JPH095909A - Silver halide emulsion and its manufacture and silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE: To provide a silver halide emulsion high in sensitivity, a θ value, and image quality and superior in rapid processing aptitude, storage stabil1ity, and resistance to processing fluctuation and to provide its manufacture and the silver halide photographic sensitive maternal and its processing method. CONSTITUTION: [1] The silver halide emulsion contains at least >=50mol% silver chloride and flat silver halide grains in >=50% of the projection areas of the total silver halide grains and these flat grains have principal faces (100) each having an ajacent side ratio of <10 and an average aspect ratio of >=2 and a $ 20 % variation coefficient of the diameters of projected principal faces, and [2] the manufacturing method of the emulsion comprises a series of (1) a process adding a silver salt and initiating formation of nuclei on the absence of iodide and (2) a process adding a silver salt and executing formation of nuclei and/or crystals in the presence of iodide, and [3] the silver halide photographic sensitive material contains the emulsion of [1] in at least one of the emulsion layers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion, a method for producing a silver halide emulsion, a silver halide photographic light-sensitive material and a processing method thereof. In particular, in the fields related to silver halide emulsions containing tabular silver halide grains, a technique is provided that has high sensitivity, high γ, high image quality, rapid processing suitability, and excellent storage stability and processing fluctuation characteristics. It is a thing.

[0002]

2. Description of the Related Art In recent years, with regard to the development processing of silver halide photographic light-sensitive materials, it has been increasingly desired to shorten the processing time and the processing waste liquid. For example, in the medical field, inspections including regular medical examinations, widespread use of medical checkups, and diagnostics in general medical care have rapidly increased, which has resulted in an increase in the number of X-ray photographs taken and a further speeding up of the development process after photography. And the demand for further reduction of processing waste liquid is increasing more and more.

However, in order to speed up processing, development,
It is necessary to shorten the processing time of each processing step such as fixing, washing with water, and drying, which increases the load on each step. For example, if the developing time is simply shortened, in the conventional photosensitive material, the image density is lowered, that is, the sensitivity is lowered and the gradation is deteriorated. Further, if the fixing time is shortened, the fixing of silver halide becomes incomplete, which causes deterioration of image quality. Therefore, in order to solve such a problem, it is necessary to accelerate the developing speed and the fixing speed.

In order to accelerate the developing speed and fixing speed,
It is preferable to reduce the silver iodide content of the silver halide grains. However, it is known that when the average silver iodide content is lowered, the intrinsic sensitivity of silver halide is lowered.
Further, when the silver iodide content on the silver halide surface is reduced, the adsorptivity of the spectral sensitizing dye is deteriorated and the spectral sensitivity is lowered, or the sensitometric fluctuation with time increases,
It is known that pressure resistance may deteriorate. Further, it is known that if the silver iodide content in the silver halide is reduced, the pressure resistance may deteriorate.

Therefore, in the field of silver halide photographic light-sensitive materials, it is desired to develop a technique for accelerating the developing speed and the fixing speed.

It is known that it is preferable to add silver chloride to silver halide grains in order to accelerate the developing speed and fixing speed.

On the other hand, however, the use of silver chloride causes a great deal of desensitization and an increase in fog, and the sensitivity and gradation of the development process are largely varied, which makes it very difficult to put into practical use.

By the way, in recent years, many techniques for improving sensitivity and high image quality using tabular silver halide grains have been disclosed, and examples thereof are disclosed in JP-A-58-111935,
58-111936, 58-111937, 58-113927, 59-99433 and the like.

These tabular silver halide grains have a large surface area in the same volume as compared with so-called normal crystal silver halide grains such as hexahedron, octahedron, etc., so that the adsorption amount of the sensitizing dye on the grain surface is increased. This is possible, and as a result, there is an advantage that high sensitivity can be achieved.

Further, JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content inside a tabular silver halide grain, and JP-A-63-151618 discloses a hexagonal tabular shape. The technique of using silver halide grains is disclosed and the effect of increasing the sensitivity is shown.

In addition to this, JP-A-63-106746
JP-A-1-183644 and JP-A-1-27923.
No. 7 and the like disclose techniques relating to the composition distribution of tabular silver halide grains. In addition, JP-A-5-281640
No. 5,313,273 and No. 6-19028 disclose the technology of tabular silver halide grains having a (100) plane as a main plane, all of which have high sensitivity and high image quality. This is a targeted technique for grains having a high silver iodide content, and no solution to the problem of grains having a high silver chloride content is described.

For tabular grains containing silver chloride, (11
1) Several tabular grains having the principal plane of the (1) plane have been proposed and published, but all of these are techniques for forming the (111) plane with an additive. It had a great adverse effect, and further breakthrough was necessary for practical use.

Further, in Japanese Patent Laid-Open No. 5-204073, (1
Although silver chloride tabular grains having a (00) plane are disclosed, the grains have a low γ and are not practical. US Patent 5,
No. 320,938 discloses silver chloride-containing tabular grains having a (100) plane, and effects such as sensitization in color light-sensitive materials are described, but rapid processing suitability of development processing is described. Not not. Further, JP-A-6-28
No. 9517 discloses a technique in which silver iodide is contained on the surface of a silver chloride tabular grain having a (100) main plane to enhance color sensitization sensitivity, but it is still low γ and is not practical.

Incidentally, in many cases, hydroquinones have been conventionally used as a developing agent in a developing solution used for developing a black-and-white light-sensitive material. However, from the viewpoint of improvement in work safety and environmental protection, development is carried out. A proposal has recently been made to replace the main drug with ascorbic acid, for example, US Pat.
No. 236,816 discloses a developer using ascorbic acid.

However, since the developing solution using ascorbic acid has a lower activity than the developing solution using hydroquinone and is more deteriorated over time, it has a drawback that it is difficult to obtain a constant silver image. There is a strong demand for technologies to overcome.

[0016]

Therefore, the first object of the present invention is to provide high sensitivity, high γ, high image quality and excellent suitability for rapid processing.
Another object of the present invention is to provide a silver halide emulsion and a silver halide photographic light-sensitive material excellent in storage stability and processing variability.

A second object is to provide a method for producing a silver halide emulsion having such performance.

A third object is to provide a method for processing a silver halide photographic light-sensitive material having such a property in a rapid, safe and environmentally friendly manner.

[0019]

According to the invention of claim 1 of the present application, in a silver halide emulsion containing at least 50 mol% of silver chloride, the silver halide grains contained in the silver halide emulsion are 50% or more of the total projected area is a tabular silver halide grain, and the main plane of the tabular silver halide grain is a (100) plane having an adjacent side ratio of less than 10, and the tabular silver halide grain The average aspect ratio is 2 or more, and the variation coefficient of the projected area diameter of the main plane of the tabular silver halide grains is 20% or less (hereinafter, such tabular silver halide grains are referred to as It may be abbreviated as tabular silver halide grains and the like.), Which solves the above problems.

The invention according to claim 2 of the present application is the silver halide emulsion according to claim 1, characterized in that the average aspect ratio is 2 or more and less than 8 according to claim 1. Is achieved.

The invention according to claim 3 of the present application is the silver halide emulsion according to claim 1 or 2, characterized in that the average silver iodide content is less than 1.5 mol%. This achieves the above object.

The invention of claim 4 of the present application is at least 5
A method for producing a silver halide emulsion containing 0 mol% or more of silver chloride, which comprises at least (1) a step of adding a silver salt in the absence of iodide to start nucleation, and (2) continuously. A method for producing a silver halide emulsion, which comprises two steps of adding a silver salt in the presence of iodide and performing nucleation and / or crystal growth, thereby achieving the above object. To do.

The invention of claim 5 of the present application is at least 5
A silver halide emulsion containing 0 mol% or more of silver chloride, wherein 50% or more of the total projected area of silver halide grains contained in the silver halide emulsion is a flat plate whose main plane is the (100) plane. And a step of starting nucleation by adding a silver salt in the absence of iodide, and (2) the presence of iodide. A method for producing a silver halide emulsion, which comprises two steps of adding a silver salt below and performing nucleation and / or crystal growth, which achieves the above object. is there.

The invention according to claim 6 of the present application is a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, and at least one of the emulsion layers is claim 1. A silver halide photographic light-sensitive material containing the above silver halide emulsion, which achieves the above object.

According to the invention of claim 7 of the present application, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on each side of a support, at least one of the emulsion layers is claimed. A silver halide photographic light-sensitive material containing the silver halide emulsion described in 1, which achieves the above object.

The invention of claim 8 of the present application is characterized in that the silver halide photographic light-sensitive material according to claim 6 or 7 is treated with a developing solution containing substantially no dihydroxybenzenes in the developing solution. And a method for processing a silver halide photographic light-sensitive material, which achieves the above object.

The invention according to claim 9 of the present application is characterized in that the silver halide photographic light-sensitive material according to claim 6 or 7 is processed in a total processing time of 10 to 45 seconds. A method for processing a light-sensitive material, which achieves the above object.

The present invention will be described in more detail below.

The tabular silver halide grains of the present invention contained in the silver halide emulsion of the present invention contain at least 50 mol% of silver chloride, preferably 70 mol% or more, and 90 mol% or more. More preferably.

In the tabular silver halide grains of the present invention, silver chloride, silver iodochloride, silver iodobromochloride, silver bromochloride, etc. can be used as the silver halide. Of these, silver chloride and silver iodochloride are preferable. In the case of silver iodochloride, the content of silver iodide is
The average silver iodide content of the whole silver halide grains was 0.1%.
The amount is preferably 01 mol% or more and 1.0 mol% or less. 0.01
More preferably, it is not less than mol% and not more than 0.5 mol%.

In the present invention, the silver iodide content and the average silver iodide content of individual silver halide grains are determined by the EPMA method (E
Electron Probe Micro Analysis
zer method). According to this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, and an X-ray analysis by electron beam excitation and electron beam excitation is performed. By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the silver halide composition of each grain can be determined. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content is determined from the average thereof.

The tabular silver halide grains of the present invention preferably have a more uniform iodide content between grains. When the iodine content distribution between particles is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

In the present invention, the tabular silver halide grains preferably contain silver iodide, but it is preferred that the tabular silver halide grains are contained at least inside. In the case of the inside, it is more preferable that it exists at least in the central portion. Further, it is also preferable that it is present on the outermost surface.

In this case, the internal composition preferably contains silver iodide in an amount of 0.1 mol% or more and 5 mol% or less. Here, the silver halide composition distribution inside the silver halide grain is
It can be obtained by pretreating the particles into ultrathin sections, and then observing and analyzing with a transmission electron microscope while cooling.

Specifically, after taking out silver halide grains from the emulsion, they are embedded in a resin and cut with a diamond knife to prepare a slice having a thickness of 60 nm. While cooling this section with liquid nitrogen, observation and point analysis were performed with a transmission electron microscope equipped with an energy dispersive X-ray analyzer, and it was obtained by quantitative calculation (Inoue, Nagasawa, Photographic Society, 1987). See page 62 of the conference proceedings).

It is also preferable to add silver iodide to the outermost surface. In this case, the silver iodide content on the outermost surface is 1 mol%.
It is preferably at least 10 mol%. Here, the silver iodide content on the outermost surface of the tabular silver halide grains means XP
S method (X-ray Photoelectron Sp
refers to the silver iodide content of a portion up to a depth of 50Å analyzed by X-ray photoelectron spectroscopy,
It can be obtained as follows.

The sample was cooled to -110 ° C. or less in an ultrahigh vacuum of 1 × 10 ^-8 torr or less, and MgKα as an X-ray for a probe was irradiated with an X-ray source voltage of 15 kV and an X-ray source current of 40 mA to obtain Ag3d5 /. 2, Br3d, I3d 3/2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the halide composition on the outermost surface is determined from these intensity ratios.

