JPH11133535A - Silver halide emulsion, silver halide photographic sensitive material and treatment of this sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic emulsion high in sensitivity and low in fog and high in the gamma value by adding fine silver halide grains subjected to reduction sensitization in the insides and/or the surfaces during and/or after formation of silver halide grains. SOLUTION: The fine silver halide grains subjected to reduction sensitization in their insides and/or their surfaces are added during and/or after formation of the silver halide grains of the emulsion at the time of preparation of the photographic emulsion. The silver halide emulsion is sensitized by using a selenium compound or a tellurium compound. The fine silver halide grains can be obtained, for example, by subjecting them to reduction sensitization with a reduction sensitizing agent, such as, stannous salts, amines or polyamines, while adding water-soluble silver salts and water-soluble alkali halides to form silver halide grains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion, a silver halide photographic light-sensitive material, and a method for developing a silver halide photographic light-sensitive material having high sensitivity and low fog generation.

[0002]

BACKGROUND OF THE INVENTION An image is formed on a silver halide photographic material by exposure and development.

In recent years, there has been a demand from customers for obtaining photographing results quickly, and it has been demanded to reduce the development processing time of silver halide photographic materials. Further, from the viewpoint of preventing the occurrence of pollution, there is an increasing demand for a reduction in the treatment waste liquid.

[0004] For example, in the medical field, regular medical examinations, health check-ups, and the like have become widespread, and diagnoses and tests have also increased in general medical care. X-ray photography is used for these diagnostic tests, and the number of X-ray photography is rapidly increasing. In order to process this large amount of X-rays and to promptly inform doctors and patients of the results, it is necessary to reduce the time required for the development processing. Since the treated waste liquid causes environmental pollution, it has been demanded to reduce the generation of the treated waste liquid.

In order to rapidly process a silver halide photographic material, it is necessary to reduce the time required for processing the photographic material such as development, fixing, washing and drying. However, if the development time is shortened, the image density and sensitivity are significantly reduced, and the gradation is deteriorated. In addition, if the fixing time is shortened, a fixing failure occurs, silver halide remains, and the image quality is deteriorated. Therefore, in order to speed up the processing, the silver halide photographic material itself is improved, the developing speed, the fixing speed, the drying speed, etc. are increased, and even if rapid processing is performed, the image density, sensitivity, gradation, It is necessary to prevent deterioration of image quality and the like.

Conventionally, to increase the developing speed and the fixing speed,
Use silver halide emulsions with a low solubility of silver iodide with low solubility, use silver chlorobromide, silver chloride emulsions with high solubility, make silver halide grains finer, It is considered advantageous to use silver halide grains. However, when the silver iodide content of the silver halide emulsion is reduced, silver chlorobromide or silver chloride is used, or when the silver halide grains are made finer, the sensitivity is reduced.

In order to enhance sensitivity and development progress, a technique of incorporating a silver halide solvent (for example, a thiocyanate compound) into silver halide grains or a photosensitive material is disclosed in, for example, US Pat. No. 2,222,264. Description, U.S. Pat.
320,069 and JP-A-62-18538. However, when these silver halide solvents are used, the storage stability of the silver halide photographic material over time deteriorates.

In order to increase the sensitivity, sensitization techniques such as reduction sensitization, selenium sensitization, and tellurium sensitization, and chemical ripening have been energetically studied. As a result, fog has risen and further study is required.

Regarding reduction sensitization, Carroll in US Pat. No. 2,487,850 discloses the use of tin compounds, and Lowe et al. In US Pat. No. 2,51.
In U.S. Pat. No. 2,925, the use of polyamine compounds is described by Fallens et al. In GB 789,82.
No. 3 proposes to use thiourea dioxide-based compounds and discloses that each is useful as a reduction sensitizer. Also, Collier said, "Photogr
aphic Science and Engineer
ring, Vol. 23, page 113 (1979), dimethylaminoborane, stannous chloride, hydrazine,
The properties of silver nuclei produced by various reduction sensitization methods using high pH ripening, low pAg ripening and the like are compared. Regarding the technique of the reduction sensitization method, see US Pat. No. 2,518,
No. 698, U.S. Pat. No. 3,201,254, U.S. Pat. No. 3,411,917, U.S. Pat. No. 3,779,777, U.S. Pat.
It is also disclosed in Japanese Patent Application No. 0,867.

