JP2000056420A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material low in fog with high sensitivity and small residual dye stains and superior in resistance to high temperature and high humidity. SOLUTION: This silver halide photographic sensitive material is constituted of photosensitive silver halide emulsion layers provided on a support. The silver halide grains contained in at least one of the layers are grown, while an aqueous solution containing salts is properly extracted from the product solution by ultrafiltration, and are chemically sensitized by at least one kind of compounds represented by the formula, R11-R12-Au(1)-R13-R14, wherein R12 and R13 are each a -SO2S-, -(S)m-, -(Se)m-, or -(Te)m- and (m) is 1-6; and R11 and R14 are each a substd. or unsubstd. aliphatic or aromatic hydrocarbon or heterocyclic ring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion having high sensitivity, little dye contamination and excellent storage stability, and a photographic material using the same. The present invention relates to a processing method and a photographing method.

[0002]

2. Description of the Related Art In recent years, the demand for rapid processing has been increasing with the increase in processing of silver halide photographic light-sensitive materials. For example, a similar tendency is seen in the field of medical X-ray films. With the spread of health examinations and the increase in examination items for improving the accuracy of diagnosis, the number of X-ray photographs taken increases. In addition, there is a need to notify the examinee of the diagnosis result earlier, and therefore, there is a strong demand for ultra-rapid development processing after photographing and reduction of processing waste liquid due to environmental problems.

However, in order to speed up processing, development,
Although it is necessary to shorten the processing time of each processing step such as fixing, washing, and drying, the load of each processing increases.
For example, if the development time is simply shortened, with a conventional photosensitive material,
This is accompanied by a decrease in image density, that is, a decrease in sensitivity and a decrease in gradation. On the other hand, when the fixing time is shortened, the fixing of silver halide becomes incomplete and causes deterioration of image quality. Further, shortening the time of each processing step is accompanied by deterioration of image quality due to residual dye (residual color) because the sensitizing dye is not sufficiently eluted in each of the processing of development, fixing and washing. Therefore, in order to solve such a problem, it is necessary to increase the developing speed and the fixing speed, to reduce the amount of the dye, and to accelerate the detachment and / or decolorization of the dye.

On the other hand, in order to reduce development processing waste liquid,
It is necessary to reduce the fatigue of the processing solution and / or the replenishing solution, but this involves the same problems as the above-mentioned speedup.

As techniques for improving these problems, EP-A-506,584, JP-A-5-88293, JP-A-5-93975 and the like disclose benzoimidazolocarbocyanines having good decolorizing performance as spectral sensitizing dyes. A technique using is disclosed. Also, JP-A-5-61148 describes that
Oxacarbocyanines and benzimidazolocarbocyanines are used in combination at a specific ratio as a spectral sensitizer in a silver halide emulsion having an iodine content of 1 mol% or less, and further subjected to chemical sensitization with a selenium compound and / or tellurium compound. Application techniques are disclosed.

[0006] However, these disclosed techniques alone improve the residual color property or the speed of development, but are still insufficient to satisfy the recent demand levels for various performances. In particular, they have the disadvantages that they are not sufficient in terms of high sensitivity and safelight resistance, and that when the photosensitive material is stored under high humidity and high temperature, the sensitivity is greatly reduced.

On the other hand, various basic studies have been carried out on the adsorption of silver halide grains and sensitizing dyes for a long time. When adsorbing a sensitizing dye to silver halide grains, studies have been conducted to uniformly and selectively adsorb sensitizing dyes within and between grains. As a method for adding a sensitizing dye, it is also known that chemical sensitization is performed in the presence of a sensitizing dye to control chemical sensitization and reduce intrinsic desensitization. However, these techniques are also inadequate with respect to storage, pressure resistance, safelight resistance and illuminance failure.

For high sensitivity, reduction sensitization attempts have been studied for a long time. U.S. Pat. No. 2,487,850,
Nos. 2,512,925 and 2,518,698
No. 3,930,867 and British Patent No. 789,8.
No. 23, etc. However, these reduction sensitization methods have not yet reached practical levels.

Meanwhile, in the field of medical X-ray photographic materials, in order to improve patient service and workability, in addition to rapid development processing and reduction of processing waste liquid, simplification of the entire processing work is strongly required. Requested. However, since the liquid processing agent which dilutes the concentrated solution of the developing agent and replenishes it into the processing tank has a large weight and a large volume, it is difficult to improve the work efficiency. As an alternative to this, in recent years, a solid processing agent supplied with a solid component and dilution water to a processing tank of an automatic developing machine has been proposed. As a result, the transportation cost, the storage space, and the working efficiency are reduced, and the amount of packaging material used can be reduced.

However, due to the solubility of the solid components,
In particular, when the development processing is performed for an extremely short time, there is a problem that it is difficult to obtain sufficiently stable running performance.

On the other hand, various basic studies have been carried out on the adsorption of silver halide grains and sensitizing dyes for a long time. When adsorbing a sensitizing dye to silver halide grains, studies have been conducted to uniformly and selectively adsorb sensitizing dyes within and between grains. It is also known that chemical sensitization is performed in the presence of a sensitizing dye to control chemical sensitization and reduce intrinsic desensitization. However, these techniques are also inadequate with respect to storage, pressure resistance, safelight resistance and illuminance failure.

The gold compound sensitizer is (I) or (III)
It may include gold in an oxidized state. However,
(I) The oxidized state is preferred because the oxidized state of the gold compound may cause a side reaction to oxidize the gelatin or other components in the emulsion. Among the gold (I) compounds, trisodium gold (I) thiosulfate is generally known as a chemical sensitizer, but is not versatile because this compound cannot be conveniently provided. Proposed gold (I) compounds include Tavernier et al., US Pat.
No. 3,749, which is a gold (I) thiolate. However, the production process of such a gold (I) compound involves the use of dangerously explosive gold thunderous acid, which is not desirable for practical use.

As a method of increasing the sensitivity of a silver halide emulsion, US Pat. No. 4,956,269 discloses a technique for introducing a transition line into tabular silver halide grains. It is generally known that when pressure is applied to silver halide grains, fogging or desensitization occurs.However, grains having dislocation lines introduced therein have a problem that they are significantly desensitized by application of pressure. Was. JP-A-3-189642 discloses that tabular silver halide grains having an aspect ratio of 2 or more and having 10 or more dislocation lines in a fringe portion, and the size distribution of the tabular silver halide grains are simple. Dispersed silver halide emulsions are disclosed. However, this technique does not improve the significant desensitization caused by the pressure caused by introducing dislocation lines.

When developing silver halide photographic emulsions, not limited to tabular silver halide emulsions, there is an important viewpoint other than performance in terms of production cost. An effective method in terms of production cost is to increase the amount of emulsion produced at one time, in other words, to increase the yield of silver halide at the end of grain growth in a reaction vessel for preparing a silver halide emulsion. I do. That is, the concentration of silver halide in the emulsion at the end of grain growth is increased, and a direct method is concentration of the silver halide emulsion.

As a method of concentrating the volume of the reaction product (silver halide emulsion) in the emulsion preparation step, a technique using an ultrafiltration method is disclosed in JP-B-59-43727 or JP-A-3-14094.
No. 6, for example. However, these methods do not include suggestions on how to prepare tabular grains or even monodispersed tabular silver halide emulsions. Further, it is not intended to control the average intergranular distance of silver halide grains when preparing a silver halide emulsion.

Japanese Patent Application Laid-Open No. 6-67326 discloses that ultrafiltration is applied during the preparation of a tabular silver halide emulsion to concentrate the reaction product, improve the yield, and improve the intermediate aspect ratio (2 to 8). ) Are disclosed. In this publication, utilizing the fact that the aspect ratio of silver halide grains systematically decreases with concentration, the tabular grains having a high aspect ratio are condensed by ultrafiltration during grain formation to provide an intermediate. Has an aspect ratio. However, it is generally difficult to monodisperse tabular grains having a high aspect ratio, so that a method of reducing the aspect ratio by concentrating tabular grains having a high aspect ratio by nature is expected to sufficiently improve the distribution. Can not. In fact, the silver halide emulsions described in the examples of this publication have a coefficient of variation of 0.3% in terms of volume equivalent grain size for both the control emulsion and the invention emulsion.
These values indicate the above, and cannot be a technique for solving the problems in performance of conventional tabular grains.

[0017]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material having low fog, high sensitivity, high image quality, little dye contamination and excellent storage stability. .

A second object of the present invention is to provide a silver halide photographic light-sensitive material having the above-mentioned performance, a photographic method and a processing method thereof. Other objects will be apparent from the description in the following specification.

[0019]

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

(1) In a silver halide photographic material having a photosensitive silver halide emulsion layer on a support, the silver halide grains contained in at least one of the silver halide emulsion layers are subjected to ultrafiltration. Is produced by performing grain growth while appropriately extracting an aqueous solution containing a salt from the reaction solution, and chemically sensitized with at least one compound represented by the following general formula (1). A silver halide photographic light-sensitive material.

General formula (1) R ₁₁ -R ₁₂ -Au ^(I) -R ₁₃ -R _{14 wherein} R ₁₂ and R ₁₃ are -SO ₂ S-,-(S) _m -,-
(Se) _m -,-(Te) _m- , where m is 1 to 6. R ₁₂ and R ₁₃ may be the same or different. R ₁₁ and R ₁₄ represent a substituted or unsubstituted aliphatic hydrocarbon, aromatic hydrocarbon or heterocycle, and may be the same or different. (2) In a silver halide photographic material having a photosensitive silver halide emulsion layer on a support, silver halide grains contained in at least one of the silver halide emulsion layers are reacted by ultrafiltration. The silver halide photographic material is manufactured by performing grain growth while appropriately extracting an aqueous solution containing a salt from the product solution, and contains at least one compound represented by the following general formula (2) in at least one layer of the silver halide photographic material. A silver halide photographic material.

