JPH09160152A - Silver halide emulsion and its manufacture, and silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide emulsion high in sensitivity and the gamma value and low in fog and superior in aptitude to rapid processing by forming the nuclei of flat silver halide grains having (100) principal crystal faces and amounting to the specified fraction of the projection areas of the total silver halide grains in the presence of bromine ions. SOLUTION: The silver halide emulsion containing at least >=30mol% silver chloride contains the flat silver halide grains having the (100) principal crystal faces in an amount of >=50% of the projection areas of the total silver halide grains, and the nuclei of the flat silver halide grains are formed in the presence of bromine ions. Silver bromochloride or iodobromochloride and the like can be used for the silver halide and it is preferred for the silver halide emulsion to contains the flat silver halide grains in an amount of, preferably, >=50mol%, further, >=70mol%, especially, >=90mol%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silver halide emulsion containing tabular silver halide grains and a method for producing the same. Further, it relates to a silver halide photographic light-sensitive material and a processing method thereof.

[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 reduce the processing time and the processing waste liquid. For example, in the medical field, regular health checkups,
The spread of medical checkups and the number of examinations including diagnosis in general medical care have increased sharply, the number of X-ray photographs taken has increased, and further development processing after photography has been desired. Also, from the viewpoint of environmental protection, it is planned to prohibit the dumping of processing solutions into the ocean from 1996, and there is a strong demand for reduction of processing waste solutions. Is desired.

However, in order to speed up the processing, it is necessary to shorten the processing time of each processing step such as developing, fixing, washing with water, and drying, and the load on each step increases.

For example, if the developing time is simply shortened, the image density of the conventional photosensitive material is lowered, that is, the sensitivity is lowered and the gradation is deteriorated. Further, when the fixing time is shortened, the fixing of silver halide becomes incomplete and 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 of the silver halide surface is reduced,
It is known that the adsorptivity of the spectral sensitizing dye may be deteriorated to lower the spectral sensitivity, or the pressure characteristics may be deteriorated. Further, it is known that if the silver iodide content inside the silver halide is lowered, the pressure characteristics may deteriorate.

Therefore, it is desired to develop a technique of containing silver iodide and 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 the fixing speed.

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

By the way, in recent years, many techniques for improving sensitivity and image quality using tabular silver halide grains have been disclosed, for example, JP-A Nos. 58-111935 and 58-58.
No. 111936, No. 58-111937, No. 58-1
No. 13927, No. 59-99433, and the like.

These tabular silver halide grains are hexahedral,
Compared with so-called regular crystal silver halide grains such as octahedron, the surface area is large in the same volume, so it is possible to increase the adsorption amount of the sensitizing dye on the grain surface, and as a result, it is possible to achieve high sensitivity. There is.

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 silver halide grain. Is disclosed, and the effect of increasing the sensitivity is shown.

In addition to this, for example, Japanese Patent Laid-Open No. 63-10674.
6, JP-A-1-183644 and 1-279237.
Discloses a technique relating to the composition distribution of tabular silver halide grains. Further, JP-A-5-281640, 5-313273, and 6-19028 disclose (10
The technology of tabular silver halide grains having the (0) plane as the main plane is also disclosed, but all of them have high sensitivity,
This is a technique for grains having a high silver iodide content or silver iodobromide grains aiming at high image quality, and no grain having a high silver chloride content is described.

For tabular grains containing silver chloride, (1
Some of tabular grains having a (11) plane as a main plane have been disclosed.
1) Since the surface is formed, the additive has a great adverse effect on the photographic performance, and further breakthrough is required 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 most 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. 36,816 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 with time, it has a drawback that it is difficult to obtain a constant silver image. There is a strong demand for technologies to overcome.

[0017]

Therefore, the first object of the present invention is to provide a silver halide emulsion and a photosensitive material which have high sensitivity, high γ, low fog, excellent suitability for rapid processing, and low processing solution replenishment. To provide the material.

A second 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.

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

[0020]

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

(1) In a silver halide emulsion containing at least 30 mol% of silver chloride, 50% of the total projected area of silver halide grains contained in the silver halide emulsion.
% Or more are tabular silver halide grains having a (100) plane as a main plane, and are obtained by allowing bromine ions to be present at the time of nucleation of the tabular silver halide grains. Silver halide emulsion.

(2) A halogen silver photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the emulsion layer contains the silver halide emulsion described in (1). Silver halide photographic light-sensitive material.

(3) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on each side of a support, wherein the emulsion layer contains the silver halide emulsion described in (1). A silver halide photographic light-sensitive material.

(4) A silver halide photographic process characterized in that the silver halide photographic light-sensitive material described in (2) to (3) is treated with a developing solution containing substantially no dihydroxybenzenes. Method of processing photosensitive material.

(5) A method of processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material described in (2) to (3) in a total processing time of 10 to 25 seconds.

(6) A silver halide emulsion containing at least 30 mol% of silver chloride, wherein the total projected area of the silver halide grains contained in the silver halide emulsion is 50.
In the method for producing a silver halide emulsion in which tabular silver halide grains whose main plane is the (100) plane is bromine ion, the tabular silver halide grains have a bromine ion at the time of nucleation. Method for producing silver halide emulsion.

The present invention will be described in more detail below.

The tabular silver halide grains contained in the silver halide emulsion of the present invention (hereinafter sometimes abbreviated as tabular silver halide grains of the present invention) contain at least 30 mol% of silver chloride. , Preferably 50 mol% or more, more preferably 70 mol% or more,
Most preferably, the content is 90 mol% or more.

In the tabular silver halide grains of the present invention, silver bromochloride, silver iodobromochloride, etc. can be used as the silver halide. In the case of silver bromochloride, the content of silver bromide is 0.01 mol% or more and 70 mol% or less, but preferably 50 mol% or less, as the average silver bromide content in the entire silver halide grains. , More preferably 30 mol% or less, most preferably 10 mol% or less. In the case of silver iodochloride, the content of silver iodide is preferably 0.01 mol% or more and 1.0 mol% or less, but 0.01 mol% or more, as the average silver iodide content in the entire silver halide grains. It is more preferably 0.5 mol% or less.

In the present invention, the halogen composition of each silver halide grain is determined by the EPMA method (Electron Pr).
of the Micro Analyzer method). This method produces a well-dispersed sample so that the emulsion grains do not touch each other,
X-ray analysis is carried out by irradiating an electron beam and exciting the electron beam, and elemental analysis of extremely small parts can be performed. By this method, the silver halide composition of each grain can be determined by determining the characteristic X-ray intensity of silver and each halogen emitted from each grain. EP for at least 50 particles
When the silver halide composition is determined by the MA method, the average silver bromide content and the average silver iodide content are determined from their averages.

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

In the tabular silver halide grain of the present invention, the position containing silver bromide may be inside or outside of the grain, but it is contained at least inside. In this case, the internal composition preferably contains silver bromide in an amount of 0.1 mol% or more and 90 mol% or less. Further, in the present invention, the tabular silver halide grains can contain silver iodide inside.
In this case, the internal composition preferably contains 0.001 mol% to 38 mol% of silver iodide. Here, the halogen composition distribution inside the silver halide grain is pretreated into ultrathin sections of the grain, and then observed with a transmission electron microscope while cooling,
It is obtained by conducting an analysis. Specifically, after taking out silver halide grains from the emulsion, they are embedded in a resin and cut with a diamond knife to obtain a thickness of 60.
Make nm sections. This section can be obtained by observation and point analysis with a transmission electron microscope equipped with an energy dispersive X-ray analyzer while cooling the section with liquid nitrogen, and by quantitative calculation (Inoue, Nagasawa: Photographic Society of Japan, 1987) Conference Abstracts p. 62).