Regarding reduction sensitization, not only selection of a reduction sensitizer but also a technique of how to use a reducing agent has been proposed. For example, Japanese Patent Publication No. 57-33572 and Japanese Patent Publication No. No. 1410, JP-A-57-179
No. 835 discloses a technique relating to a method of using a reducing agent.

A technique for improving the storage stability of a reduction-sensitized silver halide emulsion is disclosed in, for example, JP-A-57-8283.
No. 1, JP-A-60-178445.

The mechanism of reduction sensitization is described in James, "The Photographic Process", 4th Edition, Macmillan, 1977, <T. H. Jaimes,
The Theory of the Photogra
phy Process, 4thed, Macmi
llan, 1977), p. 152, the silver nucleus formed by the two atoms generated by reduction sensitization captures holes, thereby decomposing into silver ions and unstable silver atoms, and further thermally. It is stated that unstable silver atoms break down into silver ions and conductor electrons, which contribute to latent image formation. According to this mechanism, it is possible to increase the sensitivity up to twice.

The reduction sensitization technique is disclosed in Japanese Patent Application Laid-Open No. 2-19 / 1990.
1938 and JP-A-3-168632, etc., when reduction sensitization is performed on silver halide grains by these methods, fog is produced even when an oxidizing agent such as thiosulfonic acid is used in combination. High and the effect was not enough.

As described above, the conventional technique has a problem that fog increases with an increase in sensitivity.

Accordingly, there has been a strong demand for a reduction sensitization technique which provides high sensitivity and low fog.

[0016]

SUMMARY OF THE INVENTION Accordingly, the first aspect of the present invention is as follows.
It is an object of the present invention to provide a silver halide photographic emulsion having high sensitivity, low fog and high gamma.

A second object of the present invention is to obtain high sensitivity,
An object of the present invention is to provide a silver halide photographic light-sensitive material having low fog and high gamma.

A third object of the present invention is to provide a method for developing a silver halide photographic material in which a development process including a development, fixing and drying process is performed in 30 seconds or less.

[0019]

The objects of the present invention are as follows: (1) During and / or after the formation of silver halide grains, silver halide fine grains whose inside and / or surface are reduction-sensitized are added. A silver halide photographic emulsion prepared as described above, wherein the silver halide photographic emulsion is selenium sensitized and / or tellurium sensitized. (2) 2 × 1 per mole of silver on the surface of silver halide grains
The silver halide photographic emulsion according to the above (1), wherein 0 to ³ mol or more of a thiocyanate compound is present. (3) The silver halide photographic emulsion according to the above (1) or (2), wherein an oxidizing agent for silver nuclei is added during the preparation of the silver halide photographic emulsion. (4) On a support, at least one layer of the above (1)-
A silver halide photographic light-sensitive material comprising a silver halide emulsion layer formed of the silver halide photographic emulsion according to any one of (3) and (2). (5) A silver halide photographic light-sensitive material characterized in that the silver halide photographic light-sensitive material according to the above (4) is subjected to development processing including development, fixing and drying steps in a total processing time of 30 seconds or less. Development processing method. (6) In the method for continuously developing a silver halide photographic material according to the above (4) in a development step including development and fixing steps, at least one of the steps is a solid state. A method for developing a silver halide photographic light-sensitive material, wherein the method is performed using a processing solution prepared using a processing agent. Could be achieved by:

Hereinafter, the present invention will be described in detail.

In the present invention, reduction sensitized silver halide fine grains (hereinafter simply referred to as "silver halide fine grains of the present invention") are used as silver halide grains of a silver halide photographic emulsion (hereinafter referred to as "the present invention"). During the formation of silver halide-based grains), or after and after the formation. The mechanism by which the silver halide fine grains of the present invention are added during and / or after the formation of the silver halide base grains of the present invention to provide a sensitizing effect is not clear. It is presumed that the reduction sensitization nuclei of the fine grains were introduced into the silver halide base grains of the present invention. Further, by using the silver halide fine particles of the present invention,
It is easy to control the reduction sensitization nuclei in the silver halide base grains of the present invention, and the low unreacted reduction sensitizer sufficiently brings out the performance of high sensitivity and low fog. It seems that you can do it.