[0022]

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Wherein R ₁ and R ₃ each represent a substituted or unsubstituted lower alkyl group or alkenyl group, R ₂ and R ₄ each represent an alkyl group, and at least one of R ₂ and R ₄ is Represents an alkyl group substituted with a hydrophilic group. Z ₁ , Z ₂ ,
Z ₃ and Z ₄ may be the same or different, and represent a hydrogen atom or a substituent. X ₁ represents an ion necessary for neutralizing an intramolecular charge, and n represents 1 or 2. However, when an inner salt is formed, n is 1. (3) In a silver halide photographic material having a photosensitive silver halide emulsion layer on a support, silver halide grains contained in at least one of the silver halide emulsion layers are reacted by ultrafiltration. It is produced by performing particle growth while appropriately extracting an aqueous solution containing a salt from the product solution, and is represented by the above general formula (1) in the presence of at least one compound represented by the above general formula (2). A silver halide photographic material characterized by being chemically sensitized with at least one kind of compound.

(4) In a silver halide photographic material having a photosensitive silver halide emulsion layer on a support, silver halide grains contained in at least one of the silver halide emulsion layers are subjected to ultrafiltration. A silver halide photograph produced by performing grain growth while appropriately extracting an aqueous solution containing a salt from a reaction solution, and containing at least one compound represented by the following general formula (3): Photosensitive material.

[0025]

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Wherein X represents, directly or indirectly, at least one selected from —SO ₃ M, —COOM, and —OM, and an atom group capable of forming a heterocyclic ring; M represents a hydrogen atom; Represents a metal atom, a quaternary ammonium group or a phosphonium group. However, compounds partially including the following structures are excluded.

[0027]

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Here, R represents a hydrogen atom or a substituent. (5) In a silver halide photographic material having a photosensitive silver halide emulsion layer on a support, silver halide grains contained in at least one of the silver halide emulsion layers are reacted by ultrafiltration. A silver halide photographic light-sensitive material produced by performing grain growth while appropriately extracting an aqueous solution containing a salt from a product solution, and containing at least one compound represented by the following general formula (4): .

[0029]

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[Wherein (A ₁ ) is -SO ₃ M ₁ , -CO
OM ₁ or —OM ₁ , wherein M ₁ represents a hydrogen atom, a metal atom, or a quaternary ammonium group or a phosphonium group, and m is an integer of 1 to 10. (A ₂ ) represents an electron-withdrawing group, and n is an integer of 1 to 10. (A ₃ ) represents a functional group containing a sulfur atom, a selenium atom or a tellurium atom capable of binding to a silver ion, and r represents 1 or 2. Y represents an aliphatic hydrocarbon, an aromatic hydrocarbon or a heterocyclic ring. (6) In a silver halide photographic material having a photosensitive silver halide emulsion layer on a support, silver halide grains contained in at least one of the silver halide emulsion layers are reacted by ultrafiltration. A silver halide photographic light-sensitive material produced by performing grain growth while appropriately extracting an aqueous solution containing a salt from a product solution, and containing at least one compound represented by the following general formula (5): .

[0031]

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[Wherein (A ₁ ), (A ₂ ), (A ₃ ),
m, n and r each represent a group having the same meaning as in the above formula (4). (A ₁ ) ′ is —SO ₃ M ₁ , —COOM ₁ or —OM
_And M ₁ represents a group having the same meaning as M _{1 in} formula (4). (A ₂ ) ′ represents an electron-withdrawing group, and (A ₃ ) ′ represents a functional group containing a sulfur atom, a selenium atom or a tellurium atom capable of binding to a silver ion. (A ₁ ) and (A ₁ ) ′, (A ₂ ) and (A ₂ ) ′, and (A ₃ ) and (A ₃ ) ′ may be the same or different. Y ₁ and Y ₂ are aliphatic hydrocarbons,
Represents an aromatic hydrocarbon or a heterocyclic ring, which may be the same or different. Z represents a sulfur atom, a selenium atom or a tellurium atom, and p is 1 or 2. m ′ and n ′ each independently represent an integer of 1 to 10, but m + m ′ and n + n ′
Is 1 or more. (7) A silver halide produced by subjecting the silver halide grains according to any one of the above 1 to 6 to grain growth by ultrafiltration while appropriately extracting an aqueous solution containing a salt from a reaction solution. 7. The method according to any one of the above items 1 to 6, wherein the subsurface or the surface of the particles contains at least one compound represented by the general formula (3), (4) or (5). Silver halide photographic material.

Hereinafter, the present invention will be described in detail. As one embodiment of a silver halide emulsion production apparatus applicable to the production of silver halide grains according to the present invention, it is possible to arbitrarily control and maintain an average intergranular distance in a grain growth process by an ultrafiltration apparatus. An example of the apparatus for producing a silver halide emulsion will be described with reference to FIG.

The reaction vessel 1 initially contains a dispersion medium 3. The apparatus comprises a reaction vessel 1 and a silver addition line 4 for adding at least one aqueous solution of a silver salt, preferably an aqueous solution of silver nitrate, and at least one aqueous solution of a halide salt, preferably an alkali metal such as bromine, iodine or chlorine. It has a halide addition line 5 for adding an aqueous salt solution, an aqueous ammonium salt solution, or a mixture thereof. Further, it has a stirring mechanism 2 for stirring the dispersion medium and the reactant solution (a mixture of the dispersion medium and the silver halide grains) in the process of preparing the silver halide emulsion. The stirring mechanism can be in any conventional manner. Silver salt aqueous solution is silver addition line 4
From the reaction vessel at a flow rate controlled by the silver addition valve 20. The halide aqueous solution is added to the reaction vessel from the halide addition line 5 at a flow rate controlled by the halide addition valve 21. The addition of the solution through the silver addition line 4 and the halide addition line 5 may be liquid level addition, but is more preferably performed in the liquid near the stirring mechanism 2. The stirring mechanism 2 mixes the aqueous silver salt solution and the aqueous halide salt solution with a dispersion medium, and enables the soluble silver salt to react with the soluble halide salt to produce silver halide.

During the first stage of silver halide formation, ie, during the nucleation step, a dispersion (reactant solution) containing the base silver halide nucleus grains is formed. Subsequently, the nucleation step is completed through an aging step as required. Subsequently, when the addition of the aqueous silver salt solution and the aqueous halide solution is continued, the second stage of silver halide formation, that is, the growth process stage, is performed, and additional silver halide produced as a reaction product in the process is first formed. Deposited on the coated silver halide nucleus grains to increase the size of these grains. In the present invention, during the particle formation process by adding the aqueous silver salt solution and the aqueous halogen salt solution to the reaction vessel, a part of the reactant solution in the reaction vessel is sent to the ultrafiltration unit 12 through the liquid take-out line 8 by the circulation pump 13. It is sent and returned to the reaction vessel through the liquid return line 9. At that time, the pressure applied to the ultrafiltration unit 12 is adjusted by a pressure adjusting valve 18 provided in the middle of the liquid return line 9 to partially remove the water-soluble salt solution contained in the reaction solution. It is separated by a filtration unit and discharged out of the system through a permeated liquid discharge line 10. With such a method, it is possible to form grains while arbitrarily controlling the distance between grains even during the grain growth process by adding the aqueous silver salt solution and the aqueous halide salt solution to the reaction vessel.

When this method is applied in the present invention, it is preferable to arbitrarily control the permeate amount (permeate flux; also referred to as ultrafiltration flux) of the solution of the water-soluble salt separated by the ultrafiltration membrane. For example, in such a case, the ultrafiltration flux can be arbitrarily controlled using the flow control valve 19 provided in the middle of the permeate discharge line 10. At this time, in order to minimize the pressure fluctuation of the ultrafiltration unit 12, the valve 25 provided in the middle of the permeate return line 11 is opened to open the permeate return line 11.
May be used. Alternatively, the valve 25 may be closed and the permeate return line 11 may not be used, which can be arbitrarily selected according to the operating conditions. For detecting the ultrafiltration flux, the flow meter 14 provided in the middle of the permeated liquid discharge line 10 may be used, or the flux may be detected by a weight change using the permeated liquid receiving container 27 and the scale 28. .

In the present invention, the concentration by the ultrafiltration method in the particle growth process may be performed continuously throughout the particle formation process or may be performed intermittently. However, when applying the ultrafiltration method in the particle growth process, after starting the circulation of the reactant solution to the ultrafiltration step, the circulation of the reactant solution may be continued at least until the end of the particle formation. preferable. Therefore, it is preferable that the circulation of the reactant solution to the ultrafiltration unit be continued even when the concentration is interrupted. This is to avoid uneven distribution between particles in the reaction vessel and particles in the ultrafiltration step. Further, it is preferable that the circulation flow rate through the ultrafiltration step is sufficiently high. Specifically, the retention time of the silver halide reactant solution in the ultrafiltration unit including the liquid take-out line and the liquid return line is preferably within 30 seconds, and is preferably within 15 seconds.
Within 2 seconds is more preferable, and further within 10 seconds is particularly preferable.

The volume of the ultrafiltration step including the liquid take-out line 8, the liquid return line 9, the ultrafiltration unit 12, the circulation pump 13 and the like is preferably 30% or less of the volume of the reaction vessel, and is preferably 20% or less. It is more preferably at most 10%, particularly preferably at most 10%.

Thus, by applying the ultrafiltration step, the volume of the total silver halide reactant solution can be arbitrarily reduced during grain formation. Further, by adding water from the addition line 7, the volume of the silver halide reactant solution can be arbitrarily maintained.

In the present invention, there are no particular restrictions on the ultrafiltration module and the circulating pump which can be used in carrying out the ultrafiltration, but the ultrafiltration module and the circulating pump may act on the silver halide emulsion to adversely affect photographic performance and the like. It is preferable to avoid any material and structure. In addition, the molecular weight cutoff of the ultrafiltration membrane used in the ultrafiltration module can be arbitrarily selected. For example, when it is desired to remove a dispersion medium such as gelatin contained in a silver halide emulsion or a compound used in preparing an emulsion during the grain growth process, an ultrafiltration membrane having a molecular weight cut off greater than the molecular weight of the object to be removed is selected. Can also
If the removal is not desired, an ultrafiltration membrane having a molecular weight cut off less than the molecular weight of the object to be removed can be selected.

The silver halide grains used in the silver halide emulsion of the present invention use silver chloride, silver iodochloride, silver iodobromochloride, silver bromochloride, silver bromide, silver bromoiodide, etc. as silver halide. be able to. Of these, silver chloride and silver iodochloride are more preferred. The silver halide grains contained in the silver halide emulsion of the present invention preferably contain 50 mol% of silver chloride, more preferably 70 mol% or more, and more preferably 9 mol% or more.
More preferably, the content is 0 mol% or more. In the case of silver iodochloride, the content of silver iodide is from 0.01 mol% to 1.0 mol% as an average silver iodide content of the whole silver halide grains.
Or less, preferably 0.01 mol% or more and 0.5 mol% or more.
More preferably, it is at most mol%.