The purpose of cooling the sample is to eliminate the measurement error caused by the destruction of the sample (the decomposition of silver halide and the diffusion of halide (particularly iodine)) by the X-ray irradiation at room temperature, and to improve the measurement accuracy. By cooling to −110 ° C., sample destruction can be suppressed to a level that does not hinder measurement.

In the present invention, the silver halide grains contained in any one of the silver halide emulsion layers have an aspect ratio of 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion layer. It is a tabular silver halide grain having a ratio of 2 or more, and the main plane of the tabular silver halide grain is a (100) plane having a ratio of adjacent sides of less than 10, which is a tabular silver halide grain. The tabular silver halide grains are grains having two parallel main planes facing each other, and generally, those having an average ratio of grain size to grain thickness (hereinafter referred to as aspect ratio) of more than 1.3. However, the silver halide grains of the present invention have an aspect ratio of 2 or more. Here, the grain size means an average projected area (hereinafter referred to as grain size), which is a circle-equivalent diameter of the projected area of the tabular silver halide grains (diameter of a circle having the same projected area as the silver halide grains). ), And the thickness means the distance between two parallel principal planes forming a tabular silver halide grain.

The tabular silver halide grain of the present invention has an aspect ratio of 2 or more, preferably 2 or more and less than 8, more preferably 2 or more and less than 7, and most preferably 2 or more and less than 5. .

In the present invention, 50% or more of the total projected area of silver halide grains contained in any of the emulsion layers is composed of tabular silver halide grains having a (100) plane as a main plane. However, preferably 70% or more, and more preferably 90% or more are composed of tabular silver halide grains having a (100) plane as a main plane. The fact that the principal plane is the (100) plane can be confirmed by an X-ray diffraction method or the like.

In the present invention, the shape of the main plane of the tabular silver halide grains is preferably a right-angled parallelogram or a right-angled parallelogram with the corners missing or rounded. The ratio of adjacent sides of the right-angled parallelogram is preferably less than 10, more preferably less than 5, and even more preferably less than 2. In addition, the length of the side when the corner is missing or rounded is expressed by the distance between the intersection of the straight line part of the side and the straight line part of the adjacent side. To be done.

The average grain size of the tabular silver halide grains of the present invention is preferably 0.15 µ to 5.0 µ,
The thickness is more preferably from 4 to 3.0 μm, most preferably from 0.4 to 2.0 μm.

The average thickness of the tabular silver halide grains of the present invention is preferably 0.01 to 1.0 μm, more preferably 0.02 to 0.40 μm, still more preferably 0.02 to 0. It is 30 μm.

Particle size and thickness can be optimized to optimize sensitivity and other photographic properties. Optimum particle size and optimum depending on other factors constituting the photosensitive material (sensitivity of the hydrophilic colloid layer, degree of hardening, chemical ripening conditions, sensitivity setting of the photosensitive material, amount of silver, etc.) that affect the sensitivity and other photographic characteristics The thickness is different.

The tabular silver halide grains of the present invention are preferably monodisperse emulsions having a narrow grain size distribution. Specifically, (standard deviation of grain size / average grain size) × 100 = width of grain size distribution ( %), The breadth (%) of the particle size distribution when the breadth of the distribution is defined is preferably 20% or less, more preferably 18% or less, and particularly preferably 15% or less.

The tabular silver halide grains of the present invention preferably have a small thickness distribution. Specifically, when the width of the thickness distribution is defined by (standard deviation of thickness / average thickness) × 100 = width of thickness distribution (%), this is 25%.
The following is preferable, 20% or less is more preferable, and 15% or less is particularly preferable.

The tabular silver halide grains of the present invention may have dislocations. Dislocations are described in F. Hamilt
on, Photo. Sci. Eng, 57 (1967)
And T. Shiozawa, J .; Soc. Photo. S
ci. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time,
The thicker the particles, the more difficult it is for the electron beam to pass,
High pressure type (200 kV for 0.25 μm thick particles)
It is possible to observe more clearly by using the above electron microscope.

The method for producing a tabular silver halide grain-containing emulsion of the present invention comprises at least (1) a step of adding a silver salt in the absence of iodide to start nucleation, and (2) subsequent iodide. The step of adding a silver salt in the presence of nucleation and / or crystal growth.
It is characterized by having two steps.

Specifically, (a) nucleation is started in the absence of iodide, and then nucleation is performed in the presence of iodide. (B) Nucleation is started in the absence of iodide, and then crystal growth is performed in the presence of iodide. (C) Nucleation is started in the absence of iodide, and then crystal growth is performed simultaneously with nucleation in the presence of iodide. This is a manufacturing method that can be carried out in a configuration having any of the above processes. In any case, the feature is that iodide does not exist at the start of nucleation, and iodide exists immediately after that.
Hereinafter, each step will be described in detail.

(1) Step for Initiating Nucleation A silver salt and / or halide salt solution is added to a dispersion medium solution containing at least a dispersion medium and water while stirring to perform nucleation. The pCl at the start of nucleation is a value at which the (100) plane is easily formed, that is, generally preferably 0.5
It is adjusted to 3.5, more preferably 1.0 to 3.0, and even more preferably 1.5 to 2.5. The pH is preferably 1.0 or higher, more preferably 1.5 or higher, and further preferably 2.
It is 0 to 7.0. Gelatin and gelatin derivatives are preferably used as the dispersion medium, and gelatin from which impurities have been removed is more preferable. Above all, the methionine content is less than 30 μm mol / g of gelatin, preferably 15 μm.
It is preferred to use so-called low methionine gelatin at less than 1 g mol / gelatin. Also, the molecular weight is 1000 to 1.
It is preferable to use so-called low molecular weight gelatin or the like of 0 × 10 ⁴ , preferably 2000 to 6 × 10 ⁴ . These gelatins may be used alone or as a mixture of two or more. The dispersion medium concentration is preferably 0.1 to 10% by weight, more preferably 0.3 to 5% by weight.

Nucleation starts from the moment when the silver salt is added to the dispersion medium solution. Therefore, in the present invention,
“Starting nucleation in the absence of iodide” means that the solution of the dispersion medium does not contain iodide at the start of nucleation, that is, at the start of addition of a silver salt. Here, the start of the addition of the silver salt means the moment when the addition of the silver salt is started in the dispersion medium solution. The silver salt addition period in the absence of iodide is preferably 1 second to 2 minutes including this moment, more preferably 5 seconds to 30 seconds. During this period, other halide salt may or may not be added. That is, a so-called single jet method in which only a silver salt is added or a double jet method in which a silver salt and a halide salt solution is added may be used.

(2) Step of subsequently adding a silver salt in the presence of iodide to perform nucleation and / or crystal growth In the method for producing a silver halide emulsion of the present invention, as described above, iodide is absent. Immediately after adding the silver salt to the dispersion medium solution, the silver salt is subsequently added in the presence of iodide to perform nucleation and / or crystal growth. At this time, the iodide ion concentration in the dispersion medium solution can be introduced up to the solid solution limit of silver iodide and silver chloride, but is preferably 0.001 to 10 mol%, and more preferably 0. 0.01 to 8 mol%. The chloride ion concentration is preferably 50 mol% or more. The bromine ion in the dispersion medium solution at the time of nucleation may be present as long as chlorine ion is present at 50 mol% or more.

As a method of allowing the iodide to be present in the dispersion medium solution, for example, a method of adding an iodide salt to a halide salt solution and adding this can be used. At this time, any method such as a double jet method in which a silver salt solution is added at the same time, a method in which only a halide solution is added and then a silver salt solution is added, and the like can be used. The silver salt addition period in the presence of iodide is preferably 1 second to 5 minutes, and 5 seconds to
2 minutes is more preferable, and 10 seconds to 1 minute is the most preferable.

In the production method of the present invention, the temperature of the step of starting the nucleation step and the step of subsequently adding a silver salt in the presence of iodide to perform the nucleation and / or crystal growth is preferably 10 ° C. or higher. 20-70 degreeC is especially preferable.

In the production method of the present invention, the amount of silver added during nucleation is preferably 0.1 mol% to 10 mol% of the total silver amount.

The production method of the present invention comprises a ripening step following the step of starting the nucleation step and the step of subsequently adding a silver salt in the presence of iodide to cause nucleation and / or crystal growth. Is preferred. In the ripening process, tabular grains generated during nucleation by Ostwald ripening can be further grown and other grains can be eliminated. The temperature during aging is preferably from 20 to 90C, more preferably from 30 to 85C, most preferably from 40 to 80C. The temperature during aging may be constant or may be changed, but when there is a crystal growth process described later, a method of changing the aging temperature is advantageously used. The pCl during aging is 0.5 to 3.
5 is preferable and 1.0-3.0 is more preferable. Also,
The pH is preferably from 1 to 12, more preferably from 2 to 8, and most preferably from 2 to 6. The ripening is preferably carried out in the absence of a so-called silver halide solvent such as ammonia.

In the production method of the present invention, following the aging,
It may have a crystal growth process. The pCl at the time of crystal growth is adjusted in the range of 0.5 to 3.5, preferably 1.0.
To 3.0, more preferably 1.5 to 2.5.
The pH is preferably 1 to 12, more preferably 2 to
8, most preferably 2-6. The temperature during crystal growth is preferably 40 to 90 ° C, more preferably 45 to 80 ° C.
C., most preferably 50-75.degree. The method of adding silver ions and halogen ions during crystal growth is a double jet method of adding a silver salt and halide salt solution,
Any method may be used, such as a method for supplying a fine grain prepared by adding a fine grain emulsion of silver halide prepared in advance or a combination of both. Among these, the fine particle supply method is preferably used. When the fine particle supply method is used, the diameter of the fine particles is preferably 0.15 μm or less, more preferably 0.1 μm or less, and most preferably 0.06 μm or less.

A method in which the growth is temporarily stopped on the way and seed grains are used to deposit silver halide on the seed grains for growth is also preferably used.

Specifically, a dispersion medium solution and seed particles may be present in a reaction vessel in advance, and a silver salt solution, a halide salt solution, or silver halide fine particles may be supplied as necessary to grow seed particles. it can.

In the preparation of the tabular silver halide grains of the present invention, a known silver halide solvent such as ammonia, thioether or thiourea can be present.

In the production of tabular silver halide grains of the present invention, a silver salt solution and a halide solution are added at the time of growth by the double jet method, and the rate of addition is such that new nucleation does not occur depending on the growth of grains, Further, particles having a desired particle size and distribution can be obtained by a method in which the size distribution is not broadened due to Ostwald ripening, that is, a method of gradually changing it within a range of 30 to 100% of the speed at which new nuclei are generated. As another condition for further growth, a method in which silver halide grains are added and dissolved and recrystallized to grow the grains is also preferably used, as shown in 88 of the Annual Meeting of the Japan Photographic Society 1983. In particular, silver iodide fine grains, silver bromide fine grains, silver iodobromide fine grains, and silver chloride fine grains are preferably used.

The tabular silver halide grains of the present invention may be so-called halogen conversion type (conversion type) grains. The halogen conversion amount is preferably from 0.2 mol% to 0.5 mol% based on the silver amount, and the conversion may be carried out during physical ripening or after physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition of the grain surface before the halogen conversion is usually added. At this time, the size of the fine particles is preferably 0.2 μm or less, more preferably 0.
It is 02 to 0.1 μm.

When silver iodide on the outermost surface of the tabular silver halide grains of the present invention is contained, as a method therefor, a silver nitrate solution and a solution containing iodine ions are added to an emulsion containing tabular grains as a base. A method of simultaneously adding, a method of adding fine silver halide grains such as silver iodide, silver iodobromide or silver chloroiodobromide, a method of adding potassium iodide or a mixture of potassium iodide and potassium bromide, etc. are applied. it can. Of these, the method of adding fine silver halide grains is preferable. Especially preferred is the addition of fine silver iodide grains.