First, the silver halide fine particles of the present invention will be described.

The silver halide fine grains of the present invention can be prepared by a known method. For example, it may be prepared by any method such as an acidic method, a neutral method, and an ammonia method.

The soluble silver salt and the soluble halide are
The reaction may be performed using any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. As one type of the double jet method, there is a method in which the pAg in a liquid phase in which silver halide is formed is kept constant, that is, a control double jet method, and a soluble silver salt and a soluble halide are used by using this method. The reaction is preferable because a silver halide emulsion having a narrow grain size distribution can be obtained.

The halogen composition of the silver halide fine grains may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide and silver chloroiodobromide. The halogen composition of the silver halide fine grains may be the same as or different from the halogen composition of the silver halide base grains.

The silver halide fine particles of the present invention are cubic,
It may have a regular crystal form such as an octahedron or a tetrahedron, or may have a crystal form such as a sphere or a plate. Further, the particles may have different halogen compositions between the inside and the surface of the particles, or may have a uniform halogen composition.

The particle size of the silver halide fine particles of the present invention is as follows:
0.01 to 0.1 μm is preferable, and 0.01 to 0.07
μm is more preferred.

In the silver halide fine grains of the present invention,
Reduction sensitization may be applied to any part of the silver halide fine grains. That is, reduction sensitization may be performed on the surface of the particles, may be performed on the inside of the particles, or may be performed on both the surface of the particles and the inside of the particles.

The silver halide fine particles of the present invention include, for example,
It can be obtained by performing reduction sensitization during physical ripening of silver halide fine grains, and performing reduction sensitization during formation of silver halide fine grains by adding a water-soluble silver salt and a water-soluble alkali halide. . When reduction sensitization is performed during the formation of silver halide fine grains by adding a water-soluble silver salt and a water-soluble alkali halide, reduction sensitization may be performed by temporarily suspending the addition during the reduction sensitization. .

After completion of the formation of silver halide fine grains, reduction sensitization may be performed to form reduction sensitized silver nuclei on the surface.

The reduction sensitization may be carried out by any method. For example, a method of adding a reduction sensitizer to carry out reduction sensitization, a method called silver ripening, and a method of halogenating under a low pAg atmosphere of pAg1 to pAg7 to p7. A method of performing reduction sensitization by growing or ripening silver grains, or a method of performing reduction sensitization by growing or ripening silver halide grains in a high pH atmosphere of pH 7 to 11, which is called high pH ripening, can be used. . Also,
Two or more reduction sensitization methods can be used in combination.

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

Examples of the reduction sensitizer used here include stannous salts, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. In the present invention, these known reduction sensitizers can be selected and used for reduction sensitization, and two or more reduction sensitizers can be used in combination.

The amount of the reduction sensitizer to be added cannot be specified because it depends on the production conditions of the silver halide fine grains, but is generally 1 × 10 ⁻⁷ mol or more and 1 × 10 ⁻⁷ mol per mol of silver halide. The range of 10 ^-2 mol or less is suitable, and the range is more preferably 1 × 10 ⁻⁶ mol or more and 1 × 10 ⁻³ mol or less.

The reduction sensitizer can be used by dissolving or dispersing it in water or a solvent such as alcohols, glycols, ketones, esters and amides.

The reduction sensitizer may be added to the reaction vessel in advance, but is preferably added at an appropriate time during grain growth. Alternatively, a reduction sensitizer may be added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance, and silver halide fine particles may be formed using these aqueous solutions. In addition, a method of adding the solution of the reduction sensitizer in several portions during the formation of the silver halide fine particles and a method of continuously adding the solution over a long period of time are also preferable.

The silver halide fine grains of the present invention are desalted,
A newly prepared protective colloid dispersion is preferable because unreacted reduction sensitizer used for reduction sensitization can be removed.

