed as follows using an automatic developing machine FP-360B manufactured by Fuji Photo Film Co., Ltd. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in Hatsumei Kyokai Disclosure Technique No. 94-4992.

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

(Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5mL Fixing (1) 50 seconds 38.0 ° C-5L Fixing ( 2) 50 seconds 38.0 ℃ 8 mL 5L water washing 30 seconds 38.0 ℃ 17 mL 3L stable (1) 20 seconds 38.0 ℃-3L stable (2) 20 seconds 38.0 ℃ 15 mL 3L drying 1 minute 30 seconds 60.0 ℃ * replenishment amount Is per 35 m of photosensitive material and 1.1 m in width (equivalent to 24 Ex. 1 line)

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

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

The composition of the processing liquid is shown below.

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

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

(Fixing (1) tank liquid) A 5/95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid (pH:
6.8).

(Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 721 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 13 39 Add water 1.0L 1.0L pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45.

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 m.
g / L or less, followed by sodium diisocyanurate 20 mg / L and sodium sulfate 150 mg / L
Was added. The pH of this solution was in the range of 6.5 to 7.5.

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

In order to evaluate the pressure property of the sample, the following test was performed. The sample was conditioned at 25 ° C and 55%, and the load was 4 g.
The surface of the emulsion was scratched in a fixed direction with a fine needle of 0.05 mm overlaid with, and then exposed and developed by the method described above.

Table 3 shows the obtained results. Further, after the sample is subjected to the same scratching treatment as described above, the emulsion of the 14th layer high-sensitivity blue-sensitive layer is carefully so as not to apply pressure as to generate new dislocation lines in the grains contained therein. The sample was taken out, placed on a mesh for an electron microscope, and observed by a transmission method in a state where the sample was cooled with liquid nitrogen so as to prevent damage to the electron beam. In the table, the symbol ○ means that pressure desensitization by the fine needle is hardly observed in the yellow part, and ×
Means that pressure desensitization was observed.

[0310]

[Table 3]

As is clear from Tables 1 and 3, the grains having no dislocation line within 80% of the projected area from the center of the grains have few stress dislocations, and do not exhibit pressure desensitization. It can be seen that the emulsion was excellent. Samples 102, 104, 105, 106, 107 using the emulsion of the present invention,
And No. 108 were able to realize a multilayer color photosensitive material having high sensitivity and excellent pressure resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) G03C 1/035 G03C 1/035 L 1/015 1/015 7/00 510 7/00 510 7/20 7 / 20

Claims (10)

[Claims] 1. In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, 50% or more of the projected area of all silver halide grains contained in the emulsion layer is projected. The silver halide grains having an area diameter of 2.0 μm or more are occupied by silver halide grains having a projected area diameter of 2.0 μm or more when a specific pressure is applied to the photosensitive material. (A) does not include stress dislocations. 2. The halogenated silver halide according to claim 1, wherein 90% or more of the total projected area of the silver halide grains having a projected area diameter of 2 μm or more are tabular grains having an aspect ratio of 2 or more. Silver photographic photosensitive material. 3. The halogenated halide according to claim 1, wherein 90% or more of the total projected area of the silver halide grains having a projected area diameter of 2 μm or more are tabular grains having an aspect ratio of 10 or more. Silver photographic photosensitive material. 4. The silver halide grains having a projected area diameter of 2 μm or more, wherein grains having no dislocation line within 80% from the center of the main surface occupy 90% or more of the whole grains. Item 4. The silver halide photographic material according to any one of Items 1 to 3. 5. The silver halide grain having a projected area diameter of 2 μm or more, wherein the average AgI content within 70% from the center of the grain is 5 mol% or more. 5. The silver halide photographic light-sensitive material according to any one of 4. 6. The silver halide grain having a projected area diameter of 2 μm or more, in which dislocations are localized substantially only in a corner portion of the silver halide grain. 2. The silver halide photographic light-sensitive material according to item 1. 7. A silver halide grain having a projected area diameter of 2 μm or more, wherein the grain has a form in which a silver halide epitaxial grain is substantially bonded to a silver halide base grain. A silver halide photographic material according to any one of claims 1 to 5. 8. In the silver halide grains having a projected area diameter of 2 μm or more, the growth of grains having at least 50% of the total silver amount is performed simultaneously with the addition of the silver salt aqueous solution and the halogen salt aqueous solution. 8. The silver halide photograph according to claim 1, wherein the fine particles are formed by adding silver iodide fine particles formed outside the container to the container in which the growth is performed. Photosensitive material. 9. In the silver halide grains having a projected area diameter of 2 μm or more, at least 50% or more of the total silver amount is grown outside the vessel in which the silver halide grains are grown. 8. A silver halide photographic light-sensitive material according to claim 1, wherein said silver halide photographic light-sensitive material is prepared by adding phthalocyanine to a vessel in which growth is performed. 10. The photosensitive silver halide emulsion layer according to claim 1, wherein
The silver halide photographic light-sensitive material according to any one of claims 1 to 9, wherein the light-sensitive silver halide emulsion layer is located farthest from the support among all the light-sensitive silver halide emulsion layers.