In the tabular silver halide grain of the present invention, it is also preferable that silver bromide and silver iodide are present on the outermost surface. In this case, the silver bromide content on the outermost surface is preferably 1 mol% or more and 90 mol% or less, and the silver iodide content on the outermost surface is preferably 1 mol% or more and 10 mol% or less. Further, silver bromide and silver iodide may coexist on the outermost surface. Here, the silver bromide content on the outermost surface of the tabular silver halide grains,
The silver iodide content means the XPS method (X-ray Photo
Electron Spectroscopy (X-ray photoelectron spectroscopy) is the content rate of a portion up to a depth of 50 A, which can be determined as follows.

The sample was cooled in an ultrahigh vacuum of 1 × 10 ^-8 torr or less to -110 ° C. or less, and MgKα was irradiated as an X-ray for a probe 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 the emulsion are tabular silver halide grains.

The tabular silver halide grains in the present invention are
A particle having two parallel main planes facing each other, and having a particle diameter to particle thickness ratio (hereinafter referred to as an aspect ratio) of more than 1.3. Here, the main plane is a plane having the largest area in the tabular silver halide grains. The grain size is a projected area diameter (hereinafter referred to as grain size), and is a circle-equivalent diameter of the projected area of the main plane of the tabular silver halide grain (diameter of a circle having the same projected area as the silver halide grain). ), And the thickness means the distance between two parallel principal planes forming a tabular silver halide grain.

In the present invention, the average aspect ratio of the tabular silver halide grains is preferably 2 or more, more preferably 2 or more and less than 8.

The present invention is characterized in that 50% or more of the total projected area of the silver halide grains contained in the emulsion consists of tabular silver halide grains having the (100) plane as the principal plane, but preferably. 70% or more, more preferably 90% or more, is 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 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 most preferably less than 2. Also,
The length of the side when the corner is missing or rounded is the length up to the intersection with the line that extends the straight line part of the side of the right-angled parallelogram and extends the straight line part of the adjacent side. expressed.

The average grain size of the tabular silver halide grains of the present invention is preferably 0.15 to 5.0 μm,
The thickness is more preferably 2 to 3.0 μm, most preferably 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 0.2 μm. It is 30 μm.

The 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 hydrophilic colloid layer, hardness, chemical ripening conditions, sensitivity of photosensitive material, amount of silver coating, etc.) that affect sensitivity and other photographic characteristics The thickness is different.

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

The tabular silver halide grains of the present invention preferably have a narrow thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width of thickness distribution (%), it is preferably 25% or less, more preferably 20%. It is as follows, particularly preferably 15% or less.

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 particles of 0.25 μm thickness)
It is possible to observe more clearly by using the above electron microscope.

The method for producing tabular silver halide grains of the present invention is characterized by the presence of bromine ions during nucleation. It is considered that the presence of bromine ions at the time of nucleation appropriately increases the probability of dislocation generation, increases the ratio of tabular grains, and narrows the width of the grain size distribution. Although the reason is not clear, the above effect cannot be sufficiently obtained in the case of iodine ion.

Specifically, a method of preliminarily containing bromine ions in the dispersion medium at the time of nucleation, a method of incorporating bromine ions in a halide salt solution as an additive solution, and the like can be mentioned. Incidentally, it is technically difficult to produce tabular silver halide grains having a (100) plane as a main plane without adding odor ions and iodine ions, and good performance cannot be obtained.

The manufacturing method will be described in detail below.

Nucleation is carried out by adding a silver salt and / or halide salt solution to a dispersion medium solution containing at least a dispersion medium and water while stirring. PCl during nucleation is (10
0) surface is easy to form, that is, 0.5 to 3.5, preferably 1.0 to 3.0, and more preferably 1.5 to 2.
Adjust to 5. Moreover, pBr is adjusted to 0.5 to 4.0, preferably 1.0 to 3.0, and more preferably 1.5 to 2.5. Further, bromine ions in the dispersion medium solution during nucleation are preferably present in an amount of 1 mol% to 99 mol% of all halogen ions. The pH is preferably 1.0 or higher, more preferably 1.5 or higher, and even more preferably 2.0 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 30 μm
It is preferable to use so-called low methionine gelatin having an ol / gelatin of less than 1 g, preferably less than 15 μmol / gelatin of less than 1 g. Further, the molecular weight is 1000 to 10 × 10.
⁴ , preferably 2000 to 6 × 10 ⁴ , so-called low molecular weight gelatin or the like is preferably used. 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,
0.3 to 5% by weight is more preferable.

Nucleation starts from the moment when the silver salt is added to the dispersion medium solution. Therefore, in the present invention,
The phrase "bromine ion is present during nucleation" means that the bromine ion is contained in the dispersion medium solution 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 period during which the silver salt is added and nucleated in the presence of bromide ions is preferably 1 second to 5 minutes, more preferably 5 seconds to 2 minutes, and most preferably 10 seconds to 1 minute. During this time, pCl, p
Other Br salt may or may not be added as long as Br is in the above preferred range. 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.

In the production method of the present invention, the temperature in the process of causing nucleation is preferably 10 ° C. or higher, and 20 to 70 ° C.
Is particularly preferred.

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.

In the present invention, a silver salt may be added by further allowing iodide ions to be present at the time of nucleation. The iodine ion concentration in the dispersion medium solution at this time can be introduced up to the solid solution limit of silver iodide and silver chloride / silver bromide, but 0.001 to 10
It is preferably set to mol%, more preferably 0.01
８8 mol%. As a method of allowing the iodine ions to be present in the dispersion medium solution, for example, a method of previously containing the iodine ions in the dispersion medium solution or a method of adding the iodine ions to the halide salt solution and adding them can be used. At this time, any method such as a double jet method in which a silver salt solution is simultaneously added, 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 production method of the present invention follows the nucleation process,
It is preferable to have an aging process and / or a crystal growth process. The aging process and the crystal growth process may be the same, or may be the order of ripening-crystal growth or the order of crystal growth-aging,
Also, both processes can be repeated alternately multiple times,
It is preferable to first have a crystal growth process following the nucleation process, or to perform aging and crystal growth at the same time.

In the ripening process, the tabular grains generated during nucleation can be further grown by Ostwald ripening, and the other grains can be eliminated. Aging temperature is 20
To 90 ° C. is preferable, 30 to 85 ° C. is more preferable, and 40 to 80 ° C. is most preferable. Although the temperature during aging may be constant or changed, a method of changing the aging temperature is advantageously used when a crystal growth process is further performed. The pCl during aging is preferably 0.5 to 3.5.
0 to 3.0 is more preferable. The pH is preferably 1-12, more preferably 2-8, most preferably 2-6.
It is. The ripening is preferably carried out in the absence of a so-called silver halide solvent such as ammonia.

The pCl during crystal growth is adjusted within the range of 0.5 to 3.5, preferably 1.0 to 3.0, more preferably 1.5 to 2.5. Moreover, pH is 1 to 1.
2 is preferable, 2 to 8 is more preferable, and 2 to 6 is the most preferable. The temperature during crystal growth is preferably 20 to 90 ° C, more preferably 30 to 85 ° C, and most preferably 40 to 80 ° C. The method of adding silver ions and halide ions during crystal growth is any of a double jet method in which a silver salt and a halide salt solution is added, a fine particle supply method in which a previously prepared AgX fine particle emulsion is added, and a combination of both methods. May be used. Of these,
A fine particle supply method is preferably used. When using the fine particle supply method, the diameter of the fine particles is preferably 0.15 μm or less,
0.1μ or less is more preferable, most preferably 0.06
μ 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 the 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 the 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 the 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 of growing by adding silver halide fine particles, dissolving and recrystallizing as described in the 88th Annual Meeting of the 1983 Annual Meeting of the Photographic Society of Japan is also preferably used. Especially silver iodide fine particles,
Silver bromide fine particles, silver iodobromide fine particles, silver bromochloride fine particles, and silver chloride fine particles are preferably used.