As a desalting method, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method can be used. Examples of the coagulation sedimentation method include a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like. The temperature of desalting is selected depending on the purpose, but is generally 5 ° C to 5 ° C.
It is preferable to select within the range of 0 ° C. The pH at the time of desalting is selected according to the purpose, but generally, it is preferably selected in the range of 2 to 10. A more preferred pH range is 3 to
8 The pAg at the time of desalting is also selected depending on the purpose, but is generally preferably selected in the range of 5 to 10.

The silver halide photographic emulsion of the present invention can be prepared by adding the silver halide fine grains of the present invention during and / or after the formation of the silver halide base grains of the present invention. By the above preparation, the silver halide fine grains of the present invention are deposited on the silver halide base grains of the present invention.

The deposition of the silver halide fine grains of the present invention on the silver halide base grains of the present invention is not merely aggregation,
Once the silver halide fine particles of the present invention are dissolved, the temperature, p
By controlling the particle growth environment such as H
It is considered that silver halide is regenerated from the dissolved silver halide fine grains of the present invention, and reduction-sensitized silver nuclei are incorporated into the entire surface of the silver halide base grains of the present invention or localized sites such as sides and vertices. Have been.

The temperature, pH and time for dissolving and depositing the silver halide fine grains of the present invention can be freely selected. When dissolving and depositing the silver halide fine grains of the present invention during physical ripening, physical ripening is performed. Temperature should be above 30 ℃ and 80 ℃
The temperature is preferably at most 40 ° C and at most 70 ° C. Further, the pH is preferably 2 or more and 10 or less, more preferably 3 or more and 7 or less.

The silver halide fine grains of the present invention can be deposited on the silver halide base grains of the present invention during or after the formation of the silver halide base grains of the present invention. Both during and after formation may be performed.

When the silver halide fine grains of the present invention are added during the formation of the silver halide base grains of the present invention, they may be added immediately after the nuclei of the silver halide grains are generated. It may be added during the process.

When the silver halide fine grains of the present invention are added after the silver halide grains are formed, they may be added immediately before starting the desalting step, before starting physical ripening, during physical ripening or after ending physical ripening. It may be added later, before the start of chemical ripening, during chemical ripening, or after the completion of chemical ripening. Further, it may be added before or after the addition of the spectral sensitizing dye.

The silver halide fine grains of the present invention are preferably added in an amount of 1 × 10 ⁻⁷ mol to 5 × 10 ⁻¹ mol per mol of silver of the silver halide base grains of the present invention,
More preferably, silver is added in an amount of 1 × 10 ^-6 mol or more and 1 × 10 ^-1 mol or less.

Such a reduction-sensitized silver halide emulsion is
This is a completely new emulsion that has not been known until now.

Next, the silver halide base grains of the present invention will be described.

The silver halide constituting the silver halide base grains of the present invention includes silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver iodochloride, and silver chloroiodobromide. Can be used, and silver bromide and silver iodobromide are more preferable.

Preferred silver halide grains are 90 mol%
The above are silver halide grains which are silver bromide. Further, it is more preferable to contain 95 mol% or more of silver bromide.
It is particularly preferable to contain 9 mol% or more. When the silver halide grains are composed of silver iodobromide, silver iodide is
The average silver iodide content of all silver halide grains is 0.01
It is preferably contained in an amount of from 0.01 to 1.0 mol%, more preferably from 0.01 to 0.5 mol%.

The silver iodide content and the average silver iodide content of each silver halide grain were determined by the EPMA method (Electron Probe Mic).
ro analyzer method). According to the EPMA method, it is possible to perform elemental analysis on a very small portion. In the EPMA method, a sample in which silver halide grains are dispersed so as not to be in contact with each other is prepared, irradiated with an electron beam, and the characteristic X-ray intensity of silver and iodine emitted from each grain by electron beam excitation is determined. Can determine the silver halide composition of the grains. If the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content can be determined from the average thereof.

The shape of the silver halide base grains of the present invention may be any, for example, cubic, octahedral, tetradecahedral, spherical, tabular, potato-like, etc., but is particularly preferred. Are tabular grains.

Hereinafter, the silver halide base grains of the present invention will be described with reference to tabular silver halide grains which are typical silver halide grains preferably used in the present invention.