The shape of the silver halide grains used in the present invention may be any shape. For example, cube, octahedron,
The shape may be a tetrahedron, a sphere, a flat plate, a potato, or the like. Particularly preferred are tabular grains.

Hereinafter, tabular grains will be described as typical examples of silver halide grains preferably used in the present invention.

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

The tabular silver halide grains used in the present invention preferably have a more uniform iodine content between grains. When the distribution of iodine content between grains was measured by the EPMA method, the relative standard deviation was 35% or less, and the relative standard deviation was 20% or less.
% Is preferable.

In the present invention, the tabular silver halide grains preferably contain silver iodide, but the silver iodide is preferably contained at least inside. If inside,
More preferably, it exists at least at the center. In this case, the internal composition contains silver iodide in an amount of 0.1 mol% to 5 mol%.
It is preferable to contain the following. Here, the halogen composition distribution inside the silver halide grains can be determined by pre-treating the grains into ultrathin sections, and then observing and analyzing them with a transmission electron microscope while cooling. Specifically, silver halide grains are taken out of the emulsion, embedded in a resin, and cut with a diamond knife to produce a 60-nm-thick section. 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).

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

The sample was cooled to −110 ° C. or less in an ultra-high vacuum of 1 × 10 ⁻⁸ torr or less, and irradiated with MgKα as a probe X-ray at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA. 2, measured for Br3d and I3d3 / 2 electrons. 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 measurement errors caused by destruction of the sample by X-ray irradiation at room temperature (decomposition of silver halide and diffusion of halide (particularly iodine)), and to enhance measurement accuracy. By cooling to −110 ° C., sample destruction can be suppressed to a level that does not hinder measurement.

It is also preferred that silver bromide be present on the outermost surface. In this case, the silver bromide content on the outermost surface is preferably from 1 mol% to 10 mol%.

The average aspect ratio of the tabular silver halide grains of the present invention is preferably 8 or less, more preferably less than 7, and most preferably less than 5.

In the present invention, 20% or more of the total projected area of the silver halide grains contained in the emulsion is preferably composed of tabular silver halide grains having a (100) plane as a main plane, but preferably 50%. More preferably, 70% or more is composed of tabular silver halide grains having a (100) plane as a main plane. The fact that the main 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 shape of a right-angled parallelogram with no corners or a rounded shape. The adjacent side ratio of the right-angled parallelogram is less than 10, preferably less than 5,
More preferably, it is less than 2. When the corner is missing or rounded, the length of the side is the length of the straight line of the side of the right-angled parallelogram, and the length of the side to the intersection with the line that extends the straight line of the adjacent side. It is represented by

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

The average thickness of the tabular silver halide grains of the present invention is preferably from 0.01 to 1.0 μm, more preferably from 0.02 to 0.40 μm, even more preferably from 0.02 to 0.4 μm. 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 monodisperse grains having a narrow particle size distribution. Specifically, when the width of the distribution is defined by (standard deviation of particle size / average particle size) × 100 = width (%) of particle size distribution, it is 20% or less, preferably 18%. Below, more preferably 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%. The content is 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 0.25 μm thick particles)
The above can be observed more clearly using an electron microscope.

Next, the compound represented by formula (1) will be described in detail. In the general formula (1), examples of the substituted or unsubstituted aliphatic hydrocarbon represented by R ₁₁ and R ₁₄ include a linear or branched alkyl or alkenyl having 1 to 30, preferably 1 to 20 carbon atoms. Alkynyl or cycloalkyl groups are mentioned. Specifically, for example, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-butyl, 2-ethylhexyl, allyl, 2-butenyl, 7-octenyl, propargyl, 2-butynyl, cyclopropyl, cyclopentyl , Cyclohexyl, cyclododecyl and the like.

The substituted or unsubstituted aromatic hydrocarbon represented by R ₁₁ and R ₁₄ includes those having 6 to 20 carbon atoms. Specific examples include phenyl, naphthyl, anthranyl and the like.

The hetero ring represented by R ₁₁ and R ₁₄ may be a single ring or a condensed ring, and may be N, O, S, Se or T.
Heterocyclic groups having at least one of the atoms of e in the ring are mentioned. Specifically, for example, pyrroline, furan, tetrahydrofuran, pyridine, piperidine, morpholine, thiadiazole, thiatriazole, benzothiazole, benzoxazole, benzimidazole, benzoselenazole, benzotriazole, indazole,
Quinoline, quinaldine, pyrrolidine, thiophene, oxazole, thiazole, imidazole, selenazole,
Examples include tellurazole, triazole, tetrazole, and oxadiazole. R ₁₁ and R ₁₄ may be the same or different. The compound represented by the general formula (1) is soluble in water or any of various solvents including an organic solvent such as acetone or methanol, and the most preferred compound is a water-soluble compound.
Further, when dispersed and added as fine solid particles, a higher effect may be obtained. The compound represented by the general formula (1) is added as a gold sensitizer during the production process of a silver halide emulsion. Chemical sensitization process conditions such as pH, pAg,
The temperature, time and the like are not particularly limited, and the reaction can be performed under conditions generally performed in the art. It is preferable to use it in combination with another sensitization method.

The amount of the compound represented by the general formula (1) is 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol / AgX mol, preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻⁴ mol / AgX mol. Is a mole.

Hereinafter, specific examples of the compound represented by the general formula (1) (gold (monovalent) sensitizer) of the present invention will be described.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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The spectral sensitizing dye used in the present invention is not particularly limited as long as it has a spectral sensitizing function. The compound represented by the general formula (2) described in claim 2 is adsorbed on silver halide emulsion grains. And measured the reflection spectrum, J
It is preferable that the maximum absorption wavelength of the cohesive zone is 555 nm or less. In addition, in application to an X-ray medical photosensitive material using a phosphor that emits green light, the general formula (2) of the present invention is used.
The compound represented by is adsorbed on silver halide emulsion grains,
It is preferable that the J-band is formed in the same wavelength range as the green light from the phosphor when the reflection spectrum is measured. That is, the maximum absorption wavelength is preferably 520
J- at which the absorption is maximum in the range of nm to 555 nm.
It is preferable to select and combine spectral sensitizing dyes such that a band is formed. More preferably, 530 to 553.
nm, most preferably 540-550 nm.

In the general formula (2), R ₁ and R ₃ are each
Represents a substituted or unsubstituted alkyl group or alkenyl group.
Examples of the alkyl group include linear or branched groups such as ethyl, propyl, and 3-methylbutyl groups. Examples of the substituted alkyl group include 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, ethoxycarbonylethyl, Examples include allyl, phenethyl, methanesulfonylethyl, and 3-oxobutyl groups.

The alkyl groups represented by R ₂ and R ₄ include, for example, straight-chain and branched groups such as methyl, ethyl, butyl, and isobutyl groups. , Carboxy, methanesulfonylaminocarbonyl, methanesulfonylaminosulfonyl,
There are dissociable groups such as acetylaminosulfonyl, sulfoamino, trifluoroacetylaminosulfonyl, acetylaminocarbonyl, and N-methylsulfamoyl, and specific examples include, for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 5-sulfopentyl,
2-N-ethyl-N-sulfoaminoethyl, carboxymethyl, carboxyethyl, 3-sulfoaminopropyl, 6-sulfo-3-oxahexyl, 10-sulfo-
Examples include 3,6-dioxadecyl, 6-sulfo-3-thiahexyl, o-sulfobenzyl, p-carboxybenzyl, methanesulfonylaminocarbonylmethyl, and acetylaminosulfonylmethyl groups.

Z ₁ , Z ₂ , Z ₃ and Z ₄ may be the same or different, and each has a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, iodine atom, etc.) and an alkyl group (eg, methyl , Ethyl, propyl and other lower alkyl groups), alkoxy groups (for example, methoxy, ethoxy, propoxy and the like), and halogen-substituted alkoxy groups (for example, fluoromethoxy, trifluoromethyl,
2,2,2-trifluoroethyl group, etc.), aryloxy group (eg, phenoxy, p-bromophenoxy group, etc.), acyl group (eg, acetyl, benzoyl group, etc.),
Acyloxy groups (eg, acetyloxy, propionyloxy groups, etc.), alkylthio groups (eg, methylthio, ethylthio groups, etc.), halogen-substituted alkylthio groups (eg, trifluoromethylthio, difluoromethylthio groups, etc.), and alkoxycarbonyl groups (eg, methoxycarbonylmethyl) , Ethoxycarbonyl group, etc.), carbamoyl group (for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-diethylcarbamoyl, N, N-3-oxa-pentamethylenecarbamoyl, N-phenylcarbamoyl group, etc.) ), Sulfamoyl groups (eg, N-methylsulfamoyl, N, N
-Tetramethylenesulfamoyl, N, N-3-oxapentamethylenesulfamoyl, N-phenylsulfamoyl, N, N-diethylsulfamoyl group, etc.), haloalkyl group (for example, monofluoromethyl, difluoromethyl, Trifluoromethyl, monochloromethyl group, etc.),
A sulfonyl group (eg, methanesulfonyl, ethanesulfonyl, trifluoromethanesulfonyl, fluorosulfonyl, benzenesulfonyl, p-toluenesulfonyl, etc.), an acylamino group (eg, N-acetylamino, N
-Trifluoroacetylamino group, etc.), substituted or unsubstituted aryl groups (eg, phenyl, o-fluorophenyl, p-cyanophenyl, m-chlorophenyl group, etc.),
The heterocyclic group includes substituted or unsubstituted ones (for example, 1-pyrrolyl, 2-furyl, 2-benzoxazolyl group, etc.).

The ion necessary for neutralizing the intramolecular charge may be an anion or a cation. Examples of the anion include a halogen ion (chloro,
Bromo, iodine and the like), perchlorate, ethyl sulfate, thiocyanate, p-toluenesulfonate, perfluoroborate and the like. Examples of the cation include hydrogen ion, alkali metal ion (ion such as lithium, sodium and potassium). , Alkaline earth metal ions (ions such as magnesium and calcium), ammonium ions, and organic ammonium ions (ions such as triethylammonium, triethanolammonium, and tetramethylammonium).