The time for adjusting the silver iodide content on the outermost surface is from the final step of the production step of silver halide crystals to the chemical ripening step and further to the end of the solution preparation step immediately before the coating of the silver halide emulsion. Although it can be selected in the meantime, it is preferable to adjust it by the end of the chemical ripening step. The chemical ripening step referred to here is a point in time when physical ripening and desalting of the silver halide emulsion of the present invention are completed, when a chemical sensitizer is added, and thereafter, an operation for stopping chemical ripening is performed. Up to. Further, the addition of silver halide fine grains may be carried out several times with a time interval, or after the addition of the fine grains, another chemically ripened emulsion may be added. In the present invention, when the silver halide fine grains are added, the temperature of the emulsion liquid is preferably in the range of 30 to 80 ° C., and more preferably 40.
The range of to 65 ° C is particularly preferable. The present invention is preferably carried out under the condition that the silver halide fine grains to be added partially or wholly disappears after the addition and immediately before coating. More preferable condition is 20 of the added silver halide fine grains. % Or more means that it disappears just before coating.

In producing the tabular silver halide grains of the present invention, the stirring conditions during production are extremely important. As the stirring device, the device shown in JP-A-62-160128, in which the additive liquid nozzle is installed in the liquid near the mother liquid inlet of the stirrer, is particularly preferably used. Also, at this time,
The number of stirring cycles is preferably 100 to 1200 rpm.

The tabular silver halide grains of the present invention are used in the process of forming grains and / or the process of growing grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt ( It is preferable to add a metal ion using at least one selected from the group consisting of complex salts) and the iron salt (including complex salts) so that these metal elements are contained inside and / or on the surface of the particles.

In the practice of the present invention, it is also preferable to add a silver halide solvent before the desalting step in order to accelerate the developing rate. For example, a thiocyanic acid compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is added in an amount of 1 × 10 ⁻³ or more and 3 × 1 per mol of silver.
It is preferred to add 0 ^-2 mol.

In the present invention, it is preferable to use gelatin as the dispersion medium for the protective colloid of silver halide grains. Examples of the gelatin include alkali-processed gelatin, acid-processed gelatin and low-molecular weight gelatin (having a molecular weight of 20,000 to 10).
And modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used. Specifically, Research Disclosure (Resea)
rch Disclosure (hereinafter abbreviated as RD)
76 volume No. 17643 (December 1978), IX.

In the production of the tabular silver halide grains of the present invention, unnecessary soluble salts may be removed during the growth of the silver halide grains, or they may be contained therein. When removing the salts, see RD Vol.
It can be performed based on the method described in 17643, section II.

The light-sensitive material of the present invention is characterized by having an emulsion layer containing the emulsion of the present invention on both sides or one side of a support. When there are silver halide emulsion layers on both sides of the support, the amount of silver per side is 1.8 g / m ² or less, and when there is a silver halide emulsion layer on one side, the amount of silver is 3.6 g / m ² or less. Is preferable, and more preferably 0.
It is 5 to 1.5 g / m ² and 1.0 to 3.0 g / m ² .

The tabular silver halide grains of the present invention can be chemically sensitized. Chemical ripening, that is, the conditions of the step of chemical sensitization, for example, pH, pAg, temperature, time and the like are not particularly limited, and can be carried out under conditions generally used in the art. For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitization method using a selenium compound, a tellurium sensitization method using a tellurium compound, or a reducing substance is used. The reduction sensitization method to be used, gold and other noble metal sensitization methods using a noble metal can be used alone or in combination.
A selenium sensitization method, a tellurium sensitization method, a reduction sensitization method and the like are preferably used, and a selenium sensitization method is particularly preferably used.

In the case of selenium sensitization, the selenium sensitizers used include a wide variety of selenium compounds. For example, in this regard, US Pat. Nos. 1,574,944 and 1,602,592.
No. 1623499, JP-A-60-150046.
No., JP-A-4-25832, JP-A-4-109240,
No. 4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylseleno). Urea, N, N,
N'-trimethyl-N'-heptafluoroselenourea,
N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea and the like), selenoketones (for example, selenoacetone, selenoacetone) Acetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophos Fates (eg, tri-
p-triselenophosphate, etc.) and selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, and selenides.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patents. US Patent 15749
No. 44, No. 1602592, No. 1623499,
No. 3297446, No. 3297447, and No. 3320
069, 3408196, 3408197,
No. 3442653, No. 3420670, No. 3591.
No. 385, French Patent Nos. 2,693,038 and 209.
No. 3209, Japanese Patent Publication No. 52-34491, No. 52-34
No. 492, No. 53-295, No. 57-22090,
JP-A-59-180536 and JP-A-59-185330.
Nos. 59-181337 and 59-187338
No. 59-192241, No. 60-150046
No. 60-151637 and No. 61-246738.
No. 3, Unexamined Patent Publication No. 3-4221, No. 3-24537, No.
-111838, 3-116132, 3-14
No. 8648, No. 3-237450, No. 4-16838
No. 4, No. 4-25832, No. 4-32831, No. 49.
No. 6059, No. 4-109240, No. 4-14073
No. 8, No. 4-140739, No. 4-147250,
No. 4-149437, No. 4-184331, No. 4-
190225, 4-191729, 4-195.
035, British Patent 255,846, and 86,1984.
issue. In addition, H. E. FIG. Journal by Spencer et al.
of Photographic Science
It is also disclosed in scientific literatures such as Journal, Vol. 31, pp. 158-169 (1983).

The amount of the selenium sensitizer used varies depending on the selenium compound used, the silver halide grains, the chemical ripening conditions, etc., but is generally 10 ^-8 to 10 ^-4 per mol of silver halide.
Use molar amounts. In addition, the addition method may be a method of adding it by dissolving it in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent depending on the properties of the selenium compound used, or by adding it in advance with a gelatin solution. Alternatively, the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used.

The temperature of the chemical ripening using the selenium sensitizer is
A range from 40 to 90C is preferred. More preferably, 45
It is not less than 80 ° C and not less than 80 ° C. The pH is 4-9, pAg
Is preferably in the range of 6 to 9.5.

Regarding tellurium sensitizers and sensitizing methods, US Pat. Nos. 1,623,499, 3,332,0069 and 37,
72031, 3351289, 3655394
No., British Patent Nos. 235211 and 1121496,
No. 1,295,462, No. 1,396,696, Canadian Patent No. 800958, JP-A-4-204640, and No. 4
No. 333043 is disclosed. Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-dimethyl tellurourea, N,
N'-dimethyl-N'phenyl tellurourea), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), Telluroamides (for example, telluroacetamide, N, N-dimethyl tellurobenzamide), telluroketones, telluroesters, isotelloocyanates, and the like.

The technique for using the tellurium sensitizer is in accordance with the technique for using the selenium sensitizer.

It is also preferable to carry out so-called reduction sensitization on the grain surface by placing it in an appropriate reducing atmosphere.

Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and their derivatives. Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

The amount of the reducing agent added is determined by the type of reduction sensitizer, the grain size of the silver halide grains, the composition and crystal habit, the temperature of the reaction system,
It is preferable to change the pH depending on environmental conditions such as pH and pAg. For example, in the case of thiourea dioxide, as a rough guide, about 0.01 to 2 per mole of silver halide is used.
Use of mg gives favorable results. In the case of ascorbic acid, about 50 mg to 2 mg / mol of silver halide is used.
The range of g is preferred.

As conditions for reduction sensitization, the temperature is about 40 to
70 ° C., time is about 10 to 200 minutes, pH is about 5 to 11,
pAg is preferably in the range of about 1-10 (here, p
The Ag value is the reciprocal of the Ag ⁺ ion concentration).

As the water-soluble silver salt, silver nitrate is preferable.
By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. The pAg during silver ripening is suitably 1 to 6, and preferably 2 to 4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range. As a stabilizer for a silver halide photographic emulsion containing reduction-sensitized silver halide grains, a general stabilizer described below can be used, but the oxidation disclosed in JP-A-57-82831 is used. Inhibitor and / or V.I. S. Ga
Hler's paper [Zeitshift fur w
issenschaftliche Photogra
phi Bd. 63, 133 (1969)] and the thiosulfonic acids described in JP-A No. 54-1019 are often used together with good results. The addition of these compounds may be carried out at any stage of the emulsion production process from crystal growth to the preparation process immediately before coating.

The tabular silver halide grains according to the present invention are
It may be spectrally sensitized by methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobola cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonone dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

These dyes can be applied to any of the commonly used nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. A renin nucleus, a benzindolenin nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethine structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazoline-2,4-dione nucleus, Rhodanine nucleus, thiobarbituric acid nucleus, etc.
A 6-member heterocyclic nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for the purpose of supersensitization. Also, with the sensitizing dye itself,
A dye having no spectral sensitizing property or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect may be contained in the emulsion layer. For example, a substituted aminostilbene compound having a nitrogen-containing heterocyclic nucleus group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), an aromatic organic acid formaldehyde condensate (for example, US (Described in Japanese Patent No. 3,743,510), cadmium salt, azaindene compound, etc. may be contained.

US Pat. Nos. 3,615,613 and 3,6.
No. 15,641, No. 3,617,295, No. 3,63
The combinations described in No. 5,721 and the like are particularly useful. The sensitizing dye may be added during or during each step of nucleation, growth, desalting, chemical sensitization, or after chemical sensitization.

For the tabular silver halide grains according to the present invention, the following cyanine or carbocyanine dyes can be used alone or in combination.

Further, in the silver halide emulsion of the present invention, and in the light-sensitive material of the present invention, at least any one of the silver halide emulsion layer and constituent layers other than the emulsion layer.
It is also preferably used from the viewpoint of sharpness, that the layer contains a dye that can be decolorized or / and flowed out during the development processing. The dye used in the light-sensitive material may be appropriately selected from dyes capable of improving sharpness by absorbing a desired wavelength and removing the influence of the wavelength, depending on the light-sensitive material. it can. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and the color is not visually recognized when the image is completed.

The above dyes are preferably substantially insoluble in water at pH 7 or less and substantially water-soluble at pH 8 or more. For example, specifically, dyes selected from the dyes represented by the following general formulas [1] to [6] are preferable.

[0092]

Embedded image [In the formula, A and A ′ may be the same or different and each represents an acidic nucleus, B represents a basic nucleus, Q represents an aryl group or a heterocyclic group, and Q ′ represents a heterocyclic group. , X
And Y, which may be the same or different, each represents an electron-withdrawing group, and L ¹ , L ² and L ³ each represent a methine group. m represents 0 or 1, n represents 0, 1 or 2, and p represents 0 or 1. However, general formula [1]-
The dye represented by [6] has at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule. ]

The acidic nuclei represented by A and A'in the general formulas [1], [2] and [3] are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanin, hydantoin and thio. Hydantoin, oxazolone,
Examples include isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, and pyrazolopyridone.

The basic nucleus represented by B in the general formulas [3] and [5] is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole,
Thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole, indole.