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

The tabular silver halide grains preferably contain silver iodide.

Tabular silver halide grains having silver iodide present therein are preferred tabular silver halide grains. In this case, the silver halide composition inside the grains is preferably a silver halide composition containing silver iodide of 0.1 mol% or more and 3 mol% or less.

The silver halide composition inside the tabular silver halide grains can be determined by cutting the grains into ultrathin sections, observing them with a transmission electron microscope while cooling, and performing analysis. Specifically, silver halide grains are taken out of the emulsion, embedded in a resin, and cut with a diamond knife to produce an ultrathin section having a thickness of 60 nm. Observation and point analysis are performed with a transmission electron microscope equipped with an energy dispersive X-ray analyzer while cooling the ultrathin section with liquid nitrogen, and the quantity is determined by quantitative calculation. (See Inoue and Nagasawa: Abstracts of Annual Meeting of the Photographic Society of Japan, 1987, p. 62) Tabular silver halide grains having silver iodide on the outermost surface of the silver halide grains are also preferred. In this case, the silver halide composition on the outermost surface preferably has a silver iodide content of 0.1 mol% or more and 5 mol% or less.

The silver iodide content on the outermost surface of the tabular silver halide grains as referred to herein means an XPS method (X-ray Photoelectron).
n Spectroscopy: X-ray photoelectron spectroscopy) means the silver iodide content of a portion up to a depth of 50 °,
Specifically, 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 Mg was used as a probe X-ray.
Kα rays are generated and irradiated at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA, and Ag3d52, Br3d, 13d
It measures about 32 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 the intensity ratio.

When the sample is cooled, the sample is destroyed when irradiated with X-rays [decomposition of silver halide and halide (particularly iodine)].
Of -110 ° C.
If cooled down, the destruction of the sample can be suppressed to a level that does not hinder the measurement, and the measurement accuracy can be increased.

The average aspect ratio of the tabular silver halide grains is preferably 2 or more and 10 or less, more preferably 7 or less, and most preferably 5 or less.

In the present invention, the tabular silver halide grains preferably account for 50% or more, more preferably 70% or more, of the total projected area of the silver halide grains in the silver halide photographic emulsion. In the present invention, a particularly preferred silver halide photographic emulsion is one in which 90% or more of the total projected area of the silver halide grains is composed of tabular silver halide grains having a (111) plane as a main plane. Main plane is (111)
The plane can be confirmed by an X-ray diffraction method or the like.

The average particle diameter of the tabular silver halide grains is preferably from 0.15 to 5.0 μm, more preferably from 0.4 to 5.0 μm.
More preferably, it is 3.0 μm, most preferably 0.4 to 2.0 μm. The average thickness of the tabular silver halide grains is preferably from 0.01 to 1.0 μm, more preferably from 0.02 to 0.40 μm, and still more preferably from 0.02 to 0.30 μm. is there.

The particle size and thickness can be optimized to optimize sensitivity and other photographic properties. Optimal particle size,
The optimum thickness depends on the sensitivity and other factors constituting the photosensitive material that affect the photographic properties (thickness of the hydrophilic colloid layer, hardness, chemical ripening conditions, sensitivity setting of the photosensitive material, silver coating amount, etc.). different.

The tabular silver halide grains are preferably monodisperse grains having a narrow particle size distribution. Specifically, the width of particle size distribution (%) = (standard deviation of particle size / average particle size)
When the width of the particle size distribution is defined by × 100, the width of the particle size distribution is 20% or less, preferably 18% or less, more preferably 15% or less.

The tabular silver halide grains preferably have a narrow thickness distribution. Specifically, width of thickness distribution (%) = (standard deviation average thickness of thickness) x
When the width of the distribution is defined by 100, the width of the thickness distribution is preferably 25% or less, more preferably 20% or less.
The content is particularly preferably 15% or less.