Next, specific examples of the compound (spectral sensitizing dye) represented by the above formula (2) will be given, but the present invention is not limited to these.

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The spectral sensitizing dye of the present invention may be used in combination with another spectral sensitizing dye. 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 nuclei commonly used. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus,
Selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc., these nuclei are fused with an alicyclic hydrocarbon ring, that is, indolenine nucleus, benzindolenine nucleus,
Indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has pyrazoline- as a nucleus having a ketomethine structure.
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.

In addition to these spectral sensitizing dyes, dyes having no spectral sensitization or substances which do not substantially absorb visible light and exhibit supersensitizing action are added to the emulsion layer. Is preferred.

In the present invention, the amount of the spectral sensitizing dye added is
Type of dye and structure, composition, ripening condition of silver halide,
Depending on the purpose and application, the coverage of the monomolecular layer on the surface of each photosensitive particle in the silver halide emulsion is 30% or more and 90% or more.
% Or less, preferably 40% or less.
80% is particularly preferred.

In the present invention, the monolayer coverage is 5%.
The saturated adsorption amount when an adsorption isotherm is prepared at 0 ° C. is relatively determined as an amount corresponding to a coverage of 100%.

The appropriate amount per mol of silver halide varies depending on the total surface area of the silver halide grains in the emulsion.
Less than 00 mg is preferred. Further, it is preferably 450 mg or less.

In order to further increase the sensitivity and improve the residual color, the ratio of the spectral sensitizing dye represented by the general formula (2) of the present invention is preferably 30% or more of all the dyes in the photographic material.

As a solvent for the sensitizing dye, a conventionally used water-miscible organic solvent can be used. For example, alcohols, ketones, nitriles, alkoxy alcohols and the like have been used. Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol,
There are 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol and the like.

As a dispersant for the spectral sensitizing dye, a surfactant has conventionally been used. Surfactants include anionic, cationic, nonionic and amphoteric surfactants, and any of these surfactants can be used in the present invention.

In the present invention, however, the effect is increased by adding the spectral sensitizing dye as a dispersion in the form of solid fine particles, as compared with the case of adding it as a solution of an organic solvent.
In particular, at least one of the spectral sensitizing dyes is added in the form of a solid fine particle dispersion substantially insoluble in water dispersed in an aqueous system substantially free of an organic solvent and / or a surfactant. Is preferred.

On the other hand, the present invention is intended to uniformly and effectively adsorb the photographic spectral sensitizing dye on the surface of silver halide grains. The purpose and effect are different.

In the present invention, an organic solvent and / or
Alternatively, the aqueous system free of a surfactant is water containing impurities at a level not adversely affecting the silver halide photographic emulsion, and more preferably refers to ion-exchanged water and distilled water.

The solubility of the spectral sensitizing dye in the present invention in water is preferably 2 × 10 ⁻⁴ to 4 × 10 ⁻² mol / l, more preferably 1 × 10 ⁻³ to 4 × 10 ⁻² mol / l. is there.

If the solubility is lower than this range, the dispersion particle size is very large and non-uniform, so that after the dispersion is completed, a precipitate of the dispersion is formed or the dispersion is added to the silver halide emulsion. Occasionally, the process of adsorbing the dye onto silver halide may be hindered.

On the other hand, when the solubility is higher than the above range, the viscosity of the dispersion increases more than necessary, and bubbles are involved, which hinders the dispersion, and the dispersion becomes impossible at a higher solubility. This has become clear from the study of the present inventors.

In the present invention, the solubility of the spectral sensitizing dye in water was measured by the following method.

That is, 30 ml of ion-exchanged water was put into a 50 ml Erlenmeyer flask, an amount of the dye which was not completely dissolved visually was added thereto, the temperature was kept at 27 ° C. in a constant temperature bath, and the mixture was stirred with a magnetic stirrer for 10 minutes.

The suspension was filtered with a filter paper no. 2 (Toyo Corporation)
The filtrate was filtered with a disposable filter (manufactured by Tosoh Corporation), the filtrate was appropriately diluted, and the absorbance was measured with a spectrophotometer U-3410 (manufactured by Hitachi, Ltd.). Next, based on the measurement results, the solubility was determined according to Lambert-Beer's law, and the solubility was further determined.

D = εlc where D: absorbance, ε: spectral extinction coefficient, 1: cell length for absorbance measurement, c: concentration (mol / liter).

In the present invention, the spectral sensitizing dye can be added during the chemical ripening step, particularly preferably at the start of the chemical ripening step, and from the nucleation step to the desalting step of the silver halide emulsion according to the present invention. By adding it by the end, a high-sensitivity silver halide emulsion having excellent spectral sensitization efficiency can be obtained.However, at any time after the completion of the desalting step and immediately before the coating step through the chemical ripening step, A spectral sensitizing dye according to the present invention which is the same as or different from the dye added in the step (from the nucleation step to the end of the desalting step) may be additionally added.

Next, the compounds represented by formulas (3), (4) and (5) of the present invention will be described in detail.

In the general formula (3), X represents —SO ₃ M,
A heterocyclic residue directly or indirectly having at least one selected from -COOM and -OM, for example, an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring,
Triazole ring, tetrazole ring, thiadiazole ring,
Oxadiazole ring, pentazole ring, pyrimidine ring,
A thiazine ring, a triazine ring, a thiodiazine ring or a ring bonded to another carbon chain or a heterocyclic ring, such as a benzothiazole ring, a benzotriazole ring, a benzimidazole ring, a benzoxazole ring, a benzoselenazole ring, a naphthoxazole ring, and triazaindole. It is a lysine ring, a diazaindolizine ring, a tetraazaindolizine ring or the like, and preferably an imidazole ring, a tetrazole ring, a benzimidazole ring, a benzothiazole ring, a benzoxazole ring, and a triazole ring.

The compounds represented by the general formula (3) are described in US Pat. Nos. 2,585,388 and 2,541,924;
JP-B-42-21842, JP-A-53-50169
No., British Patent No. 1,275,701; A. Ber
ges et. al. , “Journal of He
terocyclic Chemistry "15,9
81 (1978), "The Chemistry o
f Heterocyclic Chemistry "
Imidazole and Derivatives
part I, p. 336-339, Chemica
l Abstract, 58, 7921 (1963),
p. 394, E.C. Hoggarth "Journal
of Chemical Society ", p.11
60-1167 (1949); R. Saudle
r, W.S. Karo “Organic Functiona”
l Group Preparation "Acade
mic Press, p. 312 to 315 (196
8), M.P. Champdon, et. al. , Bulle
tin de la Society Chimique
ede France, 723 (1954); A.
Shirley, D .; W. Alley, J.M. Amer.
Chem. Soc. 79, 4922 (1954);
Wohl, W.C. Marchwald “Ber.” 22,
p. 568 (1889); Amer. Chem. S
oc. 44, p. 1502-1510, U.S. Pat.
017,270, British Patent No. 940,169, JP-B-49-8334, JP-A-55-59463, "A
advanced in Heterocyclic C
hemistry ", West German Patent No. 2,716,707
No., “The Chemistry of Heter
occyclic Compounds Imidazo
le and Derivatives ", 1, p.3
85, “Org. Synth.” IV. , 569 (196
3), "Ber." 9, 465 (1976), "JA.
mer. Chem. Soc. "45, 2390 (192
3), JP-A-50-89034 and JP-A-53-28426.
No. 55-21007, JP-B-40-28496, and the like.

Next, the compound represented by formula (4) or (5) will be described. —SO ₃ M ₁ , —CO represented by (A ₁ ) and (A ₁ ) ′ in the general formulas (4) and (5)
As the metal atom represented by M ₁ in OM ₁ or —OM ₁ , a transition metal capable of binding to sulfur such as alkali metal, silver, gold, palladium, selenium or tellurium, or the like is preferable.

(A_Two) And (A_TwoElectron attraction represented by) '
Functional groups include a fluorine atom, a chlorine atom,
Tyl group, cyano group, nitro group, -SOCF_ThreeGroup, -SO_Two
NH _TwoGroup, -SO_TwoCH_ThreeGroups and the like are preferred.

The functional group containing a sulfur atom, a selenium atom or a tellurium atom which can bind to a silver ion represented by (A ₃ ) and (A ₃ ) ′ is a mercapto group, a thione group, -SeH
Group, = Se group and the like are preferable.

The aliphatic hydrocarbon represented by Y, Y ₁ or Y ₂ preferably has 4 to 20 carbon atoms, and the aromatic hydrocarbon is preferably a benzene ring, a naphthalene ring or the like.

The compound represented by formula (4) or (5) further includes a halogen atom other than fluorine, a hydroxyl group, an amino group, an acylamino group, an alkylamino group, an alkyl group, an alkenyl group, a cycloalkyl group, Aryl group, alkoxy group, aryloxy group, alkylthio group, alkoxycarbonyl group, carbamoyl group, alkoxyalkyl group, aminoalkyl group, acylaminoalkyl group, hydroxyalkyl group, carboxyalkyl group, sulfoalkyl group, alkylsulfonamide group, etc. May have a substituent.

These compounds are described in "J. Chem. So
c. Sect. C "p.626 (1965) & p.13
47 (1971), "J. Org. Chem."
p. 534 (1969), JP-A-60-184057.
And No. 60-204742. Some are available as commercial products.

The specific examples of the compounds represented by formulas (3), (4) and (5) are shown below, but the invention is not restricted thereto.

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The compound represented by formula (3), (4) or (5) may be added at the time of grain formation, before or after chemical sensitization, or during chemical sensitization. When added before the end of chemical sensitization, a high fogging inhibitory effect may be obtained. When added separately before and after the end of the chemical sensitization, a better effect can be obtained, and there is also an effect of improving the covering power. The compounds may be used in combination of two or more, or may be used in combination with other inhibitors.

As a method of addition, powder may be added as it is, or a solution dissolved in a low-boiling organic solvent such as methanol, ethanol, ethyl acetate or the like, water, or a mixed solvent of a low-boiling organic solvent and water may be used. It may be added. If necessary, a pH adjuster may be used to enhance the solubility. or,
When dispersed and added as finely divided solids, higher effects may be obtained. In any case, the addition amount was from 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² per mol of silver before chemical sensitization.
Mole, preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻³ . After completion of chemical sensitization, the amount is 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol, preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² .