The tabular silver halide grains of the present invention may be so-called halogen conversion type grains. The halogen conversion amount is preferably from 0.2 mol% to 0.5 mol% with respect to the silver amount, and the conversion may be performed during physical ripening or after completion of physical ripening.

As a method of converting halogen, an aqueous solution of halogen or fine silver halide grains having a smaller solubility product with silver than the halogen composition on the surface of the grain before halogen conversion is usually added. The particle size at this time is 0.2 μm
The following is preferable, and more preferably 0.02 to 0.1 μm
It is.

When silver iodide is contained on the outermost surface of the tabular silver halide grains of the present invention, the method is to add a silver nitrate solution and a solution containing iodide ions to the emulsion containing the tabular grains as the 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.
Particularly preferred is the addition of fine silver iodide grains and fine silver iodobromide 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 in several times with a time interval, or another chemically ripened emulsion may be added after the addition of the fine grains.

The temperature of the emulsion of the present invention at the time of adding fine silver halide grains is preferably in the range of 30 to 80 ° C, and particularly preferably in the range of 40 to 65 ° C. Further, the present invention is preferably carried out under the condition that part or all of the silver halide fine grains to be added disappears immediately before coating immediately after the addition, more preferably 20% of the added silver halide fine grains. The above is the disappearance immediately before the application.

In producing the tabular silver halide grains of the present invention, stirring conditions during production are extremely important. As the stirring device, a device in which the additive liquid nozzle disclosed in JP-A-62-160128 is installed in the liquid near the mother liquid inlet of the stirrer is particularly preferably used.

The stirring rotation number at this time is 100 to 1200 r.
It is preferably pm.

In the tabular silver halide grain of the present invention, the 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 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 thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is added in an amount of 1 × 10 ⁻³ mol or more and 3 × 10 ³ mol / mol of silver.
It is preferable to add ^-2 mol or less.

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)
rc Disclosure. RD)
76 volume No. 17643 (December 1978).

In the production of the tabular silver halide grains of the present invention, unnecessary soluble salts may be removed after the growth of the silver halide grains, or they may be contained therein.
When removing the salts, see RD Vol. 176
It can be carried out based on the method described in Item II of 43.

In the preparation of the tabular silver halide grains of the present invention, it is preferable to remove the soluble salts after the growth of the silver halide grains has been completed to obtain a pAg ion concentration suitable for chemical sensitization. As a method for removing the salts, a Nudel water washing method, a flocculation sedimentation method or the like may be used, and a preferable water washing method is, for example, JP-B-35-16.
The method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in No. 086, or the desalting method using the polymer flocculants such as Exemplified G-3 and G-8 described in JP-A No. 2-7037. be able to. Furthermore, Research Disclosure (RD) Vol. 102, 1972, 1
January issue, Item 10208 and Vol. 131, 19
75, March issue, Item 13122, it is also preferable to perform desalting using the ultrafiltration method.

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. The conditions of the step of chemical ripening or chemical sensitization, for example, pH, pAg, temperature, time and the like are not particularly limited, and they can be carried out under conditions generally used in the art. For chemical sensitization, sulfur sensitization using a compound containing sulfur that can react with silver ions or active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, using a reducing substance Reduction sensitization, gold and other, noble metal sensitization using a noble metal and the like can be used alone or in combination, among which selenium sensitization, tellurium sensitization, reduction sensitization, etc. are preferably used, In particular, a selenium sensitization method is preferably used.

In the case of selenium sensitization, the selenium sensitizer used may be a wide variety of selenium compounds, for example, US Pat. Nos. 1,574,944 and 1,602,5.
Nos. 92 and 1,623,499, JP-A-60-150
No. 046, JP-A-4-25832 and JP-A-4-10924.
Compounds described in Nos. 0 and 4-147250 can be used. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg,
Allyl isoselenocyanate, etc.), selenoureas (e.g., N, N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-)
Heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (for example, , Selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate) And the like, selenophosphates (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 the technique of using these selenium sensitizers are described in, for example, US Pat. Nos. 1,574,944 and 1,60.
2,592, 1,623,499, 3,29
7,446, 3,297,447, 3,32
0,069, 3,408,196, 3,40
8,197, 3,442,653, 3,42
0,670, 3,591,385, French Patent 2,693,038, 2,093,209, JP-B-52-34491, JP-B-52-34492, and 53.
-295, 57-22090, JP-A-59-18
Nos. 0536, 59-185330, 59-181
No. 337, No. 59-187338, No. 59-1922
No. 41, No. 60-150046, No. 60-15163
7, JP-A-61-246738, JP-A-3-4221
No. 3, No. 24-24537, No. 3-111838, No. 3
-116132, 3-148648, 3-23
No. 7450, No. 4-16838, No. 4-25832
Nos. 4-32831, 4-96059, 4-
No. 109240, 4-140738, 4-140
No. 739, No. 4-147250, No. 4-149437.
Nos. 4-184331, 4-190225, 4-191729, 4-195,035, British Patents 255,846 and 861,984. In addition, H. E. FIG.
Spencer et al. Journal of Photo
graphic Science, Vol. 31, 158-
It is also disclosed in scientific literature such as page 169 (1983).

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

The temperature of chemical ripening using a selenium sensitizer is 4
The range is preferably from 0 to 90 ° C, more preferably from 45 ° C to 80 ° C. The pH is 4-9 and the pAg is 6
The range of -9.5 is preferable.

Tellurium sensitizers and sensitizing methods are described in, for example, US Pat. Nos. 1,623,499 and 3,320,069.
Nos. 3,772,031 and 3,531,289
No. 3,655,394, British Patent 235,211.
Nos. 1,121,496 and 1,295,462
No. 1,396,696, Canadian Patent 800,95
No. 8, JP-A-4-204640, JP-A-4-33304
No. 3 and the like. Examples of useful tellurium sensitizers include telluroureas (e.g., N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'-dimethyl). -N'phenyltellurourea), phosphine tellurides (e.g., tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluramides (e.g., , Telluroacetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro esters, isotellurocyanates and the like.

The technique for using the tellurium sensitizer is similar to that for the selenium sensitizer.

It is also preferable to carry out so-called reduction sensitization on the grain surface by placing it in a suitable 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 according to environmental conditions such as pH and pAg, but in the case of thiourea dioxide, for example, as a rough guide, about 0.01 to 2 mg per mol of silver halide is used.
Is used with good results. In the case of ascorbic acid, the range is preferably about 50 mg to 2 g per mol of silver halide.

As the conditions for reduction sensitization, the temperature is about 40 to 7
0 ° C., time is about 10 to 200 minutes, pH is about 5 to 11, p
Ag is preferably in the range of about 1 to 10 (here, pAg
The value is the reciprocal of the Ag ⁺ ion concentration).

Silver nitrate is preferred as the water-soluble silver salt. So-called silver ripening, which is one of reduction sensitization techniques, is performed by adding a water-soluble silver salt. 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 silver halide grains subjected to reduction sensitization, the following general stabilizers can be used, but the antioxidant disclosed in JP-A-57-82831 can be used. Agent and / or V.I. S. Paper by Zehler [Zeitshift fur wissensc
haftriche Photographie B
d. 63, 133 (1969)] and JP-A-54-1.
Good results are often obtained in combination with the thiosulphonic acids described in 019. These compounds may be added at any stage of the emulsion production process from the 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. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobora cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

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, pyrazoline-
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei 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. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, a substituted aminostilbene compound which is a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
33,390 and 3,635,721), formaldehyde condensates of aromatic organic acids (for example, those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like. Good.