The tabular silver halide grains may have dislocations. For example, dislocations. JFHamilton, Phot.Sci.En
g, 57 (1967) and T.M. Shiozawa, J.Soc.Phot.Sci.Ja
Pan, 35, 213 (1972), which can be observed by a direct method using a transmission electron microscope at a low temperature. Specifically, silver halide grains taken out so as not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope to prevent damage (printout, etc.) by electron beams. The observation can be performed by observing the sample in a cooled state by a transmission method. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a sharper observation can be obtained by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). it can.

In the present invention, it is preferable to use an oxidizing agent for silver during the emulsion production process. The oxidizing agent for silver refers to a compound having an action of converting metallic silver into silver ions. In particular, a compound which converts very fine silver particles by-produced in the process of forming silver halide grains and in the course of chemical sensitization into silver ions is effective. The silver ions generated here may form a water-insoluble silver salt such as silver halide, silver sulfide or silver selenide, or a silver salt easily soluble in water such as silver nitrate. A salt may be formed. The oxidizing agent for silver may be inorganic or organic.

As the inorganic oxidizing agent, for example, ozone,
Hydrogen peroxide and its adducts (eg, Na BO_Two・ H_Two
O_Two・ 3H_TwoO, 2NaCO_Three・ 3H_TwoO_Two, Na_FourP_TwoO₇・
2H_TwoO_Two, 2Na_TwoSO_Four・ H_TwoO_Two・ 2H_TwoOH), perl
Oxy acid salts (eg, K_TwoS_TwoO₈, K_TwoC_TwoO₆, K_TwoP_TwoO
₈), Peroxy complex compounds (eg, K_Two[Ti
(O_Two) C_TwoO_Four] ・ 3H_TwoO, 4K_TwoSO_Four・ Ti (O_Two)
OH / SO_Four・ 2H_TwoO, Na_Three[VO (O_Two) (C_TwoH_Four)
_Two-6H_TwoO), permanganate (eg, KMn
O_Four), Chromates (eg, K_TwoCr_TwoO₇) Such as oxygen
Acid salts, halogen elements such as iodine and bromine, perhalates
(Eg, potassium periodate), high valent metal salts
(Eg potassium hexacyanoferrate) and thio
There are sulfonates.

As the organic oxidizing agent, for example, p
Quinones such as quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-promsuccinimide, chloramine T, chloramine B).

The preferred oxidizing agents of the present invention are inorganic oxidizing agents such as ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates and organic oxidizing agents such as quinones. Particularly preferred oxidizing agents are thiosulfonates and polysulfide compounds, preferably compounds represented by the following general formulas (1) to (4), and at least one compound represented by the general formulas (1) to (4) A method in which the outermost layer is coated in a state where it is present is preferable. When a gold sensitizer is used, the compounds represented by the general formulas (1) to (4) are preferably added before adding the gold sensitizer.

General formula (1) R-SO ₂ SM General formula (2) R ¹ -SO ₂ SR ² General formula (3) R ³ -SO ₂ SL _m -SSO ₂ -R ⁴ General Formula (4) R ^5- (S) _n -R ^{6 In the} above general formulas (1) to (4), R, R ¹ , R ² , R
³ , R ⁴ , R ⁵ and R ⁶ each represent a substituted or unsubstituted aliphatic group, aromatic group or heteroheterocyclic group. Also,
R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be a divalent group forming a substituted or unsubstituted ring by bonding to each other.
n represents an integer of 2 or more and 6 or less. M represents a cation.
L represents a divalent linking group, and m represents 0 or 1. R,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different.

Specific examples of the compounds represented by formulas (1) to (4) are shown below. The compounds represented by formulas (1) to (4) which can be used in the present invention are as follows. It is not limited to these.

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[0075]

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[0076]

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[0078]

Embedded image It is a preferred embodiment to use an oxidizing agent for silver in combination with the silver halide fine particles of the present invention. A method of performing reduction sensitization with silver halide fine particles of the present invention after using an oxidizing agent for silver, a method of using an oxidizing agent for silver after performing reduction sensitization with silver halide fine particles of the present invention,
Both can be selected and used from methods of coexisting at the same time. These methods can be used in both the grain formation step and the chemical sensitization step.

A silver halide solvent can be used in the silver halide photographic emulsion of the present invention.