Examples of the aryl group represented by Q in the general formulas [1] and [4] include a phenyl group, a naphthyl group and a julolidyl group. In addition, the general formula [1],
Examples of the heterocyclic group represented by Q and Q ′ in [4] and [6] include a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, an indolyl group, a furyl group and a thienyl group. Can be given. The aryl group and the heterocyclic group include those having a substituent,
Examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, a cyano group, a hydroxy group, a mercapto group, an amino group, an alkoxy group, Aryloxy group, acyl group,
Examples thereof include a carbamoyl group, an acylamino group, a ureido group, a sulfonamide group, and a sulfamoyl group, and these substituents may have two or more kinds in combination. Preferred substituents are alkyl groups having 1 to 8 carbon atoms (eg, methyl group, ethyl group, t-butyl group, n-octyl group, 2-hydroxyethyl group, 2-methoxyethyl group, etc.), hydroxy group, cyano. A group, a halogen atom (for example, a fluorine atom,
Chlorine atom etc.), alkoxy group having 1 to 6 carbon atoms (eg methoxy group, ethoxy group, 2-hydroxyethoxy group, methylenedioxy group, n-butoxy group etc.), substituted amino group (eg dimethylamino group, diethylamino group) , Di (n
-Butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group, etc.), carboxy group, sulfonamide group (for example, methane Sulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (for example, sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.)
And these substituents may be combined.

The electron-withdrawing groups represented by X and Y in the general formulas [4] and [5] may be the same or different, and the σp value of the substituent constant Hammett (edited by Toshio Fujita, “Chemical Domain”). Special Issue No. 122 Structure-Activity Relationship of Drugs, 96-1
Page 03 (1979), Nankodo, and the like. ) Is 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, a phenoxycarbonyl group, 4 -Hydroxyphenoxycarbonyl group), a carbamoyl group (for example, a carbamoyl group, a methylcarbamoyl group, an ethylcarbamoyl group,
Butylcarbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, etc.), acyl group (eg, methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group, 4-ethylsulfonamidophenylcarbonyl group, etc.) ), Alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorosulfonyl group, etc.)
Is mentioned.

L ¹ , L ² and L of the general formulas [1] to [5]
^The methine group represented by ³ includes those having a substituent,
Examples of the substituent include an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, hexyl group, etc.), aryl group (eg, phenyl group, tolyl group, 4-hydroxyphenyl group, etc.), aralkyl group (eg, Benzyl group, phenethyl group etc.), heterocyclic group (eg pyridyl group, furyl group, thienyl group etc.), substituted amino group (eg dimethylamino group, diethylamino group, anilino group etc.), alkylthio group (eg methylthio group etc.) Can be mentioned.

In the present invention, among the dyes represented by the general formulas [1] to [6], a dye having at least one carboxy group in the molecule is preferably used, and more preferably the general formula [1]. A dye represented by the formula, and particularly preferably a dye in which Q is a furyl group in the general formula [1].

Next, specific examples of dyes that can be preferably used in the present invention will be given.

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

[Chemical 6]

[0105]

[Chemical 7]

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

[0110]

[Chemical 12]

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

Specific examples of the dye used in the present invention are further described in JP-A Nos. 52-92716 and 55-120030.
55-155350, 55-155351, 56-12639, 63-197943, JP-A No. 2-1838, No. 2-1839, and World Patent 88 /.
No. 04794, U.S. Pat. Nos. 4,861,700 and 4,
950,586, European Patent 489,973 and the like, and the synthetic method can be also carried out according to the method described in these patents.

A method for producing a solid fine particle dispersion of a dye is described in JP-A Nos. 52-92716 and 55-155.
No. 350, No. 55-155351, No. 63-1979.
No. 43, No. 3-182743, World Patent WO88 / 0
The method described in 4794 or the like can be used.
Specifically, using a surfactant, for example, a ball mill,
It can be prepared using a fine disperser such as a vibration mill, a planetary mill, a sand mill, a roller mill, a jet mill, and a disc impeller mill. Also, after dissolving the dye in a weakly alkaline aqueous solution, a method of precipitating fine solid particles by lowering the pH to weakly acidic, or a weakly alkaline solution of the dye and an acidic aqueous solution are simultaneously mixed while adjusting the pH. A dispersion of the dye can be obtained by a method of producing a fine solid. The dyes may be used alone or as a mixture of two or more. When two or more kinds are used as a mixture, they may be dispersed individually and then mixed, or they may be dispersed simultaneously.

The dye dispersed in the form of solid fine particles is preferably dispersed so that the average particle size is 0.01 μm to 5 μm, more preferably 0.01 μm to 1 μm, and particularly preferably 0.01 μm to It is 0.5 μm. The coefficient of variation of particle size distribution is 50%
It is preferably the following or less, more preferably 40% or less, and particularly preferably 30% or less. Here, the coefficient of variation of the particle size distribution is
It is a value represented by the following formula. (Standard deviation of particle size) / (average value of particle size) x 100

The conditions generally required as an antiseptic for the solid fine particle dispersion of the dye used in the photographic light-sensitive material are that it does not interact with photographic additives, and that it is resistant to microorganisms such as bacteria, yeasts and molds. On the other hand, it is a fungicide and antifungal agent that is highly effective in a small amount, has no effect on photographic performance such as desensitization, fog, graininess, and sharpness, and has no effect on photographic processing performance such as developability and fixability. There is something like that.

As the surface active agent, any of anionic surface active agents, nonionic surface active agents, cationic surface active agents and amphoteric surface active agents can be used, but preferably, for example, alkyl sulfonates, alkylbenzene sulfonates, Alkylnaphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, N-
Anionic surfactants such as acyl-N-alkyl taurines and nonionic surfactants such as savonine, alkylene oxide derivatives and alkyl esters of sugars.

The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the conditions of the dispersion liquid of the dye, but usually 1 g of the dye is used.
The amount may be 0.1 to 2000 mg, preferably 0.5
˜1000 mg, more preferably 1 to 500
mg is sufficient. The concentration of the dye dispersion is 0.01
It is used so as to be 10 to 10% by weight, preferably 0.1
~ 5% by weight. The surfactant may be added at a position before the dispersion of the dye is started, and if necessary, it may be further added to the dye dispersion after the dispersion is completed. These anionic activators and / or nonionic activators may be used alone or in combination of two or more, and both activators may be used in combination.

To the dye dispersion, a hydrophilic colloid used as a binder of a photographic constituent layer can be added before the start of dispersion or after the end of dispersion. As the hydrophilic colloid, it is advantageous to use gelatin, but in addition to the above, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, phthalated gelatin and the like, and gelatin and a monomer having a polymerizable ethylene group are used. Graft polymer, carboxymethyl cellulose, hydroxymethyl cellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-
Synthetic hydrophilic polymers such as dimethylacrylamide, poly-N-vinylpyrrolidone and polymethacrylic acid, agar, gum arabic, alginic acid, albumin and casein can be used. You may use these in combination of 2 or more types. The amount of hydrophilic colloid added to the dye dispersion of the present invention is 0.1 to 12% by weight.
It is preferable to add it so that it becomes 0.5 to 8% by weight.

The constituent layer to which the dye is added is preferably a silver halide emulsion layer or a layer closer to the support or both, and more preferably added in a coating layer adjacent to the transparent support. It is effective to do.
The dye preferably has a high concentration on the side close to the support.

The amount of the above dye added can be changed according to the sharpness target. Preferably, 0.2 to 20 m
g / m ² , more preferably 0.8 to 15 mg / m ² .

In the light-sensitive material of the present invention, when the silver halide emulsion layer is colored, a dye is added to the silver halide emulsion solution before coating, or to an aqueous solution of hydrophilic colloid,
These liquids may be applied to the support directly or through other hydrophilic colloid layers by various methods.

As described above, it is preferable that the dye has a high concentration on the side closer to the support. However, in order to fix the dye on the side closer to the support in this way, a moldant can be used. For example, a non-diffusible mordanting agent can be used as a substance to be combined with at least one of the above-mentioned dyes, and examples thereof include West German Patent No. 2,263,031 and British Patent No. 1,
Nos. 221,131 and 1,221,195;
Nos. 0-47624 and 50-71332.
-14418, U.S. Pat. Nos. 2,548,564, 2,675,316, 2,795,519, 2,839,401, 2,882,156, and 3,048. , 487, 3,184,309, 3,444,138, 3,445,231, 3,706,563, 3,709,690, 3,788,855. Compounds described in JP-A-No. 10-32 can be preferably used.

The method of binding the non-diffusible moldant and the dye may be carried out by various methods known in the art, but the method of binding in a gelatin binder is preferably applied. In addition, a method in which they are bound in a suitable binder and dispersed in an aqueous gelatin solution by ultrasonic waves or the like can also be applied.

The binding ratio is not uniform depending on the compound, but usually 0.1 part to 10 parts of the non-diffusible moldant is bonded to 1 part of the water-soluble dye. Since the amount of the water-soluble dye added is combined with the non-diffusible moldant, the dye can be used in a larger amount than when used alone.

When it is contained in the light-sensitive material, a constituent layer containing a combination of a dye and a non-diffusible moldant may be newly provided as a constituent layer, and its position can be arbitrarily selected, but it is preferably transparent. It is effective to use it as a coating layer adjacent to the support.

Silicone compounds described in US Pat. Nos. 3,489,576 and 4,047,958, which are used as slipping agents in the surface layer of the silver halide photographic light-sensitive material of the present invention, are described in JP-B-56-23139. Paraffin wax, higher fatty acid ester, starch derivative, and the like can be used in addition to the colloidal silica.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be added as a plasticizer to the constituent layer of the silver halide photographic light-sensitive material of the present invention.

Further, in the present invention, a polymer latex may be contained in any at least one of the silver halide emulsion layer and the constituent layers other than the emulsion layer for the purpose of improving pressure resistance. As the polymer latex, a homopolymer of an alkyl ester of acrylic acid, a copolymer with acrylic acid, styrene, etc., a styrene-butadiene copolymer, a polymer or copolymer comprising a monomer having an active methylene group, a water-soluble group or a crosslinkable group with gelatin is used. It can be preferably used.

In particular, a copolymer with a water-soluble group containing a hydrophobic monomer such as an alkyl ester of acrylic acid or styrene or a monomer having a crosslinkable group with gelatin is most preferable in order to increase the affinity with gelatin which is a binder. It is preferably used. Desirable examples of the monomer having a water-soluble group are acrylic acid, methacrylic acid, malylene acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, etc., and desirable examples of the monomer having crosslinkability with gelatin. Examples thereof include glycidyl acrylate, glycidyl methacrylate and N-methylol acrylamide.

In the present invention, examples of the matting agent include US Pat. Nos. 2,992,101 and 2,701,245.
Nos. 4,142,894, 4,396,706 and the like, homopolymers of polymethylmethacrylate or polymers of methylmethacrylate and methacrylic acid, organic compounds such as starch, silica, titanium dioxide, Fine particles of an inorganic compound such as strontium sulfate and barium sulfate can be used in combination. The particle size is preferably 0.6 to 10 μm, and particularly preferably 1 to 5 μm.

In the present invention, organic matting particles can also be used as the matting agent. The term “organic matter aggregated particles” refers to a substance having a particle diameter of 0.1 mm.
It refers to aggregated particles having a particle diameter of 1.0 to 20 μm in which a plurality of temporary particles having a small particle diameter of 0.5 to 0.50 μm are aggregated. The shape of the aggregated particles may be spherical or amorphous. The component as an organic substance is arbitrarily selected from alkyl methacrylate, alkyl acrylate, methacrylate in which an alkyl group is substituted with fluorine or silicon, acrylate and styrene, and may be a homopolymer or a copolymer, but polymethyl methacrylate is preferred. Specific examples include GR-5 and GR-5P manufactured by Soken Chemical Co., Ltd. The preferable addition amount is 10 to 200 mg / m ² in order to exert the effect without deteriorating the haze.