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, and chemical sensitization, or after chemical sensitization.

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

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In the light-sensitive material of the present invention, when at least one of the silver halide emulsion layer and any constituent layer other than the emulsion layer contains a dye capable of being decolorized and / or flowed out during the development processing, A photosensitive material having sensitivity, high sharpness and suitability for rapid processing can be obtained, which is preferable. The dye used in the photosensitive material may be appropriately selected from dyes that can improve sharpness by absorbing a desired wavelength and removing the influence of the wavelength, depending on the photosensitive material. I can do it. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and that the coloring is not visible when the image is completed.

The dye is a dye which is substantially insoluble in water at a pH of 7 or less and substantially water-soluble at a pH of 8 or more, and specifically represented by the following general formulas [1] to [6]. Selected from dyes.

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[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. Group, X and Y, which may be the same or different, each represents an electron-withdrawing group, L ₁ , L ₂ and L ₃
Each represents a methine group. m represents 0 or 1, and n
Represents 0, 1 or 2, and p represents 0 or 1. However, the dyes represented by the general formulas [1] to [6] have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule. The acidic nucleus represented by A and A 'in the general formulas [1], [2] and [3] is preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, Oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, 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 groups represented by Q and Q 'in [4] and [6] include pyridyl, quinolyl, isoquinolyl, pyrrolyl, pyrazolyl, imidazolyl, indolyl, furyl, thienyl and the like. Is mentioned. The aryl group and the heterocyclic group include those having a substituent, and 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,
Carboxy group, cyano group, hydroxy group, mercapto group, amino group, alkoxy group, aryloxy group, acyl group, carbamoyl group, acylamino group, ureido group,
Examples thereof include a sulfonamide group and a sulfamoyl group, and these substituents may have two or more kinds in combination. As a preferable substituent, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, t-butyl group, n-octyl group,
2-hydroxyethyl group, 2-methoxyethyl group, etc.),
Hydroxy group, cyano group, halogen atom (eg, 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.) ), A substituted amino group (for example, a dimethylamino group, a 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 (Eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (eg, 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 Area Special Issue No. 122 Structure-Activity Relationship of Drugs", 96
Pp. 103- (1979) Nankodo. ) Is preferably 0.3 or more, for example, a cyano group,
Alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl group, 4-hydroxyphenoxycarbonyl group), carbamoyl group (for example, carbamoyl group, methyl Carbamoyl, ethylcarbamoyl, butylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl, 4-carboxyphenylcarbamoyl, etc.), acyl (eg, methylcarbonyl, ethylcarbonyl, butylcarbonyl, phenylcarbonyl, 4-phenyl) Ethylsulfonamidophenylcarbonyl group, etc., alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octyls) Honiru group), an arylsulfonyl group (e.g., phenylsulfonyl group, 4-chlorosulfonyl group, etc.).

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.

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 dye represented by the general formula [1]. And particularly preferably a dye in which Q is a furyl group in the general formula [1].

Next, specific examples of the dye will be given.

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Specific examples of the dye are further described in JP-A-52-92.
No. 716, No. 55-120030, No. 55-1553
50, 55-155351, 56-12639.
No. 63-197943, JP-A No. 2-1838,
No. 2-1839, World Patent 88/04794, US 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 is described in JP-A Nos. 52-92716 and 55-155350.
No. 55-155351, No. 63-197943.
No. 3-182743, world patent WO88 / 047
The method described in No. 94 etc. can be used. Specifically, it can be prepared using a surfactant and a fine dispersing machine such as a ball mill, a vibration mill, a planetary mill, a sand mill, a roller mill, a jet mill, and a disk 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 dye may be used alone, or 2
Mixtures of more than one species may be used. 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 diameter 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) × 100 The conditions to be met as a preservative for the solid fine particle dispersion of the dye used in the photographic light-sensitive material, are as follows: It has no effect, is a bactericidal and mildew-proofing agent that is highly effective against small amounts of microorganisms such as bacteria, yeasts and molds, desensitization,
There are no influences on photographic performance such as fog, graininess and sharpness, and no influence on photographic processing performance such as developability and fixability.

As the surfactant used for dispersing the dye,
Any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, but preferably, for example, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates. , Sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, N-acyl-N-alkyl taurines and other anionic surfactants, and nonionics such as saponins, alkylene oxide derivatives, and alkyl esters of sugars It is a surfactant.

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 the dye 1 is used.
It may be 0.1 to 2000 mg per g, preferably 0.1 to 2000 mg.
It may be 5 to 1000 mg, more preferably 1 to 50 mg.
0 mg may be sufficient. The concentration in the dispersion of the dye is 0.0
It is used in an amount of 1 to 10% by weight, preferably 0.1 to 10% by weight.
1 to 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 and / or nonionic activators
Each of them may be used alone, two or more of them may be combined, or both may be used in combination.

To the dye dispersion, a hydrophilic colloid used as a binder for 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. These may be used in combination of two or more. The hydrophilic colloid added to the dye dispersion of the present invention is preferably added in an amount of 0.1 to 12% by weight, more preferably,
It is 0.5 to 8% by weight.

The constituent layer containing a dye 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 another hydrophilic colloid layer 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 compound that binds to at least one of the above-mentioned dyes. Examples of such a compound 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.
-1418, U.S. Patent Nos. 2,548,564, 2,675,316, 2,795,519, 2,839,401, 2,882,156, and 3,048 3,487,309, 3,444,138, 3,445,231, 3,706,563, 3,709,690, 3,788,855 And the like.

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 of binding in a suitable binder and dispersing in an aqueous gelatin solution by ultrasonic waves or the like can also be applied.

The binding ratio varies depending on the compound, but 0.1 part to 10 parts of the non-diffusible mordant is usually bonded to 1 part of the water-soluble dye. Since the water-soluble dye is added to the non-diffusible moldant, it can be used in a larger amount than when the dye is 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 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 can be contained in at least any one of constituent layers other than the silver halide emulsion layer or the emulsion layer for the purpose of improving pressure resistance. As the polymer latex, a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid or styrene, a styrene-butadiene copolymer, an active methylene group, a polymer or copolymer comprising a monomer having a water-soluble group or a crosslinkable group with gelatin may be used. It can be preferably used.

In particular, in order to increase the affinity with gelatin as a binder, a copolymer with a monomer having a water-soluble group mainly composed of an alkyl ester of acrylic acid, a hydrophobic monomer such as styrene or a crosslinkable group with gelatin is most preferable. It is preferably used. Desirable examples of the monomer having a water-soluble group include acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, and styrenesulfonic acid. Desirable monomers having a crosslinking property with gelatin are preferable. Examples include glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, and the like.

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 from 0.6 to 10 μm, particularly preferably from 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 the pressure resistance, the silver halide emulsion layer can 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 oxides selected from alkali metals and alkaline earth metals, silicon oxide (colloidal silica), aluminum oxide, tin oxide, vanadium oxide and yttrium oxide are preferable among them in terms of transparency and hardness. . 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.
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 per one side of the support, and more preferably 2.0 g / m ² when the emulsion layers are on both sides of the support. m ² or less. When it is on one side of the support, it 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, a medical light-sensitive material, a printing light-sensitive material, a negative light-sensitive material for general photography), a color photographic light-sensitive material (for example, a color negative). Sensitive materials, color reversal sensitive materials, color printing sensitive materials, etc.), diffusion transfer photosensitive materials, photothermographic materials, etc., but black and white silver halide photographic photosensitive materials are preferred, and medical sensitive materials are particularly preferred. Is.