In the present invention, the conditions of the step of chemical sensitization,
For example, pAg, temperature, time and the like can be performed under conditions generally performed in the art.

The silver halide emulsion of the present invention is preferably subjected to at least one chemical sensitization among sulfur sensitization, selenium sensitization and tellurium sensitization.

In the case of selenium sensitization, a wide variety of selenium compounds can be used as the selenium sensitizer, for example, US Pat. Nos. 1,574,944, 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, and selenoketones, selenides.

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. Further, a method in which the mixture is added in advance with a gelatin solution, or a method in which the mixture is added in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent by the method disclosed in JP-A-4-140739 may be used.

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 preferred.

Regarding tellurium sensitizers and sensitization methods, see, 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-4-330430
And the like.

Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-).
Dimethyltellurourea, N, N′-dimethyl-N′phenyltellurourea), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride,
Butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (e.g., telluroacetamide, N, N-dimethyltellurobenzamide), telluroketones, telluroesters, and isotellurocyanates.

The silver halide emulsion of the present invention contains selenium and / or
Alternatively, it is preferable to use a chemical sensitization other than tellurium sensitization in combination. The conditions of the chemical sensitization step, for example, pH, pAg, temperature, time and the like are not particularly limited, and can be performed under conditions generally performed in the art. Preferable chemical sensitization methods when used in combination include a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions and active gelatin, a reduction sensitization method using a reducing substance, gold and other noble metal sensitization methods using a noble metal. And the like. Among them, a sulfur sensitization method, a gold sensitization method, a reduction sensitization method and the like are preferable. It is more preferred to use reduction sensitized silver halide grains.

Examples of the sulfur sensitizer applicable in the present invention include US Pat. Nos. 1,574,944 and 2,410,
No. 689, No. 2,278,947, No. 2,728,6
No. 68, No. 3, 501, 313, No. 3, 656, 95
No. 5, West German Application Publication (OLS) 1,422,869,
Sulfur sensitizers described in JP-A-56-24937 and JP-A-55-45016 can be used.
Specific examples include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl, 3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and sulfur alone. And the like are preferred examples. In addition, as the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

Examples of the gold sensitizer include compounds other than the organic gold (monovalent) compound represented by the general formula (1), chloroauric acid, gold thiosulfate, gold thiocyanate and the like, thioureas, rhodanine and the like. , And gold complexes of various compounds.

The amount of the sulfur sensitizer used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc.
It is preferably from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁹ mol. Further, the amount is preferably 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

In the present invention, the sulfur sensitizer and the gold sensitizer may be added in the form of a solution by dissolving them in water or an alcohol or another inorganic or organic solvent, or adding a solvent insoluble in water. Alternatively, it may be added in the form of a dispersion obtained by emulsifying and dispersing using a medium such as gelatin.

In the present invention, selenium and / or tellurium sensitization, sulfur sensitization and gold sensitization may be simultaneously performed.
It may be applied separately and stepwise. It is also preferable to perform so-called reduction sensitization on the surface of the grains by placing the grains in an appropriate reducing atmosphere. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof. Other preferable reducing agents include polyamines such as hydrazine and diethylenetriamine, dimethylamineboranes, sulfites and the like.

When at least any one of the layer containing the photosensitive silver halide emulsion of the present invention or a constituent layer other than the emulsion layer contains a dye capable of decoloring and / or flowing out during development processing, A photosensitive material having high sensitivity, high sharpness, and little dye stain can be obtained. 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 used in the light-sensitive material of the present invention has a pH of 7
Below, it is substantially insoluble in water, has a pH of 8 or more, and is substantially water-soluble. The amount added can be varied depending on the sharpness goal. Preferably 0.2 mg / m ²
-20 mg / m ² , more preferably 0.8 mg / m ² -1
5 mg / m ² . As the above-mentioned dye, a known dye can be preferably used.

The silver halide light-sensitive material according to the present invention includes:
Various photographic additives can be used. Known additives include, for example, Research Disclosure No.
No. 17643 (December 1978); 18716
(November 1979) and the same No. 308119 (19
(December 1989). The types of compounds and the locations described in these three research disclosures are listed below.

Additives 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 Fogging inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 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 XVII Used for the photosensitive material of the present invention. The support can Rukoto, for example page 28 of the aforementioned RD-17643 and RD
-308119 on 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, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. The undercoat layer preferably contains an antistatic improver such as a colloidal tin oxide sol.

When the silver halide emulsion layer and the crossover cut layer are provided on both sides of the support of the photographic light-sensitive material of the present invention, a light-sensitive material having high sensitivity, high sharpness and excellent processability can be obtained. The amount of gelatin in the silver halide emulsion layer, surface protective layer and other layers is 0.5 to 0.5 in total on one side of the support.
It is preferably in the range of 3.5 g / m ² , especially 1.
The range of 0 to 3.0 g / m ² is preferred.

The latex used in the present invention is preferably one which has no or very little adverse effect on the following points even when used in a silver halide photographic element. That is, the latex surface is photographically inert and has very little interaction with various photographic additives. As an example, dyes and dyes are adsorbed and the photographic element is hardly stained with color. Further, it is difficult to adsorb a development accelerator, a development inhibitor, and the like, which affect the speed of development, and hardly affect sensitivity and fog.

The fact that the latex that can be used in the present invention has the above properties is considered to have a great influence on the monomer composition and properties of this latex.

For latex, an index called a glass transition point is often used. The higher the transition point is, the harder it becomes and cannot serve as a buffer. For this reason, considering the photographic characteristics, the selection of the composition and its use amount are not simple. Latexes using monomers such as styrene, butadiene, and vinylidene are well known. It is said that when a monomer having a carboxylic acid group such as acrylic acid, itaconic acid or maleic acid is introduced during the synthesis of latex, the influence on the photographic properties is reduced, and such synthesis is often attempted. The latex obtained by such a combination may contain a methacrylate unit to appropriately set the glass transition point according to the light-sensitive material. As a specific example, see Japanese Patent Application Laid-Open No. 2-135
No. 335, JP-A-6-308670 and JP-A-6-308670
No. 658 etc. will be helpful.

The silver halide photographic light-sensitive material of the present invention can be processed using a solid processing agent. The solid processing agent referred to in the present invention is a powder processing agent, a solid processing agent such as tablets, pills and granules, etc., which is subjected to a moisture-proof treatment as required.

In the present invention, the powder refers to an aggregate of fine crystals, and the granules refer to a powder obtained by subjecting a powder to a granulation step and have a particle size of 50 to 5000 μm.
In addition, the tablet in the present invention refers to a tablet obtained by compression-molding a powder or granules into a certain shape. The silver halide photographic material of the present invention is supplied and processed while continuously processing such a solid processing agent.

To solidify the processing agent, a concentrated solution or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded processing agent is sprayed with the water-soluble binder. Or any other means such as forming a coating layer. A preferred tablet production method is a method of granulating a powdery solid processing agent and then performing a tableting step to form the tablet.

Compared to a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet, the solubility and storage properties are improved, and as a result, the photographic performance is stabilized. As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. For tablet formation, the average particle size of the obtained granules is 100 to 800 μm, because when mixing the granules and compressing and compressing, the components become non-uniform, so-called segregation hardly occurs. Is preferably used, and more preferably 200 to 750 μm. Further, the particle size distribution is such that 60% or more of the
Those having a deviation of 0 to 150 μm are preferable. Next, when the obtained granules are compressed under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine and a briquetting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handling, or dust when used on the user side, a cylindrical type, so-called tablet, is preferable. .

Preferably, at the time of granulation, the above effect is further remarkable by separately granulating each component such as an alkali agent, a reducing agent and a preservative.

In the present invention, the solid processing agent is used for a photographic processing agent such as a developer, a fixing agent, and a rinsing agent. The developer which has a large effect of the present invention, particularly, a stabilizing effect on photographic performance is large.

In the present invention, as a supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Utility Model Application Laid-Open Nos. 63-137783 and 63-9752.
No. 2, Japanese Utility Model Laid-Open No. 1-85732, etc., but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is in the form of granules or powders, see JP-A-62-81964, 6
3-84151, JP-A-1-292375, and Japanese Utility Model Laid-Open Nos. 63-105159 and 63-105159.
A method using a screw or a screw described in -195345 or the like is known.

The place where the solid processing agent is charged may be in the processing tank, but is preferably in a place where the processing liquid is in communication with the processing section for processing the photosensitive material and the processing liquid flows between the processing section and the processing section. In addition, it is preferable that the processing solution circulates at a constant rate between the processing section and the dissolved component and moves to the processing section. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

In the developer used in the present invention, a developer which does not substantially contain a dihydroxybenzene-based agent as a developing agent, contains reductones such as ascorbic acids, and does not contain aldehyde hardeners. preferable.

The developing agent used in the present invention will be described. As the developing agent, the following developing agents may be contained in addition to reductones such as ascorbic acids. The developing agent preferably contains dihydroxybenzenes or, if necessary, a p-aminophenol compound and / or a pyrazolidone compound.

As the dihydroxybenzenes, for example,
Hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples thereof include dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, and hydroquinone monosulfonate.

Examples of the pyrazolidone compound include, for example, 3
-As pyrazolidones, for example, 1-phenyl-3-
Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3- Pyrazolidone, 1
-Phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1- (2- Benzothiazolyl)
-3-pyrazolidone, 3-acetoxy-1-phenyl-
3-pyrazolidone and the like. Examples of the aminophenols include 1-allyl-3-pyrazolis such as o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, and 2,4-diaminophenol. (For example, 1- (p
-Hydroxyphenyl) -3-aminopyrazoline, 1-
(P-amino-m-methylphenyl) -3-aminopyrazoline, etc.), pyrazolones (for example, 4-aminopyrazolone, etc.) or a mixture thereof.

The preservative may contain a sulfite such as potassium sulfite, sodium sulfite, or a reductone such as piperidinohexose reductone, preferably 0.2 to 1 mol / l. ,
It is more preferable to use 0.3 to 0.6 mol / l. Also, the addition of a large amount of ascorbic acids leads to processing stability. It is also preferable to add compounds described in JP-A-5-289255 and JP-A-6-308680 (general formulas [4-a] and [4-b]) as silver sludge inhibitors. The addition of a cyclodextrin compound is also preferred, and the compounds described in JP-A-1-124852 are particularly preferred.