In the present invention, for the purpose of improving pressure resistance, the silver halide emulsion layer may contain inorganic fine particles. The main components of the inorganic fine particles are silicon, aluminum, titanium, indium, yttrium, tin, antimony, zinc, nickel, copper, iron, cobalt, manganese, molybdenum, niobium, zirconium, vanadium,
Among the oxides selected from alkali metals and alkaline earth metals, silicon oxide (colloidal silica), aluminum oxide, tin oxide, vanadium oxide and yttrium oxide are among them in terms of transparency and hardness. preferable. When these inorganic oxides are dispersed in water to form a sol, the surface thereof may be treated with alumina, yttrium, cerium or the like in order to enhance the water dispersion stability of itself. In order to increase the affinity with gelatin, shelling may be performed with gelatin which has been crosslinked in advance. The amount of the inorganic fine particles used in the present invention is preferably 0.05 to 1.0 by dry weight ratio to gelatin used as the binder of the layer to be added, and preferably 0.1 to 0.1.
It is 0.7. The above-mentioned inorganic fine particles may be used in combination. The preferred particle size of the inorganic fine particles is 1 to 300 nm.

The silver halide photographic light-sensitive material of the present invention preferably contains a water-soluble polymer. As the water-soluble polymer, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, etc. described in US Pat. No. 3,271,158 can be effectively used. Polysaccharides such as dextrin, dextran, saccharose and pullulan are also effective. Among them, polyacrylamide, dextran and dextrin are preferable, and dextrin is particularly preferable. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less.

In the present invention, the amount of the hydrophilic binder in the silver halide emulsion layer is preferably 3.0 g / m ² or less, and more preferably 2.0 g / m ² per side of the support when the emulsion layers are on both sides of the support. m ² or less. When it is on one side of the support, the weight is preferably 6.0 g / m ² or less, more preferably 4.0 g / m ² or less.

The silver halide photographic light-sensitive material of the present invention is a black-and-white silver halide photographic light-sensitive material (for example, medical light-sensitive material, printing light-sensitive material, general photographic negative light-sensitive material, etc.), color photographic light-sensitive material (for example, Color negative photosensitive materials, color reversal photosensitive materials, photosensitive materials for color printing, etc.), diffusion transfer photosensitive materials, photothermographic materials, etc., preferably black and white silver halide photographic photosensitive materials,
Particularly preferred are medical light-sensitive materials.

Further, the silver halide photographic light-sensitive material of the present invention can be preferably processed by a rapid processing of processing the silver halide photographic light-sensitive material with a total processing time of 10 seconds to 90 seconds.

The silver halide emulsion of the present invention may contain a developing agent such as aminophenol, asconulbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in the emulsion layer or a layer having other layers. .

The silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention preferably contains an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N′-methylenebis (β)
-(Vinylsulfonyl) propionamide) such as active halogen compounds (2,4-dichloro-6-hydroxy-
s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.), isoxazoles, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Among them, JP-A-53-41221 and JP-A-53-57.
257, 59-162456, 60-80846, and the active vinyl compounds described in U.S. Pat. No. 3,325,325.
Active halogen compounds described in No. 287 are preferable.

As the hardener, a polymer hardener can be effectively used. For example, dialdehyde starch, polyacrolein, polymers having aldehyde groups such as acrolein copolymers described in US Pat. No. 3,396,029, polymers having epoxy groups described in US Pat. No. 3,623,878, Polymers having dichlorotriazine groups described in U.S. Pat. No. 3,362,827, Research Disclosure 17333 (1978),
Polymers having an active ester group described in JP-A-56-66841, JP-A-56-142524, US Pat. No. 4,161,407, and JP-A-54-6503.
3, Research Disclosure Magazine 16725 (19
78) and the like having a polymer having an active vinyl group or a group serving as a precursor thereof are preferable. Among them, an active vinyl group or a precursor thereof is provided by a long spacer as described in JP-A-56-142524. Particularly preferred are polymers in which the groups represented by are attached to the polymer backbone.

In order to make the light-sensitive material of the present invention suitable for rapid processing, an appropriate amount of a hardener is added in advance in the coating step of the light-sensitive material to adjust the water swelling rate in the developing-fixing-water washing step. By doing so, it is preferable to reduce the water content in the light-sensitive material before the start of drying.

The silver halide light-sensitive material of the present invention comprises
The swelling rate during development is preferably 150 to 250%, and the film thickness after expansion is preferably 70 μm or less. Water swelling ratio is 25
If it exceeds 0%, poor drying occurs, and for example, conveyance failure also occurs in automatic developing machine processing, particularly in rapid processing. Also,
When the water swelling ratio is less than 150%, uneven development and residual color tend to be deteriorated during development. Here, the water swelling ratio is obtained by calculating the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, dividing this by the film thickness before processing, and multiplying by 100. To tell.

The support which can be used in the silver halide photographic light-sensitive material of the present invention is, for example, RD-1 described above.
7643 and RD-308119, page 1009.

A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer.

In the silver halide photographic light-sensitive material of the present invention, various additives can be added to the silver halide emulsion according to the purpose. Examples of additives and the like used include Research Disclosure (RD) N
o. No. 17643 (December 1978); 187
16 (November 1979) and No. 16 308119
(December 1989).
The places where they are written are listed below.

Additives RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical Sensitizer 23 III 648 Upper right 996 III Sensitizing Dye 23 IV 648-649 996-8 IV Desensitizing Dye 23 IV 998 IV Dye 25 -26 VIII 649-650 1003 VIII Development accelerator 29 XXXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26-27 XI 650 right 1005-6 XI antistatic agent 27 XII 650 right 1006-7 XIII plasticizer 27 XII 650 right 1006 XII slip agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 100 ~4 IX support 28 XVII 1009 XVII

Next, preferable development processing of the light-sensitive material of the present invention will be described.

The silver halide photographic light-sensitive material of the present invention can be processed by any processing method, but a preferable processing method is that the total processing time of the silver halide photographic light-sensitive material of the present invention is 10 seconds to 45 seconds, preferably 15 seconds. It is a processing method of processing from 45 seconds to 45 seconds.

The light-sensitive material of the present invention can be processed by various developing treatments. For example, a preferable developing solution can be realized by using a developing solution containing substantially no dihydroxybenzenes. That is, as a developing agent, JP-A-4
Dihydroxybenzenes such as hydroquinone and paraaminophenols such as p-aminophenol and N-
Examples of 3-pyrazolidones such as methyl-p-aminophenol and 2,4-diaminophenol include, for example, 1-
Phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazonridone, 5,5-dimethyl-1
It is preferable to use -phenyl-3-pyrazolidone and the like, or to use them in combination. Ascorbic acids can be particularly preferably used.

Further, the above-mentioned para-aminophenols, 3-
The preferred amount of the aminopyrazolidones used is 0.004 mol / l, more preferably 0.04 to 0.1.
2 mol / l.

When ascorbic acid or the like is used, dihydroxybenzenes are not contained in all the components of the developing solution, and the total number of moles of paraaminophenols and 3-pyrazolidones is 0.1. It is preferably not more than mol / liter.

Preservatives may include sulfites such as potassium sulfite, sodium sulfite, reductones such as piperidinohexose reductone,
These are preferably used in an amount of 0.2 to 1 mol / l, more preferably 0.3 to 0.6 mol / l. Also, addition of a large amount of ascorbic acids leads to processing stability.

As the alkaline agent, sodium hydroxide,
PH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate are included. Furthermore, a buffer such as borate described in JP-A-61-28708 and saccharose, acetoxime, 5-sulfosalicylic acid, phosphate and carbonate described in JP-A-60-93439 may be used. Good. The content of these agents is generally preferably such that the pH of the developer is 9.0-1.
3, more preferably pH 10 to 12.5.

The dissolution aid may contain polyethylene glycols and esters thereof, and the sensitizer may contain, for example, a quaternary ammonium salt, a development accelerator, a surface active agent and the like.

As a silver sludge-preventing agent, JP-A-56-
No. 106244, a silver stain preventive agent, JP-A-3-
The sulfides and disulfide compounds described in Japanese Patent No. 51844 and the cysteine derivatives or triazine compounds described in Japanese Patent Application No. 4-92947 are preferably used.

As the organic inhibitor, an azole type organic antifoggant, for example, an indazole type, an imidazole type, a benzimidazole type, a triazole type, a benztriazole type, a tetrazole type, or a thiadiazole type compound is used.

Examples of the inorganic inhibitor include sodium bromide, potassium bromide, potassium iodide and the like. In addition,
L. F. A. Menson's "Photographic Processing Chemistry" published by Focal Press (19
66), pages 226-229, U.S. Pat.
No. 15,2,592,364, JP-A-48-649
No. 33 may be used. As the chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid, a chelating agent having a chelate stabilization constant of 8 or more with iron described in JP-A No. 1-193853 is used as an organic chelating agent. It is preferably used.
Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

As the development hardening agent, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used. However, for rapid processing, it is preferable that the hardener is allowed to act in the coating step of the photosensitive material in advance as described above, rather than the hardener is allowed to act in the development processing step.

The development processing temperature is preferably 25 to 50 ° C.
And more preferably 30 to 40 ° C. The development time is preferably 3 to 90 seconds, more preferably 5 to 60 seconds. The processing time of the present invention is 1 to Dry to Dry
It is 5 to 90 seconds, preferably 15 to 50 seconds.

As for replenishment, a portion corresponding to the treating agent fatigue and oxidative fatigue is replenished. Examples of the replenishment method include replenishment by width and feed speed described in JP-A-55-126243, and JP-A-60-104.
Area replenishment described in JP-A No. 946 or area replenishment controlled by the number of continuously processed sheets described in JP-A-1-149156 may be used, and a preferable replenishment amount is 500 to 150 cc / m ² .

Preferred fixing solutions can include fixing materials commonly used in the art. pH3.
8 or more, preferably 4.2 to 5.5.

As a fixing agent, ammonium thiosulfate,
It is a thiosulfate such as sodium thiosulfate, and ammonium thiosulfate is particularly preferable in terms of fixing speed. The concentration of the ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / l, more preferably in the range of 0.8 to 3 mol / l.

The fixing solution may be one that performs acid hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potassium alum and the like.

Other fixers include sulfite, if desired.
Preservatives such as bisulfite, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid, nitric acid) and organic acids (citric acid, oxalic acid, malic acid, etc.), various acids such as hydrochloric acid, and metal hydroxides ( A pH adjusting agent such as potassium hydroxide or sodium) and a chelating agent having the ability to soften water can be contained.

As the fixing accelerator, for example, Japanese Patent Publication No. 45-
No. 35754, No. 58-122535, No. 58-12
No. 2536, thiourea derivatives, U.S. Pat.
Thioether described in US Pat. No. 6,459.

Further, a method of supplying a developing agent and / or a fixing agent as a solid processing agent to a processing tank of an automatic processor is also preferably used.

Here, the solid processing agent is a powder processing agent, a solid processing agent such as tablets, pills, granules, etc., and is subjected to moisture-proof processing as necessary.

The powder means an aggregate of fine grain crystals. Granules are powders that have undergone a granulation process and have a particle size of 5
It refers to a granular material of 0 to 5000 μm. The tablet refers to a powder or granules compressed and molded into a certain shape.

To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded photographic processing agent is mixed with a water-soluble binder. Arbitrary means, such as forming a coating layer by spraying, can be adopted (Japanese Patent Application No. 2-135887,
No. 203165, No. 2-203166, No. 2-203
No. 167, No. 2-203168, No. 2-300409.
No.).

A preferable tablet manufacturing method is a method in which a solid processing agent in powder form is granulated and then a tableting step is performed to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by a tableting step by simply mixing a solid processing agent component.

As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation are used. You can
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Further, the particle size distribution is
% Is preferably within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a pre-ketting machine can be used. The solid processing agent obtained by compression under pressure can take any shape, but from the viewpoint of productivity, handleability, or from the problem of dust when used on the user side, a cylindrical type, a so-called tablet is used. preferable.