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

The silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention preferably contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
Methyloldimethylhydantoin etc.), dioxane derivative (2,3-dihydroxydioxane etc.), active vinyl compound (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'- Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine) such as methylenebis (β- (vinylsulfonyl) propionamide), mucohalogen acids (mucochloric acid, mucophenoxycyclolic acid, etc.), isoxazoles , 2-chloro-6-hydroxytriazinylated gelatin, etc. can be used alone or in combination, and among them, JP-A Nos. 53-42121, 53-57257, and 59-59.
Active vinyl compounds described in US Pat. Nos. 163,456 and 60-80846 and active halogen compounds described in US Pat. No. 3,325,287 are preferable.

Polymeric hardeners can also be effectively used as the hardener of the present invention. Polymers having aldehyde groups such as dialdehyde starch, polyacrolein, acrolein copolymers described in US Pat. No. 3,396,029, polymers having epoxy groups described in US Pat. No. 3,623,878, US Pat. , 362,827, RD-17
333 (1978) and the like, polymers having a dichlorotriazine group, JP-A-56-66841, polymers having an active ester group, JP-A-56-142524, U.S. Pat. 40
7, JP-A-54-65033, RD-16725.
Polymers having an active vinyl group described in (1978) and the like, or a group serving as a precursor thereof are preferable. Among them, an active vinyl group having a long spacer as described in JP-A-56-142524, or Particularly preferred are polymers in which the precursor group is attached to the polymer backbone.

In order to make the photographic light-sensitive material of the present invention suitable for rapid processing, an appropriate amount of a hardener is added in advance in the step of applying the light-sensitive material to adjust the water swelling rate in the developing-fixing-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 preferably has a swelling ratio during development of 150 to 250% and a film thickness after expansion of 70 μm or less. Water swelling rate is 250%
If it exceeds the above range, poor drying occurs, and, for example, defective transport occurs in automatic processor processing, especially in rapid processing.

When the water swelling ratio is less than 150%, uneven development and residual color tend to increase when developing. The water swelling ratio as referred to herein means the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, and this is divided by the film thickness before processing and multiplied by 100. .

The support usable 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 these supports may be provided with an undercoat layer for improving the adhesion of the coating layer, corona discharge or ultraviolet irradiation.

In the silver halide photographic light-sensitive material of the present invention, various additives can be further added to the silver halide emulsion according to the purpose. Examples of additives and the like used include RD-17643 (December 1978) and RD 1871.
6 (November 1979) and 308119 (1989).
December, 2012). The places where they are written are listed below.

Additive RD-17643 RD-18716 RD-308119 Page classification Page classification Page classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 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 Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVI
I Next, preferable development processing of the light-sensitive material of the present invention will be described.

The processing method of the silver halide photographic light-sensitive material of the present invention is a processing method of processing the silver halide photographic light-sensitive material of the present invention in a total processing time of 10 to 25 seconds.

As a developing solution for developing the light-sensitive material of the present invention, as a developing agent, for example, JP-A-4-15641 can be used.
Dihydroxybenzenes, for example, hydroquinone, paraaminophenols, for example, p-aminophenol, N-methyl-p-
Aminophenol, 2,4-diamiphenol, etc., 3
-As the pyrazolidones, for example, 1-phenyl-3-
Pyrazolidones, 1-phenyl-3-pyrazolidone, 1
-Phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, 5,5-dimethyl-1-phenyl-3-
Pyrazolidone and the like are ascorbic acids, and these are used alone or in combination as necessary, and ascorbic acids are particularly preferably used.

In addition, 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.

The total number of moles of dihydroxybenzenes, paraaminophenols, 3-pyrazolidones, and ascorbic acid contained in the components of all developing solutions is preferably 0.1 mol / liter or less.

The preservative may include sulfites such as potassium sulfite, sodium sulfite, reductones such as piperidinohexose reductone, and these are preferably 0.2 to 1 mol / liter. Is preferably 0.3 to 0.6 mol / liter.
In addition, adding a large amount of ascorbic acid also leads to processing stability.

The alkaline agent includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.

Further, borate described in JP-A-61-28708, saccharose described in JP-A-60-93439,
A buffering agent such as acetoxime, 5-sulfosalicylic acid, phosphate or carbonate may be used. The content of these agents is such that the pH of the developer is 9.0 to 13, preferably 10 to 10.
Choose to be 12.5.

As the solubilizing agent, polyethylene glycols and their esters can be contained, and as the sensitizing agent, for example, a quaternary ammonium salt, a development accelerator, a surfactant and the like can be contained.

As the anti-sludge agent, for example, Japanese Patent Laid-Open No. Sho 5
No. 6,106,244, a silver stain inhibitor, JP-A-3-5
The sulfides and disulfide compounds described in 1844, 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, imidazole type, benzimidazole type, triazole type, benztriazo type, tetrazole type or 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 a chelating agent for masking calcium ions mixed in tap water used in the treatment liquid, a chelating agent having a chelate stabilization constant with iron of 8 or more as an organic chelating agent described in JP-A No. 1-193853 is used. 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 advance in the coating step of the light-sensitive material by incorporating the hardener, as described above, rather than in the developing step.

The processing temperature of the developer is preferably 25 to 50.
C., more preferably 30 to 40.degree.

The developing time is preferably 1 to 15 seconds, more preferably 3 to 10 seconds. The processing time of the present invention is Dry
It is 10 to 25 seconds in to Dry.

In the present invention, the treatment liquid is replenished by the amount corresponding to the treatment agent fatigue and the oxidation fatigue. As the replenishing method, replenishment by width and feed speed described in JP-A-55-126243, area replenishment described in JP-A-60-104946, and area replenishment controlled by continuous processing number described in JP-A-1-149156. However, the preferred supplement amount is 50
It is 0 to 150 cc / m ² .

Preferred fixing solutions may include fixing materials commonly used in the art. pH is 3.
8 or more, preferably 4.2 to 5.5.

The fixing agent is a thiosulfate such as ammonium thiosulfate and sodium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint 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 forms an acidic 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 preservatives such as sulfite and 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.), hydrochloric acid, if desired. PH adjusting agents such as various acids and metal hydroxides (potassium hydroxide, sodium hydroxide) and chelating agents having a water softening ability. Examples of fixing accelerators include JP-B-45-35754 and JP-A-58-122535.
No. 58-122536 and the like, and thioethers described in US Pat. No. 4,126,459.

Further, a method of supplying a developer 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, and granules, and is subjected to a moisture-proof treatment as necessary.

The powder means an aggregate of fine crystal grains. 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. Tablets are obtained by compressing powder or granules into a certain shape.

To solidify the photographic processing agent, the concentrated solution or fine powder or granular photographic processing agent and the water-soluble binder are kneaded and molded, or the surface of the temporarily molded photographic processing agent is mixed with the 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 powdery solid processing agent is granulated and then a tableting step is performed. 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. Can be done.
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. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pre-ketting machine can be used. The solid processing agent obtained by pressurization and compression can take any shape, but from the viewpoint of productivity, handling properties or dust when used on the user side, cylindrical, so-called tablets are used. preferable.

More preferably, during granulation, the above-mentioned effect becomes 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 Nos. 51-61837, 54-155038 and 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 /
Preferably ^{cm 3 ~2.5g / cm 3, 1.0g} / cm 3
2.5 g / in terms of strength of solid obtained when larger than
When the diameter is smaller than ³ cm ³ , the solubility of the obtained solid is more preferable. When the solid processing agent is a granule 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 the developing agent has a great effect of stabilizing photographic performance.

The solid processing agent may be solidified by only a part of the components of a certain processing agent, but preferably, all the components of the processing 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 and repeatedly placed 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.
When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished in 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 alkaline 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 and 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 radiographic 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.