It is necessary to use a buffer for the developer used in the present invention. Examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, and tripotassium phosphate. , Dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate),
Examples thereof include potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). The pH of the developer may be from 9.0 to 12, and preferably from 9.0 to 11.5.

As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be exemplified by 1-phenyl-5-mercaptotetrazole as a typical example.

Further, the developer composition used in the present invention may contain, if necessary, methylcellosolve, methanol, acetone, dimethylformamide, cyclodextrin compounds, and other JP-B Nos. 47-33378 and 44-95.
No. 09 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, various additives such as an anti-stain agent, an anti-sludge agent and a layering effect promoter can be used.

In the present invention, the term “fixing solution” refers to a solution in a fixing tank. Preferred fixing solutions can include fixing materials commonly used in the art. The iodine content is preferably 0.3 g / liter or less, more preferably 0.1 g / liter or less. The pH is at least 3.8, preferably 4.2-5.5.

As the fixing solution according to the present invention, a fixing solution containing a fixing agent such as sodium thiosulfate and ammonium thiosulfate can be used, and among these, ammonium thiosulfate is preferable in terms of fixing speed. These fixing agents are generally used in an amount of about 0.1 mol to 6 mol / l.

The fixing solution may contain an aqueous solution aluminum salt as a hardening agent, and further includes aluminum chloride, aluminum sulfate, potassium alum and the like.

For the fixing solution, malic acid, tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination. It is effective to contain these compounds in an amount of 0.001 mol or more per liter of the fixing solution.
0.005 to 0.03 mol is particularly effective.

The fixing solution preferably has a pH of 3.8 or more, and preferably has a pH of 4.2 to 7.0. In consideration of the fixed hardening film or the odor of sulfurous acid, 4.3 to 4.8 is more preferable.

The photosensitive material which has been developed and fixed is subsequently washed or stabilized. Washing or stabilizing treatment
Not only is it possible to save water with a replenishment amount of 3 liters or less per 1 m ^{2 of} silver halide photographic material (including 0, that is, it can be carried out by pooled water washing), and the piping for installing an automatic developing machine is unnecessary. can do.

In the case where washing with a small amount of water is carried out,
It is more preferable to provide a squeeze roller washing tank described in -18350 and 62-287252. In addition, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, by replenishing the washing or stabilizing bath with water subjected to a fungicide according to the treatment, part or all of the overflow liquid generated from the washing or stabilizing bath is described in JP-A-60-235133. As described above, it can also be used for a processing solution having a fixing ability, which is the preceding processing step.

In addition, the treatment agent component which prevents water bubble unevenness which tends to occur when washing with a small amount of water and / or adheres to the squeeze roller is
A water-soluble surfactant or an antifoaming agent may be added to prevent transfer to the treated film. Japanese Patent Application Laid-Open No. 63-1 / 1988 describes prevention of contamination by dyes eluted from a photosensitive material.
The dye adsorbent described in No. 63456 may be installed in a washing tank. In some cases, a stabilization treatment may be performed after the water washing treatment. For example, Japanese Patent Application Laid-Open Nos. 2-201357 and 2-1
No. 32435, No. 1-125553, JP-A-46-4
A bath containing the compound described in No. 4446 may be used as the final bath of the light-sensitive material. If necessary, a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, various chelating agents, a film pH regulator, a hardening agent, a bactericide, an antifungal agent, an alkanolamine, or a surfactant may be used in this stabilizing bath. Agents can be added.

The water used in the washing step or the stabilizing step includes tap water, deionized water, halogen, an ultraviolet germicidal lamp, and various oxidizing agents (ozone, hydrogen peroxide,
For example, water sterilized by chlorate or the like can be used. Prior to the treatment, it is preferable to add a starter, and it is also preferable to solidify and add the starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

The processing temperature of the development of the present invention is preferably 2
The temperature is 5 to 50C, more preferably 30 to 40C. The development time is 3 to 15 seconds, more preferably 4 to 10 seconds. The total processing time of the present invention is Dry to Dry within 60 seconds, preferably 10 to 45 seconds, more preferably 15 to 30 seconds. The total processing time is a processing time including the steps of developing, fixing and drying the photosensitive material.

The replenishment in the present invention replenishes a treatment agent fatigue and an oxidative fatigue equivalent. As a replenishment method, JP-A-55-55
No. 126243, replenishment by width and feed speed, area replenishment described in JP-A-60-104946,
No. 49156, the area replenishment may be controlled by the number of sheets continuously processed.
The preferred replenishment amount for development and replenishment is 1 to 7 cc / 4.

The silver halide emulsion layer of the present invention preferably has a swelling ratio of 150 to 250% during the development process, and a film thickness after expansion of 70 μm or less. 250% water swelling
If the temperature exceeds the limit, drying failure occurs, and for example, conveyance failure also occurs in automatic developing machine processing, particularly in rapid processing. On the other hand, when the water swelling ratio is less than 150%, uneven development and residual color tend to be deteriorated during development. Here, the water swelling ratio is the difference between the film thickness after swelling in each processing solution and the film thickness before development processing,
This is a value obtained by dividing 100 times the film thickness before processing.

The filling rate of the phosphor in the phosphor layer of the radiation intensifying screen according to the present invention is 68% or more, preferably 70% or more, and more preferably 72% or more.

In the present invention, the thickness of the phosphor layer is 15
0 μm or more and 250 μm or less. Here, if the thickness of the phosphor layer is less than 150 μm, the sharpness sharply deteriorates.

It is preferable that the radiation intensifying screen of the present invention is filled with a phosphor in a gradient particle size 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.
5 to 2.0 μm, and those having a large particle diameter are preferably in the range of 10 to 30 μm.

In the fluorescent intensifying screen used in the combination of the present invention, the X-ray absorption of each intensifying screen is 30% per 100 μm of the thickness of the phosphor layer by increasing the filling rate of the phosphor particles. It is preferable that it is above. 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 equivalent to 2.2 mm of aluminum and passed through a 3 mm-thick aluminum plate having a purity of 99% or more are supplied by three-phase power supply. 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 the radiation intensifying screen according to the present invention include thermoplastic elastomers. Specifically, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene,
At least one type of thermoplastic elastomer selected from the group consisting of ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluororubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber and silicone rubber.

As the phosphor used in the radiation intensifying screen according to the present invention, known phosphors can be mentioned.

[0175]

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

Example 1 All the emulsions shown below were prepared in a reaction vessel having a volume of 32 liters. As an ultrafiltration unit, Asahi Kasei SIP-1013, and as a circulating pump, DAIDOR®
otory Pump was used. The volume of the emulsion circulation part of the ultrafiltration step was 1.2 l, and the emulsion was circulated at a constant flow rate of 15 l / min. Thus, the residence time of the reactant solution was 4.8 seconds, and the volume of the emulsion circulation portion of the ultrafiltration step was 3.8% of the volume of the reaction vessel. The control of the distance between particles in the particle growth process was performed by appropriately controlling the permeation flux in the ultrafiltration step. Specifically, the adjustment was performed by adjusting the flow control valve 19 in FIG.

<Preparation of Hexagonal Tabular Grains of Silver Iodobromide> Preparation of Em-1 A1 Ossein gelatin 75.5 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol solution) 6.78 ml Potassium bromide 64 0.7 g Finished to 10800 ml with water B1 0.7 N aqueous silver nitrate solution 1340 ml C1 2.0 N aqueous silver nitrate solution 1500 ml D1 1.3 N aqueous potassium bromide solution 410 ml E1 2.0 N aqueous potassium bromide solution Silver potential control amount below F1 ossein gelatin 125 g water 4000 ml G1 Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average particle size: 0.05 μm) Equivalent to 0.008 mol * 5.0% by weight of gelatin containing 0.06 mol of potassium iodide To 6.64 liters of aqueous solution, 7.06 moles of silver nitrate And 2 liters of an aqueous solution containing 7.06 mol of potassium iodide were added over 10 minutes. During the formation of the fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

At 55 ° C., JP-B-58-58288, 5
Solution A using a mixing stirrer described in JP-A-8-58289.
400 ml of the solution B1 and the entire amount of the solution D1 were added to 1 by a simultaneous mixing method over 40 seconds to form nuclei.

After the addition of the solution B1 and the solution D1, the solution F1 is added, and the temperature is raised to 70 ° C. for aging. Further, after the remaining amount of the solution B1 is added over 25 minutes, aging is performed for 10 minutes using a 28% aqueous ammonia solution, and the pH is returned to neutral with acetic acid. Simultaneous addition and mixing of the solutions C1 and E1 at a rate commensurate with the critical growth rate while maintaining pAg = 7.8,
G1 was added after all of 1 was added. After stirring for 5 minutes, soluble salts were desalted and removed by the sedimentation method.

In this emulsion, 90% or more of the total projected area of the silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains was 0.20 μm.
m and the average particle diameter (in terms of circular diameter) were confirmed to be 0.80 μm by an electron microscope. The distribution of the circle equivalent diameter is 15
%Met.

Preparation of Em-2 Particles were produced by the same ultrafiltration method as Em-1, but instead of AgI fine particles from subsurface to surface, general formula (5) was used.
(5-3) was added in an amount of 0.5 mol / Ag mol. Subsequently, the above-mentioned emulsions Em-1 and Em-2 were each divided into a predetermined amount, the temperature was adjusted to 50 ° C., an inhibitor was added as shown in Table 1, and then the spectral enhancement was performed. Dye sensitive dyes (shown in Table 1 as dye types) were added as solid fine particle dispersion. Subsequently, 3.5 mg of sodium thiosulfate, 1 mg of ammonium thiocyanate, 3.6 of triphenylphosphine selenide were used.
mg of solid particulate dispersion was added. Further, a gold sensitizer was added as shown in Table 1, and aging was performed for a total of 2 hours. After removing unreacted compounds in the emulsion by ultrafiltration, 3 mg of 1-phenyl-5-mercaptotetrazole (PMT) as a stabilizer and an inhibitor were added as shown in Table 1. The amount of addition was per mole of AgX.