More preferably, during granulation, the above-mentioned effects become more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

The method for producing the tablet treating agent is described in, for example, JP-A-51-61837, JP-A-54-155038 and JP-A-52-52.
No. 88025, British Patent No. 1213808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-10942 and 2-109.
It can be produced by a general method described in the specification of JP-A Nos. 043, 3-39735 and 3-39939. Further, the powder treating agent is described in, for example, JP-A-54-13333.
No. 2, British Patent No. 725892, No. 729862, and German Patent No. 3733861.

The bulk density of the above solid processing agent is 1.0 g /
cm ^{3 to} 2.5 g / cm ³ is preferable, 1.0 g / cm
2.5 g in terms of strength of solid obtained when it is larger than ^3.
/ Cm ³ is more preferable from the viewpoint of solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

The solid processing agent is used as a photographic processing agent such as a developing agent, a fixing agent and a rinsing agent, and it is the developing agent that has a great effect of stabilizing photographic performance.

The solid treating agent may solidify only a part of the components of a certain treating agent, but it is preferable that all the components of the treating agent are solidified. It is desirable that each component be molded as a separate solid processing agent and packaged in the same manner.
It is also desirable that the separate components are packaged in the order in which they are periodically added repeatedly in a package.

It is preferable to add all the processing agents to be replenished to the respective processing tanks as solid processing agents according to the processing amount information.
If replenishment water is required, it is replenished based on throughput information or other replenishment water control information. In this case, the liquid to be replenished to the processing tank can be only replenishing water. That is, when two or more types of processing tanks need replenishment, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the size of the automatic developing machine can be reduced. The replenishing water tank may be provided outside or externally, or may be built in an automatic developing machine, and the built-in water tank is preferable in terms of space saving and the like.

In the case of solidifying the developer, it is preferable that all of the alkali agent and the reducing agent be solid processing agents, and in the case of tablets, at least 3 agents or less, most preferably 1 agent. Is. When two or more agents are divided into solid processing agents, it is preferable that the plurality of tablets or granules be packed in the same package.

It is preferable to photograph using the light-sensitive material of the present invention and a radiation intensifying screen. The filling rate of the phosphor in the phosphor layer of the radiation intensifying screen is preferably 6
It is at least 8%, more preferably at least 70%, most preferably at least 72%.

The thickness of the phosphor layer is 150 μm or more,
250 μm or less is preferred. The thickness of the phosphor layer is 150μ
This is because if it is less than m, sharpness deteriorates sharply.

The radiation intensifying screen is preferably filled with the phosphor in a graded grain structure. In particular, it is preferable to apply phosphor particles having a large particle diameter to the surface protective layer side, and to apply phosphor particles having a small particle diameter to the support side.
The range of 5 to 2.0 μm and the range of 10 to 30 μm are preferable for those having a large particle size.

The intensifying screens used in combination have an increasing X-ray absorption rate of each intensifying screen by increasing the filling rate of the phosphor particles, and the X-ray absorption rate is 30% or more per 100 μm of the thickness of the phosphor layer. It is preferable. The amount of X-ray absorption was determined as follows. That is, an X-ray generated from a tungsten target operated at 80 KVP from an X-ray generator having an aluminum 2.2 mm equivalent intrinsic filtration with a three-phase power supply is transmitted through an aluminum plate having a thickness of 3 mm and a purity of 99% or more. Then, the target tube was made to arrive at the radiographic intensifying screen fixed at a position 200 cm from the tungsten anode, and then the X-ray absorption amount was measured at a position 50 cm after the phosphor layer of the radiographic intensifying screen using an ionization dosimeter. I asked. As a reference, the X-ray dose at the above measurement position measured without passing through the intensifying screen was used.

Preferred binders used in radiation intensifying screens include thermoplastic elastomers.
Specifically, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluororubber, polyisoprene, chlorinated polyethylene, styrene-
At least one type of thermoplastic elastomer selected from the group consisting of butadiene rubber and silicone rubber is used.

The filling rate of the phosphor can be obtained from the following equation from the porosity of the phosphor layer formed on the support.

[0186]

[Equation 1] (However, V: total volume of the phosphor layer Vair: air volume in the phosphor layer A: total weight of the phosphor layer px: density of the phosphor py: density of the binder pair: air density a: weight of the phosphor b: Weight of binder Further, in the formula (I), since the pair is almost 0, the formula (I) can be approximately represented by the following formula (II). (However, the definitions of V, Vair, A, px, py, a and b are the same as those in the formula (I).) In the present invention, the porosity of the phosphor layer was obtained by the formula (II). The filling rate of the phosphor can be determined by the following equation (III). (However, the definitions of V, Vair, A, px, py, a and b are the same as those in the formula (I).)

Preferred phosphors for use in the radiation intensifying screen include the followings. That is,
Tungstate phosphor (CaWO ₄ , MgWO ₄ ,
CaWO _4: Pb, etc.), terbium activated rare earth oxysulfide phosphor _{[Y 2 O 2 S: Tb,} Gd 2 O 2 S: Tb,
(Y, Gd) ₂ O ₂ S: Tb, Tm, etc.], terbium-activated rare earth phosphate-based phosphor [YPO ₄ : Tb, GdP
O ₄ : Tb, LaPO ₄ : Tb, etc.]), terbium-activated rare earth oxyhalide-based phosphor (LaOBr: T)
b, LaOBr: Tb. Tm, LaOCl: Tb, La
OCl: Tb. TmGdOBr: Tb, GdOCr: T
b, etc.), thulium activated rare earth oxyhalide phosphor (LaOBr: Tm, LaOCl: Tm, etc.), barium sulfate phosphor _{[BaSO 4: Pb, BaSO 4:} Eu
²⁺ , (Ba.Sr) SO ₄ : Eu ^2+, etc.] Divalent eurobium-activated alkaline earth metal phosphate-based phosphor [Ba
₃ (PO ₄ ) ₂ : Eu ²⁺ , (Ba, Sr) ₃ , (P
O ₄ ) ₂ : Eu ² etc.] Divalent eurobium activated alkaline earth metal fluoride halide phosphor [BaFCl: E]
^{u 2+, BaFBr: Eu 2+,} BaFCl:. Eu 2+ T
b, BaFBr: Eu ²⁺ . Tb, BaF _2. BaCl _2. X
BaSO _4. KCl: Eu ²⁺ , (Ba.Mg) F _2. BaC
L _2. KCl: Eu ^2+, etc.], iodide-based phosphor (CSI: N
a, CSI: Tl, NaI. KI: Tl, etc.), a sulfide-based phosphor [ZnS: Ag, (Zn.Cd) S: Ag, (Z
n. Cd) S: Cu, (Zn.Cd) S: Cu.Al
Etc.), a hafnium phosphate-based phosphor (HfP ₂ O ₇ : Cu
Etc.) can be mentioned. However, the phosphors used are not limited to these, and any phosphor that emits light in the visible or near-ultraviolet region upon irradiation with radiation can be used.

[0188]

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

Example 1 Preparation of Emulsion Em-1 (Comparative Emulsion) A tabular silver iodobromide emulsion Em-1 was prepared as follows. A1 ossein gelatin 24.2g Water 9657 ml _{HO- (CH 2 CH 2 O)} n- [CH (CH ₃₎ CH ₂ O] _{17 (CH 2 CH 2 O)} m-H 10% methanol solution 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 841 g 2825 ml D1 1.75N aqueous potassium bromide aqueous solution

At 42 ° C., Japanese Patent Publication Nos. 58-58288 and 58-5.
Using the mixing stirrer shown in No. 8-58289, 464.3 ml of each of solution B1 and solution C1 was added to solution A1 by the simultaneous mixing method over 1.5 minutes to perform nucleation.

After stopping the addition of solution B1 and solution C1, it took 60 minutes to raise the temperature of solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then re-solution. B1 and solution C1 were each mixed by the simultaneous mixing method at 55.4.
It was added at a flow rate of milliliter / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during this temperature increase from 42 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1. It was controlled to be +8 mV and +16 mV.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed.

Subsequently, after the emulsion was heated to 60 ° C.,
After adding predetermined amounts of the exemplified spectral sensitizing dyes D-2 and D-15 as a solid fine particle dispersion, a mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate and a methanol solution of triphenylphosphine selenide are added. In addition, aging was performed for a total of 2 hours. 4-hydroxy-6-methyl-1,3,3a, 7 as a stabilizer at the end of aging
-The appropriate amount of tetrazaindene (TAI) was added.

Additives other than the spectral sensitizing dye and their addition amounts (per mol of silver halide) are shown below. Ammonium thiocyanate 95 mg Chloroauric acid 12.5 mg Sodium thiosulfate 10.0 mg Triphenylphosphine selenide 2.0 mg Stabilizer (TAI) 1000 mg

A solid fine particle dispersion of a spectral sensitizing dye was prepared by a method according to the method described in Japanese Patent Application No. 4-99437.

That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been adjusted to 27 ° C. in advance and 350 is added with a high-speed stirrer (dissolver).
Obtained by stirring at 0 rpm for 30-120 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, 90% or more of the total projected area was composed of hexagonal tabular grains having a maximum adjacent edge ratio of 1.0 to 2.0, and the average grain size of hexagonal tabular grains was The tabular silver halide grains had a diameter (converted to a circle diameter) of 0.595 μm, an average thickness of 0.064 μm, an average aspect ratio of 9.3, and a grain size distribution width of 18.1%.

Preparation of Emulsion Em-2 Tabular silver iodochloride emulsion Em was prepared using the following 5 solutions.
-2 was prepared. A2 Low methionine gelatin 35.53 g Sodium chloride 1.306 g Potassium iodide 49.87 mg Water to make 2030 ml B2 Sodium chloride 1.737 g Potassium iodide 49.80 mg Water to make 30 ml C2 Silver nitrate 5.096 g Water 30 Finish with milliliters D2 Sodium chloride 46.80g Finish with water 800ml E2 Silver nitrate 135.90g Finish with water 800ml

Solution A2 was vigorously stirred in the reaction vessel while maintaining it at 40 ° C., and the total amount of solution B2 and solution C2 was added thereto by the simultaneous mixing method at a flow rate of 30 ml / min for 1 minute. During this time, pCl was kept at 1.95 throughout. The obtained core particles contained 2 mol% of iodine.

Next, after the mixed solution was kept at 40 ° C. for 10 minutes, the total amount of the solution D2 and the solution E2 was added by the simultaneous mixing method at a flow rate of 2 ml / min for 40 minutes. During this time, pCl was kept at 1.95 throughout.

Immediately after the completion of addition, desalting and washing with water were performed.
Subsequently, this emulsion was ripened in the same manner as the emulsion Em-1.

When the obtained silver halide emulsion was observed with an electron microscope, 50% or more of the total projected area had an adjacent edge ratio of 1 or more.
It is composed of right-angled parallelogrammatic tabular grains of less than 0, and the average particle size (converted to a circle diameter) of the right-angled parallelogrammatic tabular grains is 0.84μ.
m, average thickness 0.037 μm, average aspect ratio 2
3, tabular silver halide grains having a wide grain size distribution of 18.1%.

Preparation of Emulsion Em-3 A tabular silver iodochloride emulsion Em was prepared using the following 6 kinds of solutions.
-3 was prepared. A3 Low methionine gelatin 35.53 g Sodium chloride 1.324 g Water to make 2030 ml B3 Sodium chloride 0.869 g Water to make 15 ml B32 Sodium chloride 0.869 g Potassium iodide 49.80 mg Water to make 15 ml C3 Silver nitrate 5.096g Finish with water 30ml D3 Sodium chloride 46.80g Finish with water 800ml E3 Silver nitrate 135.90g Finish with water 800ml

Solution A3 was vigorously stirred in the reaction vessel while keeping it at 40 ° C., and the whole amount of solution B3 and 1 part of solution C3 were added thereto.
5 ml was added by the simultaneous mixing method at a flow rate of 30 ml / min for 30 seconds, and then the whole amount of the solution B32 and 15 ml of the solution C3 were mixed by the simultaneous mixing method at a flow rate of 30 ml / min for 30 seconds. Was added. During this time, pCl was kept at 1.95 throughout. The obtained core particles contained 2 mol% of iodine.