In the fluorescent intensifying screens used in combination, the X-ray absorption of each intensifying screen is 30% or more per 100 μm of the thickness of the phosphor layer by increasing the filling rate of the phosphor particles. It is preferable. The amount of X-ray absorption was determined as follows. That is, X-rays generated from a tungsten target operated at 80 KVP from an X-ray generator whose intrinsic filtration is equivalent to 2.2 mm of aluminum with three-phase power supply are transmitted through an aluminum plate having a thickness of 3 mm and a purity of 99% or more. The X-ray absorption amount was measured by using an ionizing dosimeter at a position 50 cm after the phosphor layer of the radiographic intensifying screen, and arriving at a radiographic intensifying screen fixed at 200 cm from the tungsten anode of the target tube. 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 radiographic 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 formula from the porosity of the phosphor layer formed on the support.

[0193]

[Equation 1]

Preferred phosphors used for the radiation intensifying screen include the following.

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, La ₂ O ₂ S: Tb, (Y, Gd) ₂ O ₂ S: Tb,
Tm etc.), terbium-activated rare earth phosphate-based phosphor (YP
O ₄ : Tb, GdPO ₄ : Tb, LaPO ₄ : Tb, etc.),
Terbium-activated rare earth oxyhalide-based phosphor (L
aOBr: Tb, LaOBr: Tb. Tm, LaOC
l: Tb, LaOCl: Tb. TmGdOBr: Tb,
GdOCr: Tb), thulium activated rare earth oxyhalide-based phosphor (LaOBr: Tm, LaOCl: T)
m, etc.), barium sulfate-based phosphor [BaSO ₄ : Pb, B
aSO 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 fluorohalide-based phosphor [BaFCl: Eu]
²⁺ , BaFBr: Eu ²⁺ , BaFCl: Eu ²⁺ . Tb,
BaFBr: Eu ²⁺ . Tb, BaF ₂ . BaCl ₂ . XB
aSO ₄ . KCl: Eu ²⁺ , (Ba.Mg) F ₂ . BaC
l ₂ . KCl: Eu ²⁺ etc.], iodide-based phosphor (CSI:
Na, CSI: Tl, NaI. KI: Tl etc.) 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
However, the phosphor used is not limited to these, and any phosphor that emits light in the visible or near-ultraviolet region upon irradiation with radiation can be used.

[0196]

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

Example 1 Preparation of Em-1 (Comparative Emulsion) The tabular silver iodochloride emulsion Em was prepared using the following 5 kinds of solutions.
-1 was prepared.

A1 low methionine gelatin 35.53 g sodium chloride 1.306 g potassium iodide 24.94 mg with water to make 2030 ml B1 sodium chloride 1.737 g potassium iodide 24.90 mg with water to make 30 ml C1 silver nitrate 5.096 g with water Make up to 30 ml D1 Sodium chloride 46.80 g Make up to 800 ml with water E1 Silver nitrate 135.90 g Make up to 800 ml with water Stir solution A1 vigorously in the reaction vessel while keeping it at 40 ° C., and add the total amount of solution B1 and solution C1 there. The mixture was added by the simultaneous mixing method at a flow rate of 30 ml per minute over 1 minute. Next, the EAg of this mixed solution was adjusted to 149 mV and the temperature was adjusted to 10 at 40 ° C.
After holding for 2 minutes, the total amount of solution D1 and solution E1 is 2 ml per minute.
Was added by the simultaneous mixing method at a flow rate of 40 minutes. During this time, EAg was kept at 149 mV throughout.

Immediately after the addition, desalting and washing with water were performed.
Subsequently, after the emulsion was heated to 60 ° C., predetermined amounts of the exemplified spectral sensitizing dyes D-2 and D-15 were added as a solid fine particle dispersion, and then a mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate was added. And a methanol solution of triphenylphosphine selenide were added, and the mixture was aged for a total of 2 hours. At the end of aging, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

Additives other than the spectral sensitizing dye and their addition amounts (per mol of AgX) 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 is disclosed in Japanese Patent Application No. 4-994.
Prepared by a method according to the method described in No. 37.

That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature was previously adjusted to 27 ° C.
Obtained by stirring at 00 rpm for 30-120 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, 45% of the total projected area was composed of right-angled parallelogrammatic tabular grains having an adjacent side ratio of less than 10, and the average grain size of the right-angled parallelogrammatic tabular grains was measured. (Converted to circle diameter) is 0.584 μm,
The average thickness is 0.078 μm, the average aspect ratio is 7.5,
The tabular silver halide grains had a wide grain size distribution of 23.5%.

Preparation of Em-2 (Comparative Emulsion) The tabular silver bromochloride emulsion Em was prepared using the following 6 kinds of solutions.
-2 was prepared.

A2 Deionized alkali treated gelatin 20.0 g Sodium chloride 0.800 g Finished with water to 1215 ml B2 Sodium chloride 7.00 g Low molecular weight gelatin (molecular weight 20,000) 0.60 g Finished with water to 100 ml C2 Silver nitrate 20.0 g Low Molecular weight gelatin (molecular weight 20,000) 0.6 g Nitric acid (1N) 0.2 ml Finish with water to 100 ml D2 Potassium bromide 2.80 g Low molecular weight gelatin (molecular weight 20,000) 0.60 g Finish with water to 100 ml E2 Silver nitrate 4.0 g Low molecular weight gelatin (molecular weight 20,000) 0.6 g Nitric acid (1N) 0.2 ml Finish with water to 100 ml F2 Sodium chloride 1.5 g Finish with water to 15 ml Solution A2 is stirred vigorously while keeping at 50 ° C in a reaction vessel. 50 ml / min of solution B2 and solution C2 there 15 seconds at a flow rate, was added at the same time mixing method. Next, to this mixed solution, a solution D2 and a solution E2 were added at a flow rate of 70 ml per minute for 15 minutes.
It was added by the simultaneous mixing method for 2 seconds. After this, solution B2 again
And the solution C2 were added by a simultaneous mixing method at a flow rate of 25 ml / min for 2 minutes. Further, the solution F2 was completely added and the temperature was adjusted to 70
The temperature was raised to 0 ° C and the mixture was aged for 5 minutes.

Then, desalting and washing with water were carried out immediately. Subsequently, this emulsion was heated to 60 ° C. and then ripened in the same manner as Em-1.

When the obtained silver halide emulsion was observed with an electron microscope, 48% of the total projected area was composed of right-angled parallelogrammatic tabular grains having an adjacent side ratio of less than 10, and the average grain size of the right-angled parallelogrammatic tabular grains was found. (Converted to circle diameter) is 0.584 μm,
The average thickness is 0.078 μm, the average aspect ratio is 7.5,
The tabular silver halide grains had a wide grain size distribution of 25.0%.

Preparation of Em-3 A tabular silver bromochloride emulsion Em was prepared using the following 6 solutions.
-3 was prepared.

A3 low methionine gelatin 35.53 g sodium chloride 1.306 g potassium bromide 44.70 mg with water to make 2030 ml B3 sodium chloride 1.737 g potassium bromide 44.60 mg with water to make 30 ml C3 silver nitrate 5.096 g with water Finish to 30 ml D3 Sodium chloride 46.80 g Finish to 800 ml with water E3 Silver nitrate 135.90 g Finish to 800 ml with water Stir solution A3 vigorously in the reaction vessel while keeping it at 40 ° C., and add the total amount of solution B3 and solution C3 there. The mixture was added by the simultaneous mixing method at a flow rate of 30 ml per minute over 1 minute. Next, the EAg of this mixed solution was adjusted to 149 mV and the temperature was adjusted to 10 at 40 ° C.
After holding for 2 minutes, the total amount of solution D3 and solution E3 is 2 ml / min.
Was added by the simultaneous mixing method at a flow rate of 40 minutes. During this time, EAg was kept at 149 mV throughout.

Then, desalting and washing with water were carried out immediately. Subsequently, this emulsion was heated to 60 ° C. and then ripened in the same manner as Em-1.