<Preparation of silver iodochloride tabular grains> Preparation of Em-3 A2 Ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g Finished to 15000 ml with distilled water B2 410 g of silver nitrate Finished to 684 ml with distilled water C2 Silver nitrate 11590 g Finished to 19316 ml with distilled water D2 KI 4 g NaCl 140 g Finished to 684 ml with distilled water E2 NaCl 3980 g Potassium hexachloroiridate (IV) 8 × 10 ^-6 mol Finished to 19274 ml with distilled water At 40 ° C., Japanese Patent Publication No. 58-58888 58-
No. 58289, solution A2 in a mixing stirrer
, The total amount of B2 and D2 was added over 1 minute. EAg
Was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the total amount of C2 and E2 was added over 320 minutes. Meanwhile, EAg was controlled at 149 mV.

Immediately after the addition was completed, desalting and washing were performed.
Em-2 thus produced was composed of tabular grains having 65% of the total projected area of the silver halide grains having the (100) plane as the main plane, with an average thickness of 0.14 μm and an average diameter of 1.
It was found by electron microscope observation that the coefficient of variation was 0 μm and the coefficient of variation was 25%.

<Production of Em-4> Particles were produced by the same ultrafiltration method as in Em-3, but the surface was changed from subsurface to Ag.
The compound (4) represented by the general formula (4)
-4) was added in an amount of 0.5 mol / Ag mol. Emulsions Em-3 and Em-4 were each divided into predetermined amounts, the temperature was raised to 55 ° C., 0.05 mg of thiourea dioxide was added, and iodination was performed after 20 minutes. 0.5 mol% of silver fine particles was added. Subsequently, an inhibitor was added as shown in Table 1, and a dispersion of the spectral sensitizing dye (shown in Table 1) in the form of solid fine particles and 0.4 g of calcium chloride were added. Subsequently, a solid particulate dispersion containing 4 mg of sodium thiosulfate, 0.5 mg of ammonium thiocyanate, and 4.1 mg of triphenylphosphine selenide was added. Thereafter, a gold sensitizer was added as shown in Table 1, and aging was performed for a total of 2 hours.

At the end of ripening, 1-phenyl-
3 mg of 5-mercaptotetrazole (PMT) and an inhibitor were added as shown in Table 1. The amount of addition was per mole of AgX.

<Comparative Em-5> Preparation of Comparative Emulsion Em-5 In preparing Em-1, a comparative emulsion Em-5 was prepared by a conventional charging method without using an ultrafiltration method.

A dispersion of the spectral sensitizing dye in the form of solid fine particles was prepared by adding a predetermined amount of the spectral sensitizing dye to water previously adjusted to 27 ° C., and using a high-speed stirrer (dissolver) at 3,500 rpm for 30 minutes.
Obtained by stirring for ~ 120 min.

[0188]

[Table 1]

[0189]

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The following additives were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a coating solution for a protective layer described below was prepared. Using both the coating solution, the silver amount per one side coated amount is 1.5 g / m ^2, gelatin with the amount of each using two slide hopper type coater so that 2.4 g / m ² min 8
Both sides were simultaneously coated on the support at a speed of 0 m, and dried for 2 minutes and 20 seconds to obtain a sample. As a support, glycidyl methacrylate 50 wt%, methyl acrylate 10 w
The copolymer aqueous dispersion obtained by diluting the concentration of the copolymer composed of three monomers of 10% by weight and 40% by weight of butyl methacrylate to 10% by weight was used as a subbing liquid, and 175 μm was obtained.
A polyethylene terephthalate film base colored blue with a density of 0.13 for an X-ray film of m 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) 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 ( 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 ammonium dihydroxybenzene-4-sulfonic acid 500 mg / m ² 2-mercaptobenzimidazole-5-sulfonate sodium 5 mg / m ² compound ^{(H) 0.5mg / m 2 n} -C 4 H 9 _{OCH 2 CH (OH) CH 2} N _{CH 2 COOH) 2 350mg / m} 2 Compound (M) 5mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.2g / m ² Dextrin (average molecular weight 1000) 0.2g / m ² of gelatin 1. 4 g / m ² Third layer (protective layer) Gelatin 0.8 g / m ² Polymethyl methacrylate matting agent (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 10,000) 0.1 g / m ² poly sodium acrylate 30 mg / m ² polysiloxane (SI) 20mg / m ² compound (I) 12mg / m ² compound (J 2 mg / m ² Compound (S-1) 7mg / m 2 Compound (K) 15mg / m ² Compound (N) 5mg / ^{m 2} Compound (O) 5mg / m ² Compound (S-2) 5mg / m 2 C 9 _{F 19 -O- (CH 2 CH 2} O) 11 -H 3mg / m 2 C 8 F 17 SO 2 N- (C 3 H 7) (CH 2 CH 2O) 15 -H 2mg / m 2 C 8 F 17 _{SO 2 N- (C 3 H 7} ) (CH 2 CH 2O) 4 - (CH 2) 4 SO 3 Na 1mg / m 2

[0194]

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[0195]

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[0196]

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The obtained coated samples were stored for 4 days under the following conditions.

A condition: 23 ° C., 40% RH B condition: 55 ° C., 80% RH The photographic characteristics were evaluated using the sample after storage. First, the sample was sandwiched between two intensifying screens described below, and a tube voltage of 80 kVp, a tube current of 100 mA, and X for 0.05 seconds were passed through an aluminum wedge.
A line was irradiated and exposed.

<Production of high-sensitivity intensifying screen> Phosphor Gd ₂ O ₂ S: Tb (average particle size: 1.8 μm) 200 g Binder Polyurethane-based thermoplastic elastomer (Demolac TPKL-5-2525 <solid content: 40%>) (Sumitomo Bayer Urethane Co., Ltd.)) 20 g of nitrocellulose (nitrification degree: 11.5%) was added to 2 g of methyl ethyl ketone solvent and dispersed with a propeller mixer to obtain a coating solution for forming a phosphor layer having a viscosity of 25 PS (25 ° C.). Prepared (binder / phosphor ratio = 1/22).

Separately, 90 g of soft acrylic resin solids and 50 g of nitrocellulose were separately used as a coating solution for forming an undercoat layer.
Is added to methyl ethyl ketone, dispersed and mixed to obtain a viscosity of 3 to
A 6PS (25 ° C.) dispersion was prepared.

250 μm thickness kneaded with titanium dioxide
Of polyethylene terephthalate (support) is placed horizontally on a glass plate, and the above-mentioned coating solution for forming an undercoat layer is uniformly applied on the support using a doctor blade, and then gradually raised from 25 ° C to 100 ° C. The coating film was dried by drying to form an undercoat layer on the support (thickness of the coating film: 15 μm).

The above-mentioned coating solution for forming a phosphor layer was uniformly coated and dried to a thickness of 240 μm using a doctor blade, and then compressed. Compression was performed using a calender roll at a pressure of 300 kgw / cm ² and a temperature of 80 ° C. After this compression, a transparent protective film having a thickness of 3 μm was formed by the method described in Example 1 of JP-A-6-75097.

The characteristics of the screen obtained were as follows.
60 μm, phosphor filling rate 68%, sharpness (CTF) 48
%Met.

Next, an automatic developing machine (manufactured by Konica Corporation. SR)
X-701) and processed with a developing solution and a fixing solution having the following formulations.

A tablet for development was prepared according to the following procedures (A, B). Procedure (A) 6000 g of sodium erythorbate as a developing agent was ground in a commercially available bantam mill until the average particle size became 10 μm. 800 g of sodium sulfite, 900 g of sodium metabisulfite, 400 g of phenidone, DTP
A 200 g, N-acetyl-D, L-penicillamine 10
g, Binder D-Sorbit 500 g, 3 in a mill
After mixing for 0 minutes and granulating by adding 30 ml of water at room temperature for about 10 minutes in a commercially available stirring granulator, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier. Thus, the water content of the granulated product was almost completely removed to obtain a granulated product (A).

Solid Developer (A) The granulated product (A) thus obtained was mixed with 140 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less using a mixer. After mixing uniformly for 10 minutes, the obtained mixture was compressed and tableted to a filling amount of 10 g per tablet with a launching machine that was modified from Tough Press Collect 1526HU manufactured by Kikusui Seisakusho Co., Ltd. to obtain a diameter of 30 m.
The solid developer (A) was prepared so as to have a cylindrical shape of m.

Operation (B) 3000 g of potassium carbonate and 1000 g of sodium carbonate are mixed and pulverized in the same manner as in operation A. 7 g of potassium iodide, 40 g of sodium 1- (3-sulfophenyl) -5-mercaptotetrazole and 5-mercapto-
8 g of sodium (1H) -tetrazolylacetate, binder D
-Add 600 g of sorbit and 1500 g of mannit,
The mixture was mixed in a mill for 30 minutes, and granulated in a commercially available stirring granulator at room temperature for 10 minutes with an addition amount of water of 30.0 ml. Thereafter, the granules were dried at 40 ° C. for 2 hours to almost completely remove the moisture of the granules to obtain granules (B).

Solid developer (B) The granulated product (B) was treated with sodium 1-octanesulfonate 15
After mixing uniformly for 10 minutes using a mixer in a room conditioned at 0 ° C. and 25 ° C., 40% RH or less, the obtained mixture is Tuff Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
Was subjected to compression tableting using a modified tableting machine with a filling amount per tablet of 10 g to produce a solid developer (B) as an alkali-developed tablet.

Next, a fixing tablet was prepared by the following operations (C, D).

Operation (C) Ammonium thiosulfate / sodium thiosulfate (90/1
15000 g in a commercially available bantam mill to an average of 10 μm. 500 g of sodium sulfite, 750 g of sodium bisulfite, 500 g of the compound represented by the following chemical formula (M1), and 1300 g of binder pine flow were added to the fine powder, the amount of water added was adjusted to 50 ml, and stirring granulation was carried out. Drying was performed at 40 ° C. with a layer dryer to remove water almost completely to obtain a granulated product (C).

Formula (M1) HO— (CH ₂ ) ₂ —S— (C
H ₂ ) ₂ —S— (CH ₂ ) ₂ —OH Operation (D) 400 g of boric acid, aluminum sulfate octahydrate 1500
g, 1200 g of succinic acid and 300 g of tartaric acid as in operation A. This fine powder is used as the binding agent Mannit 300
g, D-Sorbit 120 g, PEG # 4000 10
0 g was added, the amount of water added was 30 ml, and the mixture was stirred and granulated.
Thereafter, the granules were dried at 40 ° C. for 2 hours to almost completely remove the water content of the granules to obtain granules (D).