Next, after the mixed solution was kept at 40 ° C. for 10 minutes, the total amount of the solution D3 and the solution E3 was added by the simultaneous mixing method at a flow rate of 2 ml / min for 40 minutes. During this time, pCl was kept at 1.95 throughout.

Immediately after the completion of the addition, desalting and washing with water were performed.
Subsequently, this emulsion was ripened in the same manner as the emulsion Em-1.

When the obtained silver halide emulsion was observed with an electron microscope, 50% or more of the total projected area had an adjacent edge ratio of 1 or more.
It is composed of right-angled parallelogrammatic tabular grains of less than 0, and the average particle size (converted to a circle diameter) of the right-angled parallelogrammatic tabular grains is 0.84μ.
m, average thickness 0.037 μm, average aspect ratio 1
5, tabular silver halide grains having a wide grain size distribution of 17.2%.

Preparation of Emulsion Em-4 Tabular silver iodochloride emulsion Em-4 was prepared in the same manner as in Em-3 except that the amount of potassium iodide in solution B32 was changed to 24.90 mg in the preparation of emulsion Em-3. Was prepared.

When the obtained silver halide emulsion was observed with an electron microscope, 50% or more of the total projected area had an adjacent edge ratio of 1 or more.
It consists of right-angled parallelogrammatic tabular grains of less than 0, and the average particle size (circular diameter conversion) of the right-angled parallelogrammatic tabular grains is 0.585μ.
m, the average thickness is 0.078 μm, and the average aspect ratio is 7.
5, tabular silver halide grains having a wide grain size distribution of 17.0%.

Table 1 shows the emulsions thus obtained. AR indicates an aspect ratio.

[0211]

[Table 1] Composition of emulsion

The following additives were added to the obtained emulsion to prepare an emulsion coating solution. At the same time, a dye layer coating solution and a protective layer coating solution described below were also prepared. Three coating solutions were used to form the first dye layer, the second emulsion layer, and the third protective layer, the coating amount was 1.6 g / m ^{2 of} silver per side, and the amount of gelatin attached was Two slide hopper type coaters were used to achieve 2.7 g / m ² and both surfaces were simultaneously coated on the support at a speed of 80 m / min. 1
-No. 4 was obtained. As the support, a copolymer aqueous dispersion obtained by diluting the copolymer consisting of three types of monomers of glycidyl methacrylate 50 wt%, methyl acrylate 10 wt% and butyl methacrylate 40 wt% to 10 wt% A blue-colored polyethylene terephthalate film base having a concentration of 0.15 for a 175 μm X-ray film was used as the drawing liquid.

The additives used in the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide. First layer (dye layer) Solid fine particle dispersion dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4-dichloro-6 -Hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ²

Second Layer (Emulsion Layer) The following various additives were added to each emulsion obtained above. Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1, Ammonium 3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² n-C ₄ H ₉ OCH ₂ CH (OH ) CH ₂ N (CH ₂ COO ) ^₂ 350mg / m ₂ Compound (M) 5mg / m ² Compound (N) 5mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.2g / m ² Dextrin (average molecular weight 1000) 0.2 g / m ² However, it was adjusted to 1.0 g / m ² as the amount of gelatin.

Third Layer (Protective Layer) Gelatin 0.8 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene Amount shown in Table 3 Matting agent consisting of polymethylmethacrylate 50 mg / m ² (area average particle size 7.0 μm) Formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² Bis-vinylsulfonylmethyl ether 36 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J ) 2 mg / m ² compound (S-1) 7mg / m 2 compound (K) 15mg / m ² compound (O) 50mg / m ² compound (S-2) 5mg / m 2 C 9 F 19 -O- (CH 2 CH 2 O) 11 -H 3mg / m 2 C 8 F 17 SO 2 N- (C 3 H 7) (CH 2 CH 2 O ^{_{) 15 -H 2mg / m 2 C}} 8 F 17 SO 2 N- (C 3 H 7) (CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na 1mg / m 2

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[0219]

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The obtained sample No. Photographic characteristics were evaluated using the samples Nos. 1 to 4. First, the sample was sandwiched between two screens (KO-250 manufactured by Konica Corp.), and exposed to X-rays for 0.05 seconds at a tube voltage of 80 kvp and a tube current of 100 mA through an aluminum wedge to perform exposure. Then, using an automatic processor (Konica Corporation SRX-502), a developer having the following formulation,
Treated with fixer.

Developer formulation Part-A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine 5 acetic acid 120 g Sodium hydrogencarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-phenyl-5 -Mercaptotetrazole 0.2 g Hydroquinone 340 g Add water to finish to 5000 ml Part-B (for finishing 12 liters) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter glacial acetic acid 120g Potassium bromide 225g Add water to make 1.0 liter

Fixer Formulation Part-A (for 18 liter finish) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethylamino) ) -Ethyl-5-mercaptotetrazole 18 g Part-B Aluminum sulfate 800 g

The developer is prepared by adding Part to about 5 liters of water.
A and Part B were added at the same time, water was added while stirring and dissolving to make 12 liters, and the pH was adjusted to 10.40 with glacial acetic acid. This is used as a development replenisher.

20 ml / l of the above starter was added to 1 liter of this development replenisher to adjust the pH.
Is adjusted to 10.26 to make a working solution.

The fixing solution was prepared by adding Part to 5 liters of water.
A and Part B are added at the same time, water is added while stirring and dissolving to make 18 liters, and pH is adjusted with sulfuric acid and NaOH.
Was adjusted to 4.4. This is used as a fixing replenisher.

The processing temperature is 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing, 50 ° C. for drying, and the processing time is dry.
It is 45 seconds and 25 seconds in to dry.

After the processing, the sensitivity and contrast were measured and the fixability was evaluated. The sensitivity is expressed by the reciprocal of the exposure amount that gives a density of fog +0.5, and the sample No. The relative sensitivity is shown when the sensitivity in the treatment of No. 1 for 45 seconds is 100. The contrast is represented by the slope of the density of 0.25 to 2.0 in the characteristic curve. It is shown as a relative value when the contrast of 1 for 45 seconds is 1. The fixability is 25
Visually evaluate the transparency of the unexposed film in seconds processing,
The following three stages were used for evaluation. ◯: No problem Δ: Slightly inferior fixability (there is a problem in practical use in some cases) ×: Inferior fixability (not in practical use) The obtained results are shown in Table 2 below.

It can be seen that the sample of the present invention has high sensitivity and contrast, and does not impair the sensitivity and contrast even in rapid processing such as 25 seconds. Further, it can be seen that there is no problem in fixing property.

Next, each sample was stored for 7 days under the following two conditions. Condition A: 23 ° C., 55% RH Condition B: 40 ° C., 80% RH After storage, the same exposure and development processing as the above processing was performed, and the sensitivity was measured after the processing. For each sample, the difference in sensitivity between condition A and condition B was determined, and the sample No. It is shown as a relative value when the sensitivity difference of 1 is 100. The smaller the value is, the smaller the fluctuation is, which means that the value is excellent. Table 2 shows the obtained results.
Shown in It can be seen that the sample of the present invention has excellent storage stability.

[0231]

[Table 2]

Example 2 Preparation of Emulsion Em-5 (Comparative Emulsion) The tabular silver iodochloride emulsion Em was prepared using the following 5 kinds of solutions.
-5 was prepared. A5 Low methionine gelatin 214.37 g Sodium chloride 1.995 g Potassium iodide 149.6 mg Water to make 6090 ml B5 Sodium chloride 10.48 g Potassium iodide 149.4 mg Water to make 90 ml C5 Silver nitrate 30.58 g Water 90 Finish with milliliters D5 Sodium chloride 165.0g Finish with water 5640ml E5 Silver nitrate 479.0g Finish with water 5640ml

Solution A5 was vigorously stirred in the reaction vessel while maintaining it at 40 ° C., and the total amount of solution B5 and solution C5 was added thereto by the simultaneous mixing method at a flow rate of 180 ml / min for 30 seconds.

Next, after the mixed solution was kept at 40 ° C. for 10 minutes, the solution D5 and the solution E5 were added by the simultaneous mixing method at a flow rate of 24 ml / min for 40 minutes, and subsequently,
Furthermore, the total amount of the remaining solution D5 and solution E5 was added by the simultaneous addition method over 130 minutes while linearly increasing the flow rate so that the initial flow rate was 24 ml and the final flow rate was 48 ml. During this time, pCl was kept at 2.35 throughout.
Then, it was adjusted to 1.30 with sodium chloride, pCl was adjusted to 2.0 using an ultrafiltration membrane, and pCl was adjusted to 1.65 by adding sodium chloride.

Subsequently, this emulsion was ripened in the same manner as Emulsion Em-1. The obtained silver halide emulsion contained 0.06 mol% iodide, and when observed by an electron microscope, the average grain size (converted to a circle diameter) was 1.45 μm, and the average thickness was 0.1.
13 μm, average aspect ratio 11, width of particle size distribution 2
It was a right parallelogram tabular silver halide grain of 8.0%.

Preparation of Emulsion Em-6 (Comparative Emulsion) The tabular silver iodochloride emulsion Em was prepared using the following 5 solutions.
-6 was prepared. A6 Low methionine gelatin 214.37 g Sodium chloride 1.995 g Water to make 6090 ml B6 Sodium chloride 3.49 g Water to make 30 ml B61 Sodium chloride 6.99 g Potassium iodide 149.4 mg Water to make 60 ml C6 Silver nitrate 30.58g Finish with water 90ml D6 Sodium chloride 165.0g Finish with water 5640ml E6 Silver nitrate 479.0g Finish with water 5640ml

Solution A6 was vigorously stirred in the reaction vessel while keeping it at 40 ° C., and the entire amount of solution B6 and 1 part of solution C6 were added thereto.
/ 3 amount was added by the simultaneous mixing method at a flow rate of 180 ml / min for 10 seconds, and then the total amount of solution B61 and 2/3 amount of solution C6 were simultaneously added at a flow rate of 180 ml / min for 20 seconds. It was added by the mixing method.

Next, after the mixed solution was kept at 40 ° C. for 10 minutes, the solution D6 and the solution E6 were added by the simultaneous mixing method at a flow rate of 24 ml / min over 40 minutes.
Further, the remaining total amount of solution D6 and solution E6 was added by the simultaneous addition method over 130 minutes while linearly increasing the flow rate so that the initial flow rate was 24 ml and the final flow rate was 48 ml. During this time, pCl was kept at 2.35 throughout.
Then, it was adjusted to 1.30 with sodium chloride, pCl was adjusted to 2.0 using an ultrafiltration membrane, and pCl was adjusted to 1.65 by adding sodium chloride.

Subsequently, this emulsion was ripened in the same manner as Emulsion Em-1. The obtained silver halide emulsion contained 0.06 mol% iodide, and when observed by an electron microscope, the average grain size (converted to a circle diameter) was 1.45 μm, and the average thickness was 0.1.
13 μm, average aspect ratio 11, width of particle size distribution 1
It was a rectangular parallelepiped tabular silver halide grain of 8.5%.