The results of electron microscopic observation of the obtained silver halide emulsion are shown in Table 1.

Preparation of Em-4 In the preparation of Em-1, E-1 was prepared in the same manner as Em-1 except that the solutions A1 and B1 were changed to A4 and B4, respectively.
m-4 was prepared.

A4 low methionine gelatin 35.53 g sodium chloride 1.306 g potassium iodide 12.47 mg finished with water to 2030 ml B4 sodium chloride 1.737 g potassium iodide 12.45 mg finished with water to 30 ml The obtained silver halide emulsion Table 1 shows the results of electron microscope observation.

Preparation of Em-5 In the preparation of Em-3, E at the time of adding solutions D3 and E3
Em-5 was prepared in exactly the same manner as Em-3 except that Ag was changed to 135 mV.

The results of electron microscopic observation of the obtained silver halide emulsion are shown in Table 1.

Preparation of Em-6 In the preparation of Em-1, E-1 was prepared in the same manner as Em-1 except that the solutions A1 and B1 were changed to A6 and B6, respectively.
m-6 was prepared.

A6 low methionine gelatin 35.53 g sodium chloride 1.306 g potassium iodide 37.41 mg finished with water to 2030 ml B6 sodium chloride 1.737 g potassium iodide 37.35 mg finished with water to 30 ml The obtained silver halide emulsion Table 1 shows the results of electron microscope observation.

Preparation of Em-7 In the preparation of Em-3, E at the time of adding solutions D3 and E3
Em-7 was prepared in exactly the same manner as Em-3, except that Ag was changed to 164 mV.

The results of electron microscopic observation of the obtained silver halide emulsion are shown in Table 1.

The emulsion thus obtained is shown in Table 1.

[0221]

[Table 1]

The following additives were added to the obtained emulsion to prepare an emulsion layer 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 to No. 7 was obtained. As the support, glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%,
X-ray of 175 μm in which the copolymer aqueous dispersion obtained by diluting the copolymer consisting of three kinds of monomers of 40 wt% of butyl methacrylate to 10 wt% was used as the undercoating liquid.
A polyethylene terephthalate film base colored blue with a density of 0.15 for the line film was used.

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) Each of the emulsions obtained above was prepared as follows. Various additives were added.

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 10,000) 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 1,3-dihydroxybenzene-4-sulfonic acid ammonium salt 500 mg / m ² 2-mercaptobenzimidazole-5-sulfonic acid sodium salt 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 COOH) ₂ 350 mg / m ² compound (M) 5 mg / m ² compound (N) 5 mg / m ² colloidal silica 0.5 g / m ² latex (L) 0.2 g / m ² dextrin (average molecular weight 1000) 0 .2g / m ^2, however, was adjusted to 1.0 g / m ² as 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 (area Average particle size 7.0 μm) 50 mg / m ² 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) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound Objects (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

[0227]

Embedded image

[0228]

Embedded image

[0229]

Embedded image

Obtained sample No. Photographic properties were evaluated using 1 to 7. First, the sample was sandwiched between two screens (KO-250 manufactured by Konica Corp.), and was exposed to X-rays through an aluminum wedge at a tube voltage of 80 kvp, a tube current of 100 mA, and 0.05 seconds for exposure. Then, using an automatic developing machine (Konica Corp. SRX-502), a developer having the following formulation,
Treated with fixer.

Developer Formulation Part-A (for 12 l finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriamine pentaacetic acid 120 g Sodium hydrogen carbonate 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 12 l finishing) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter glacial acetic acid 120 g Potassium bromide 225 g Add water to make 1.0 liter.

Fixer formulation Part-A (for 18-liter finishing) 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 18g Part-B Aluminum sulphate 800g The developer is prepared by adding Part A and Part B simultaneously to about 5 liters of water and adding 12 while stirring and adding water.
The pH was adjusted to 10.40 with glacial acetic acid. This is used as a development replenisher.

20 ml / l of the aforesaid starter was added to 1 liter of this development replenisher to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part A and P to about 5 liters of water.
artB was added at the same time, and water was added while stirring and dissolving.
and the pH was adjusted to 4.4 using sulfuric acid and NaOH. This is used as a fixing replenisher.

The processing time is 45 seconds and 25 seconds in dry to dry. In the case of dry to dry for 45 seconds, the processing temperature is as follows: development 35 ° C., fixing 33 ° C., water washing 2
It is 0 ° C and dried at 50 ° C. In addition, dry to dry
For 25 seconds, development 37 ° C, fixing 35 ° C, water washing 30
℃ and dry 50 ℃.

After the processing, fog, sensitivity, contrast were measured and fixability was evaluated. Fog is sample No. 1
It was shown as a relative value when the fog in the processing of 25 seconds was set to 100. The sensitivity is expressed by the reciprocal of the exposure amount that gives a density of fog +0.5, and the sample No. Sensitivity in 45 seconds of 1 is 100
The relative sensitivity is shown. 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 in the case of 1 for 45 seconds is 1. Further, the fixing property was evaluated by visually observing the transparency of the unexposed film after processing for 25 seconds, and evaluated in the following three stages.

◯: No problem Δ: Slightly inferior fixing property (there may be a problem in practical use) ×: Inferior fixing property (not acceptable for practical use)

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

[0239]

[Table 2]

Example 2 Preparation of Em-8 (Comparative Emulsion) The tabular silver iodochloride emulsion Em was prepared using the following 5 solutions.
-8 was prepared.

A8 low methionine gelatin 214.37 g sodium chloride 1.995 g potassium iodide 149.6 mg finished with water to 6090 ml B8 sodium chloride 10.48 g potassium iodide 149.4 mg finished with water to 90 ml C8 silver nitrate 30.58 g with water Finish to 90 ml D8 Sodium chloride 165.0 g Finish to 5640 ml with water E8 Silver nitrate 479.0 g Finish to 5640 ml with water Stir solution A8 vigorously in the reaction vessel while keeping it at 40 ° C., and then add all the amounts of solution B8 and solution C8 there. 180 ml per minute
At the same flow rate over 30 seconds.

Next, this mixed solution was kept at 40 ° C. for 10 minutes, and then solution D8 and solution E8 were added at a flow rate of 24 ml / min.
Add by the simultaneous mixing method over 0 minutes, and then simultaneously add the remaining total amount of the solution D8 and the solution E8 over 130 minutes while linearly increasing the flow rate so that the initial flow rate is 24 ml and the final flow rate is 48 ml. Method was added. During this time,
The 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 Em-1.

The silver halide emulsion obtained had an iodide of 0.0
When observed by an electron microscope, the average particle size (in terms of circular diameter) was 1.45 μm, and the average thickness was 0.13 μm.
m, average aspect ratio 11, width of particle size distribution 28.0%
Of a right-angled parallelogram tabular silver halide grain (tabular grain ratio of 50% or more).

Preparation of Em-9 A tabular silver bromochloride emulsion Em was prepared using the following 5 solutions.
-9 was prepared.

A9 low methionine gelatin 214.37 g sodium chloride 1.995 g potassium bromide 536.2 mg with water to make 6090 ml B9 sodium chloride 10.48 g potassium bromide 535.5 mg with water to make 90 ml C9 silver nitrate 30.58 g with water Finish to 90 ml D9 Sodium chloride 165.0 g Finish to 5640 ml with water E9 Silver nitrate 479.0 g Finish to 5640 ml with water Stir solution A9 vigorously while keeping it at 40 ° C in the reaction vessel, and add all the amounts of solution B9 and solution C9 thereto. 180 ml per minute
At the same flow rate over 30 seconds.