Solid fixing agent 2800 g of sodium acetate was added to the obtained granulated product (C).
300 g of octanesulfonic acid was added, while 1500 g of sodium acetate and 60 g of 1-octanesulfonic acid were added to the granules (D) at 25 ° C. and 40% RH, respectively.
The resulting mixture was uniformly mixed for 10 minutes using a mixer in a humidified room, and the resulting mixture was compressed and compressed at a rate of 10 g per tablet using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. To prepare solid fixing agents (C) and (D).

The obtained solid developers (A) and (B) and the solid fixing agents (C) and (D) are 100 l each, and 4.5 l of these are taken out and the solid developer (A) is removed. And (B) and the solid fixing agents (C) and (D) were mixed and sealed in pillow bags containing aluminum for moisture prevention.

[0214] Both the developing and fixing versions of the SRX-701 were remodeled, and the opened solid packaging bags were set at the inlets of the respective solid preparations. The tablets were dropped into the built-in chemical mixer, and simultaneously hot water (25-30 ° C) was added. Water is added, and the mixture is adjusted to 4.5 l with a dissolution time of 20 minutes while stirring and dissolving. The built-in chemical mixer is divided into a liquid preparation tank and a preparatory tank tank. The preparatory tank and the liquid preparation tank are 4.5 liters in volume, and a preparatory tank is provided so as not to be replenished during the tablet dissolution preparation.

The pH of the solution in which the developer is dissolved is acetic acid, KOH
Adjust to pH 10.30 with. The pH of the fixer is adjusted to 4.60. This was used as a replenisher for the developer and the fixer.

The replenisher is supplied to a developing tank and a fixing tank of an automatic developing machine to be filled. The following starter was added thereto to obtain a starting solution. The pH of the starting solution was adjusted to 9.95. The starter addition amount was 70 ml / l.

Starter formulation KBr 4.5 g HO- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -OH 0.05 g N-acetyl-D, L-penicillamine 0.10 g acetic acid (90%) 7.5 g Diethylene glycol 40 g Water was added to make 1 liter.

The photosensitive material prepared above was exposed to light so that the optical density after the development processing was 1.0, and running was performed. For the running, an automatic developing machine SRX-701 equipped with a charging member for a solid processing agent and modified so as to be able to process at a processing speed of 15 seconds was used.

During the running, the photosensitive material was 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 0.
2 pieces of the above-mentioned C agent, 1 piece of the D agent and 7 pieces of water per 62 m ^2.
4 ml was added. The rate of addition of water to each processing agent was started almost simultaneously with the addition of the processing agent, and was added at a constant speed for 10 minutes in approximately proportion to the dissolution rate of the processing agent.

Processing Conditions Development 39 ° C. 5.0 seconds Fixing 36 ° C. 3.5 seconds Washing 35 ° C. 2.5 seconds Squeeze 1.5 seconds Drying 50 ° C. 2.5 seconds Total 15 seconds Measurement of photographic performance for each sample Was done. Sample No. The result of No. 1 was shown as a relative value with reference (100).

Regarding the evaluation of the residual color, the spectral absorption density at 500 nm of the sample after the development was measured with a spectrophotometer. Table 2 shows the results.

[0222]

[Table 2]

As is clear from Table 2, the sample of the present invention has low fog, high sensitivity, high Dmax, excellent residual color and preservability, and 15% when a solid processing agent is used. It can be seen that the sensitivity is hardly impaired even in rapid processing such as seconds and low replenishment processing, and there is no problem at all.

[0224]

According to the present invention, the sensitivity is high, the preservability and the residual color are excellent, and when a solid processing agent is used, the sensitivity is hardly impaired even in rapid processing such as 15 seconds, and there is no problem at all.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a silver halide emulsion manufacturing apparatus applicable to the manufacturing equipment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reaction container 2 Stirring mechanism 3 Dispersion medium 4 Silver addition line 5 Halide addition line 6 Dispersion medium addition line 7 Addition line 8 Liquid take-out line 9 Liquid return line 10 Permeate discharge line 11 Permeate return line 12 Ultrafiltration unit 13 Circulation Pump 14 Flow meter 15, 16, 17 Pressure gauge 18 Pressure adjusting valve 19 Flow adjusting valve 20 Silver addition valve 21 Halide addition valve 22 Liquid extraction valve 23, 24, 25 Valve 26 Ultrafiltration permeate 27 Permeate receiver 28 scales

Claims (7)

[Claims] In a silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on a support, silver halide grains contained in at least one of the silver halide emulsion layers are subjected to ultrafiltration. Produced by performing particle growth while appropriately extracting an aqueous solution containing a salt from the reaction solution,
And silver halide grains chemically sensitized with at least one compound represented by the following general formula (1). General formula (1) R ₁₁ -R ₁₂ -Au ^(I) -R ₁₃ -R ₁₄ [wherein R ₁₂ and R ₁₃ are -SO ₂ S-,-(S) _m -,-
(Se) _m -,-(Te) _m- , where m is 1 to 6. R ₁₂ and R ₁₃ may be the same or different. R ₁₁ and R ₁₄ represent a substituted or unsubstituted aliphatic hydrocarbon, aromatic hydrocarbon or heterocycle, and may be the same or different. ] 2. A silver halide photographic material having a photosensitive silver halide emulsion layer on a support, wherein silver halide grains contained in at least one of the silver halide emulsion layers are subjected to ultrafiltration by an ultrafiltration method. At least one compound represented by the following general formula (2) is produced by performing grain growth while appropriately extracting an aqueous solution containing a salt from the reactant solution, and adding at least one compound represented by the following general formula (2) to at least one layer of the silver halide photographic light-sensitive material. A silver halide photographic light-sensitive material characterized by containing: Embedded image [Wherein, R ₁ and R ₃ each represent a substituted or unsubstituted lower alkyl group or alkenyl group, R ₂ and R ₄ represent an alkyl group, and at least one of R ₂ and R ₄ is a hydrophilic group. Represents an alkyl group substituted with Z ₁ , Z ₂ , Z ₃ and Z ₄ may be the same or different, and represent a hydrogen atom or a substituent. X ₁ represents an ion necessary for neutralizing an intramolecular charge, and n represents 1 or 2. However, when an inner salt is formed, n is 1. ] 3. A silver halide photographic material having a photosensitive silver halide emulsion layer on a support, wherein silver halide grains contained in at least one of the silver halide emulsion layers are subjected to ultrafiltration by an ultrafiltration method. It is manufactured by performing particle growth while appropriately extracting an aqueous solution containing a salt from the reaction product solution, and at least one of the compounds represented by the above general formula (2).
A silver halide photographic material characterized by being chemically sensitized with at least one of the compounds represented by the general formula (1) in the presence of a seed. 4. A silver halide photographic material having a light-sensitive silver halide emulsion layer on a support, wherein silver halide grains contained in at least one of the silver halide emulsion layers are subjected to ultrafiltration by an ultrafiltration method. It is manufactured by performing particle growth while appropriately extracting an aqueous solution containing a salt from the reaction product solution, and at least one of the compounds represented by the following general formula (3).
A silver halide photographic light-sensitive material comprising a seed. Embedded image [Wherein X is, -SO ₃ M, has the at least one directly or indirectly selected from -COOM and -OM, and represents a form capable atomic group of a heterocyclic ring, M is a hydrogen atom, a metal atom or Represents a quaternary ammonium group or a phosphonium group. However, compounds partially including the following structures are excluded. Embedded image Here, R represents a hydrogen atom or a substituent. ] 5. A silver halide photographic material having a photosensitive silver halide emulsion layer on a support, wherein silver halide grains contained in at least one of the silver halide emulsion layers are subjected to ultrafiltration by an ultrafiltration method. It is produced by performing particle growth while appropriately extracting an aqueous solution containing a salt from the reaction product solution, and at least one of the compounds represented by the following general formula (4).
A silver halide photographic light-sensitive material comprising a seed. Embedded image [Wherein (A ₁ ) is -SO ₃ M ₁ , -COOM ₁ or -O
Represents M _1, M ₁ represents a hydrogen atom, a metal atom or a quaternary ammonium group or phosphonium group, m is an integer of from 1 to 10. (A ₂ ) represents an electron-withdrawing group, and n is 1 to 10
Is an integer. (A ₃ ) represents a functional group containing a sulfur atom, a selenium atom or a tellurium atom capable of binding to a silver ion;
Represents 1 or 2. Y represents an aliphatic hydrocarbon, an aromatic hydrocarbon or a heterocyclic ring. ] 6. A silver halide photographic material having a photosensitive silver halide emulsion layer on a support, wherein silver halide grains contained in at least one of the silver halide emulsion layers are subjected to ultrafiltration by ultrafiltration. It is produced by performing particle growth while appropriately extracting an aqueous solution containing a salt from the reaction product solution, and at least one of the compounds represented by the following general formula (5).
A silver halide photographic light-sensitive material comprising a seed. Embedded image [In the formula, (A ₁ ), (A ₂ ), (A ₃ ), m, n and r each represent a group having the same meaning as in the above general formula (4).
(A ₁₎ 'represents a -SO ₃ M _1, -COOM ₁ or -OM _1, M ₁ represents M ₁ group having the same meaning as in the general formula (4).
(A ₂ ) ′ represents an electron-withdrawing group, and (A ₃ ) ′ represents a functional group containing a sulfur atom, a selenium atom or a tellurium atom capable of binding to a silver ion. (A ₁ ) and (A ₁ ) ′, (A ₂ ) and (A ₂ ) ′, and (A ₃ ) and (A ₃ ) ′ may be the same or different. Y ₁ and Y ₂ are aliphatic hydrocarbons,
Represents an aromatic hydrocarbon or a heterocyclic ring, which may be the same or different. Z represents a sulfur atom, a selenium atom or a tellurium atom, and p is 1 or 2. m ′ and n ′ each independently represent an integer of 1 to 10, but m + m ′ and n + n ′
Is 1 or more. ] 7. A halogen produced by subjecting the silver halide grains according to claim 1 to grain growth by ultrafiltration while appropriately extracting an aqueous solution containing a salt from a reaction solution. The subsurface or the surface of silver halide grains contains at least one compound represented by the above general formula (3), (4) or (5).
6. The silver halide photographic light-sensitive material according to claim 1.