Using the resulting emulsion, in the same manner as in Example 1, coated sample No. 5, no. No. 6 was created.
The obtained sample No. The results of the same evaluations as in Example 1 using 5 and 6 are shown in Table 3. Sensitivity, contrast,
As for the storability, the sample No. It was expressed as a relative value when the value of 5 was set to 100, and the fixability was evaluated by visual observation in three stages.

[0241]

[Table 3]

As is clear from Table 3, the samples of the present invention have high sensitivity and contrast, and do not impair the sensitivity and contrast even in rapid processing such as 25 seconds. Further, it can be seen that there is no problem in fixing property and storage property is excellent.

Example 3 Using Samples 1 to 4 prepared in Example 1, the sensitivity and fixability were evaluated.

The sample was sandwiched between two screens (KO-250 manufactured by Konica Corporation), and exposed through an aluminum wedge with an X-ray of a tube voltage of 80 kvp and a tube current of 100 mA for 0.05 seconds. Then, an automatic processor (SRX-502 manufactured by Konica Corporation) was used to perform processing with a developer and a fixer having the following formulations.

A developing supplement tablet was prepared according to the following procedure (A, B). Operation (A) 3,000 g of hydroquinone as a developing agent is ground in a commercially available Bandham mill until the average particle size becomes 10 μm. 3000g of sodium sulfite and 20g of potassium sulfite in this fine powder
00g and Dimezone S1000g were added and mixed in a mill for 30 minutes, and then in a commercially available stirrer for about 10 minutes at room temperature.
After granulating by adding 0 ml of water,
The granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granulated product. 100 g of polyethylene glycol 6000 was added to the granulated product thus prepared.
Was evenly mixed for 10 minutes in a room whose humidity was adjusted to 25 ° C and 40% RH or less, and then the obtained mixture was mixed with a tableting machine which was modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho. Filling amount per tablet 3.84g
After that, the tablets were compressed and compressed into 2,500 developing replenishment tablets A.
A preparation was made.

Operation (B) DTPA 100 g, potassium carbonate 4000 g, 5-methylbenzotriazole 10 g, 1-phenyl-5-mercaptotetrazole 7 g, 2-mercaptohypoxanthine 5 g, KOH 200 g, N-acetyl-D, L-penicillamine 10 g were added. Pulverize and granulate as in the operation (A).
The amount of water added is 30.0 ml, and after granulation, 50 ℃
For 30 minutes to remove the moisture of the granules almost completely. The mixture obtained in this way is used by Kikusui Seisakusho KK
Using a tableting machine modified from Tough-Presto Correct 1527HU, the filling amount per tablet was 1.73 g, and compression tableting was performed to prepare 2500 developing replenishing tablet B agents.

Next, a fixing supplementary tablet was prepared by the following procedure. Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is ground in the same manner as in (A), and then uniformly mixed with a commercially available mixer.

Then, in the same manner as in (A), the amount of water added was adjusted to 5
Granulate to 00 ml. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. In this way, 4 g of sodium N-lauroylalanine was added to the prepared granules, and the mixture was added at 25 ° C. and 40%.
Mix for 3 minutes with a mixer in a room conditioned below RH. Next, the obtained mixture was mixed with a tableting machine obtained by modifying a tough press collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
Compression tableting was performed at a filling amount per tablet of 6.202 g, and 2500 fixing supplement replenishing tablets C were prepared.

Operation (D) 1000 g of boric acid, 150 parts of aluminum sulfate-18 hydrate
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
Grain and granulate in the same manner as in the operation (A). The amount of water added is 100 ml, and after granulation, the granulated product is dried for almost 30 minutes at 50 ° C. to almost completely remove water. 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and the mixture was mixed for 3 minutes, and then the obtained mixture was mixed with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Filling amount is 4.562
The mixture was compressed to g and compressed to give 1250 fixing replenishment tablets D preparation.

[Starter composition] 2.98 g of glacial acetic acid 4.0 g of KBr Water was added to make 1 liter.

At the start of processing of the developing solution (starting of running), 16.5 liters of the developing solution prepared by diluting the developing tablet with diluting water was added to 330 ml of the starter, and the developing tank was filled with the solution to start the processing. Started. The pH of the developer containing the starter was 10.
45.

The light-sensitive material prepared above was exposed to light so that the optical density after development was 1.0, and was run. For the running, an automatic developing machine SRX-502 equipped with a charging member of a solid processing agent and modified so as to be able to process at a processing speed of 25 seconds was used.

During running, the developing solution contained a light-sensitive material of 0.6.
It was carried out by adding 2 each of the above-mentioned agents A and B and 76 ml of water per 2 m ² . The pH when each of A and B was dissolved in 38 ml of water was 10.70. To the fixing solution, ² parts of the above C agent, 1 part of D agent and 74 ml of water were added per 0.62 m ² of the light-sensitive material. Each treatment agent 1
The rate of addition of water to each piece was started almost at the same time as the addition of the treatment agent, and was added at a constant rate for 10 minutes in proportion to the dissolution rate of the treatment agent. Processing conditions Development 39 ° C 5.0 seconds Fixing 36 ° C 3.5 seconds Washing 35 ° C 2.5 seconds Squeeze 1.5 seconds Drying 50 ° C 2.5 seconds Total 15 seconds Developer solution Potassium carbonate 40 g Hydroquinone 30 g Dimezone S 10 g Diethylenetriamine penta Acetic acid-5Na 1g (DTPA) Potassium bromide g 5-Methylbenzotriazole 0.1g 1-Phenyl-5-mercaptotetrazole 0.07g 2-Mercaptohypoxanthine 0.05g Sodium sulfite 30.00g Potassium sulfite 25g KOH 2g Diethylene glycol 50 g N-acetyl-D, L-penicillamine 0.1 g These were dissolved in 300 ml of water, and finally purified to 400 ml. This concentrate was diluted with water to 1 liter to prepare a replenisher. The pH of this replenisher is 1
It was 0.70. The amount of replenisher is 7 ml /
Used in quarters.

Sodium thiosulfate 42.0 g Potassium thiosulfate 98.0 g Sodium sulfite 15.0 g Boric acid 10.0 g Sodium hydrogen acetate 30.0 g Glacial acetic acid 17.3 g Sodium acetate 12.7 g Tartaric acid 2.0 g These 400 ml of these It was dissolved in water and finally made up to 500 ml with pure water. This concentrate was diluted with water to 1 liter to prepare a replenisher. The pH of this replenisher was 4.50. The amount of replenisher is 7 ml /
Used in quarters.

The results obtained are shown in Table 4.

[0256]

[Table 4]

As is clear from Table 4, the samples of the present invention are
It can be seen that the sensitivity is high and the sensitivity is not impaired even in the ultra-rapid processing such as 15 seconds. Also, it can be seen that there is no problem in fixing property.

Example 4 In Example 3, the following procedure (E) and procedure (F) were adopted in place of the procedure (A) and the procedure (B) in the method for preparing a developing replenishing tablet, and the developer was used as a developing agent. Development was carried out using sodium erythorbate instead of hydroquinone, but the same results as above were obtained regardless of the type of developing agent. That is, the problem in the case of not using hydroquinone was overcome by the application of the present invention.

Operation (E) 12500 g of a developing agent, sodium erythorbate, is pulverized in a commercially available bandam mill until the average particle size becomes 10 μm. To this fine powder, 2000 g of sodium sulfite, 2700 g of dimezone S, 1250 g of DTPA, 12.5 g of 5-methylbenzotriazole, 4 g of 1-phenyl-5-mercaptotetrazole and 12.5 g of N-acetyl-D, L-penicillamine were added, and the mixture was stirred in a mill for 30 minutes. After mixing for 30 minutes and granulating by adding 30 ml of water in a commercially available stirring granulator at room temperature for about 10 minutes, the granulated product is dried in a fluidized bed dryer at 40 ° C. for 2 hours. To almost completely remove the water content of the granulated product. To the granulated product thus prepared, 1670 g of polyethylene glycol 6000 and 1670 g of Mannitol 1670 g were uniformly mixed for 10 minutes using a mixer in a room where the humidity was adjusted to 25 ° C. and 40% RH or less,
The obtained mixture was compressed into tablets with a filling amount of 8.77 g per tablet using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., and 2500 tablets for developing replenishment E were prepared. Created.

Operation (E) 4,000 g of potassium carbonate, 2100 g of mannitol, and 2100 g of polyethylene glycol 6000 were operated (A).
Pulverize and granulate as in The amount of water added was 30.0 ml, and after granulation, the granulated product was dried for 30 minutes at 50 ° C. to almost completely remove water. The mixture thus obtained was manufactured by Kikusui Seisakusho Co., Ltd. Tough Presto Correct 15
Using a tableting machine modified from 27HU, the filling amount per tablet was set to 3.28 g, and compression tableting was carried out to prepare 2500 developing replenishing tablet F agents.

The obtained sample No. 5-No. 6 was used and the same evaluation as in Example 1 was performed. Further sharpness (CTF)
Was evaluated as follows. After development, the portion having an optical density of 1.0 was measured with an aperture of 30 μm × 500 μm, and the CTF value at a spatial frequency of 1.0 cycle / mm was measured. The relative value when 5 is set to 100 is shown. Table 5 shows the obtained results. It can be seen that the present invention provides excellent results.

[0262]

[Table 5]

[0263]

As described above, according to the present invention, a silver halide emulsion having high sensitivity, high γ, high image quality, excellent rapid processing, storage stability and processing variability, and a method for producing the same, and To provide a silver halide photographic light-sensitive material, and to provide a method for rapidly processing a silver halide photographic light-sensitive material having such performance by a processing method which is safe and environmentally friendly. I was able to.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 5/29 G03C 5/29

Claims (9)

[Claims] 1. A silver halide emulsion containing at least 50 mol% of silver chloride, wherein 50% or more of the total projected area of silver halide grains contained in said silver halide emulsion is tabular silver halide grains. And the main plane of the tabular silver halide grain has an adjacent edge ratio of 10
Is less than (100) face, the average aspect ratio of the tabular silver halide grains is 2 or more, and the variation coefficient of the projected area diameter of the main plane of the tabular silver halide grains is 20 or less.
% Or less, a silver halide emulsion characterized by being below. 2. The average aspect ratio according to claim 1,
2. The silver halide emulsion according to claim 1, which is not less than 8 and less than 8. 3. The silver halide emulsion according to claim 1, wherein the average silver iodide content is less than 1.5 mol%. 4. A method for producing a silver halide emulsion containing at least 50 mol% of silver chloride, wherein at least (1) the step of adding a silver salt in the absence of iodide and initiating nucleation. And (2) a method for producing a silver halide emulsion, which comprises two steps of subsequently adding a silver salt in the presence of an iodide to perform nucleation and / or crystal growth. 5. A silver halide emulsion containing at least 50 mol% or more of silver chloride, wherein 50% or more of the total projected area of silver halide grains contained in the silver halide emulsion is (100) plane. A method for producing a silver halide emulsion which is a tabular silver halide grain having a main plane of at least (1) a step of adding a silver salt in the absence of iodide to start nucleation, and (2) ) A method for producing a silver halide emulsion, which comprises two steps of subsequently adding a silver salt in the presence of an iodide to perform nucleation and / or crystal growth. 6. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the emulsion layers contains the silver halide emulsion according to claim 1. A silver halide photographic light-sensitive material characterized by the above. 7. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on each side of a support, wherein at least one of said emulsion layers comprises the silver halide emulsion according to claim 1. A silver halide photographic light-sensitive material characterized by containing. 8. A silver halide photographic light-sensitive material, characterized in that the silver halide photographic light-sensitive material according to claim 6 or 7 is treated with a developer containing substantially no dihydroxybenzenes in the developer. Processing method. 9. A method of processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to claim 6 or 7 for a total processing time of 10 to 45 seconds.