Next, this mixed solution was kept at 40 ° C. for 10 minutes, and then the solution D9 and the solution E9 were added at a flow rate of 24 ml / min.
Add by the simultaneous mixing method over 0 minutes, and then continuously add the remaining total amount of the solution D9 and the solution E9 over 130 minutes while linearly increasing the flow rate so that the initial flow rate is 24 ml and the final flow rate is 48 ml. Method was added. During this time,
The 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 Em-1.

The obtained silver halide emulsion was observed with an electron microscope to find that the average grain size (circle diameter conversion) was 1.45 μm.
It was a right parallelogram tabular silver halide grain having an average thickness of 0.13 μm, an average aspect ratio of 11 and a grain size distribution width of 19.9% (tabular grain ratio of 50% or more).

Using the resulting emulsion, in the same manner as in Example 1, coated sample No. 8, No. 9 was produced.
The obtained sample No. Table 3 shows the results of the same evaluations as in Example 1 using 8 and 9. The fog, sensitivity, and contrast were the same as in Example 1, and the sample No. It was expressed as a relative value when the value of 8 was set to 100, and the fixability was evaluated by visual observation in three grades.

[0251]

[Table 3]

As can be seen from Table 3, the samples of the present invention have high sensitivity and contrast, and have low fog even in rapid processing such as 25 seconds, so that sensitivity and contrast are not impaired. Further, it can be seen that there is no problem in fixing property.

Example 3 Sensitivity and fixability were evaluated using Samples 1 to 7 produced in Example 1.

[0254] The sample was put on two screens (Konica Corporation).
Made. KO-250), a tube voltage of 80 kvp, a tube current of 100 mA, and an X of 0.05 seconds through an aluminum wedge.
A line was irradiated and exposed. Next is an automatic processor (Konica Corporation)
Made. SRX-502) was used for processing with a developer and a fixer having the following formulations.

Tablets for development replenishment were prepared according to the following procedure (A, B).

Operation (A) 3,000 g of hydroquinone as a developing agent is pulverized 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 commercial stirred granulator at room temperature for about 10 minutes, 3
After granulation by adding 0 ml of water, the granules are dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granules. 25 g of 100 g of polyethylene glycol 6000 was added to the granules thus prepared.
After mixing uniformly for 10 minutes using a mixer in a room humidified at 40 ° C. and below 40% RH, one tablet of the obtained mixture was obtained using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Compression tableting was performed with the filling amount per unit being 3.84 g to prepare 2500 tablets A for development replenishment.

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. Is pulverized and granulated in the same manner as in the operation (A). The amount of water added was 30.0 ml, and after granulation, 3 at 50 ° C
After drying for 0 minutes, the water content of the granules is almost completely removed. The mixture thus obtained was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 1.73 g, and 2500 developing replenishers were used. Tablet B formulation was prepared.

Next, a fixing replenishing tablet B agent 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.
4 g of sodium N-lauroylalanine is added to the granules thus prepared, and mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the obtained mixture was compressed into tablets using a tableting machine which was modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 6.202 g and the mixture was compressed to 250
Zero fixing 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 granules are dried for 30 minutes to almost completely remove the water content. 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and the mixture was mixed for 3 minutes, and the resulting mixture was mixed with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. The filling amount was 4.562 g, and compression tableting was performed to prepare 1250 fixing replenishment tablet D agents.

<Starter Composition> Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make 1 liter.

At the start of processing of the developing solution (starting of running), the developing tank was filled with a starting solution of 16.5 liters of the developing solution prepared by diluting the developing tablet with diluting water to start the processing. did. still,
The pH of the developer to which the starter was added was 10.45.

The light-sensitive material prepared above was exposed to light so that the optical density after development was 1.0, and running was carried out. 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.
The above-mentioned ^two agents A and B and 2 ml of water were added per 2 m ² . When each of A and B was dissolved in 38 ml of water, the pH was 10.70. The fixing solution contains a light-sensitive material 0.
2 pieces of the above C agent, 1 piece of the D agent and 7 pieces of water per 62 m ^2.
4 ml was added. The rate of water addition to each of the treatment agents 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.

[0266] Developer Potassium carbonate 40 g Hydroquinone 30 g Dimezone S 10 g Diethylenetriamine pentaacetic acid-5Na (DTPA) 1 g Potassium bromide g 5-Methylbenzotriazole 0.1 g 1-Phenyl-5-mercaptotetrazole 0.07 g 2-Mercaptohypoxanthine 0 0.05 g sodium sulfite 30.00 g potassium sulfite 25 g KOH 2 g diethylene glycol 50 g N-acetyl-D, L-penicillamine 0.1 g These were dissolved in 300 ml of water and finally 400 m of pure water.
finished to 1. This concentrate was diluted to 1 liter with water to prepare a replenisher. The pH of this replenisher was 10.70. still,
The amount of replenisher used was 7 ml / quarter.

Fixing solution 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 Dissolved in water and finally with pure water 500m
finished to 1. This concentrate was diluted to 1 liter with water to prepare a replenisher. The pH of this replenisher was 4.50. The amount of replenisher used was 7 ml / quarter.

The results obtained are shown in Table 4.

[0269]

[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 instead 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.

Operation (E) 12500 g of sodium erythorbate as a developing agent is ground in a commercial Van Dam 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, 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 commercial stirred granulator at room temperature for about 10 minutes, the granulated product is dried in a fluid bed dryer at 40 ° C. for 2 hours. The water content of the granulated product is almost completely removed. In this way, 1670 g of polyethylene glycol 6000 was added to the granules prepared,
After 670 g of the mixture was uniformly mixed for 10 minutes using a mixer in a room whose humidity was adjusted to 25 ° C. and 40% RH or less, the obtained mixture was toughly pressed to collect 152 by Kikusui Seisakusho KK
Using a tableting machine modified from 7HU, the filling amount per tablet was adjusted to 8.77 g, and compression tableting was carried out to prepare 2,500 developing replenishing tablet E agents.

Operation (F) Operation (A) of 4000 g of potassium carbonate, 2100 g of mannitol, and 2100 g of polyethylene glycol 6000.
Pulverize and granulate as in The amount of water to be added is 30.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture obtained in this manner was applied to Kikusui Seisakusho Co., Ltd. Tough Presto Collect 1527HU.
Tableting machine was modified to reduce the filling amount per tablet to 3.28.
g, and compression tableting was carried out to prepare 2500 development replenishing tablets F.

[0274]

INDUSTRIAL APPLICABILITY The silver halide emulsion and the method for producing the same, the silver halide photographic light-sensitive material and the method for processing the same according to the present invention have the effects of high sensitivity, high γ, low fog and excellent suitability for rapid processing. . Further, it also had an excellent effect on low replenishment.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 5/30 G03C 5/30

Claims (6)

[Claims] 1. In a silver halide emulsion containing at least 30 mol% of silver chloride, 50% or more of the total projected area of silver halide grains contained in the silver halide emulsion is predominantly (100) plane. A tabular silver halide grain having a flat surface, which is obtained by allowing bromine ions to be present at the time of nucleation of the tabular silver halide grain. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, said emulsion layer containing the silver halide emulsion according to claim 1. Silver photographic light-sensitive material. 3. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on each side of a support, wherein the emulsion layer contains the silver halide emulsion according to claim 1. Silver halide photographic light-sensitive material. 4. A silver halide photographic light-sensitive material characterized in that the silver halide photographic light-sensitive material according to any one of claims 2 to 3 is treated with a developer containing substantially no dihydroxybenzenes in the developer. Processing method. 5. A method of processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to claim 2 in a total processing time of 10 to 25 seconds. 6. A silver halide emulsion containing at least 30 mol% 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. In the method for producing a silver halide emulsion which is a tabular silver halide grain whose main plane is, a bromine ion is present at the time of nucleation of the tabular silver halide grain. .