Examples of the silver halide solvent used include those described in US Pat. No. 3,271,157 and US Pat.
No. 531,289, U.S. Pat. No. 3,574,62.
No. 8, JP-A-54-1019, JP-A-54-1019
Organic thioethers described in JP-A-158917, JP-A-53-82408, JP-A-55-77
No. 737, JP-A-55-2982 and the like, and a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. A silver halide solvent, imidazoles described in JP-A-54-100717,
Sulfite, thiocyanate, JP-A-57-196228
And the like.

Particularly preferred silver halide solvents include thiocyanate and tetramethylthiourea. Thiocyanates include metal thiocyanate and N
Water-soluble salts such as H ₄ SCN can generally be used. When using a metal salt, care should be taken to use a metal element that does not adversely affect photographic performance.
And NaSCN are preferred. Further, a sparingly soluble salt such as AgSCN may be added in the form of fine particles.

The silver halide solvent may be added at any stage during the preparation of the emulsion, but is preferably added both before the desalting step and during chemical sensitization.

The addition amount of the silver halide solvent varies depending on the kind. For example, in the case of thiocyanate, the total addition amount from the time of grain formation to the end of chemical sensitization is 2 × 10 ⁻³ mol per mol of silver halide. It is preferably at least 5 × 10 ^-2 mol.

When tabular silver halide grains are formed in the presence of a silver halide solvent, the silver iodide content is preferably at most 1.0 mol%, more preferably at most 0.5 mol%. It is particularly preferably 0.4 mol% or less. It is also preferred that 0.4 mol% or less is formed before the desalting step, and further 0.6 mol% or less is formed during chemical ripening.

As the protective colloid used for preparing the silver halide photographic emulsion of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Various kinds of synthetic hydrophilic polymer substances such as a homopolymer or a copolymer such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used. As gelatin, besides lime-processed gelatin, acid-processed gelatin and Bul
l. Soc. Sci. Photo. Japan. No.
16. Enzyme-treated gelatin as described in p30 (1996) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used.

The protective colloid described above can be used as a binder for other hydrophilic colloid layers of a silver halide photographic light-sensitive material.

The silver halide photographic emulsion of the present invention is preferably desalted and dispersed in a newly prepared protective colloid. The temperature of desalting can be selected according to the purpose.
It is preferable to select within the range of 0 ° C. The pH at the time of desalting can be selected according to the purpose, but is preferably selected from 2 to 10.
More preferably, it is in the range of 3 to 8. PAg for desalination
Can be selected according to the purpose, but is preferably selected from 5 to 10. As a desalting method, it can be used by selecting from a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. The coagulation sedimentation method can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like.

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

The silver halide photographic emulsion of the present invention may be spectrally sensitized with a spectral sensitizing dye.

The spectral sensitizing dye refers to a dye that is adsorbed on silver halide grains and contributes to spectral sensitization. The spectral sensitizing dye used in the present invention is arbitrary as long as it has a spectral sensitizing function.

The spectral sensitizing dye may be added at any time after the formation of the grains. The addition amount of the spectral sensitizing dye is preferably from 1 × 10 ⁻⁷ mol to 1 × 10 ⁻¹ mol per mol of silver,
More preferably, it is 1 × 10 ⁻⁵ mol or more and 1 × 10 ⁻² mol or less. The amount of the spectral sensitizing dye to be added depends on the particle size, but it is preferable to coat at a coverage of 30 to 90% (surface area ratio).

When the silver halide photographic light-sensitive material is a X-ray medical light-sensitive material utilizing a phosphor that emits green light, a spectral sensitizing dye is adsorbed on silver halide emulsion grains, and the reflection spectrum is measured. It is preferable that the J-band is formed in the same wavelength region as the green light from the phosphor. That is, it is preferable to select and combine spectral sensitizing dyes such that a J-band having the maximum absorption in the region of 520 nm to 555 nm is formed. More preferably 530-553 nm, most preferably 54 nm.
0 to 550 nm.

The addition time of the spectral sensitizing dye is during the chemical ripening step, particularly preferably at the start of the chemical ripening. Further, in the silver halide photographic emulsion according to the present invention, by adding the spectral sensitizing dye from the nucleation step to the end of the desalting step, excellent spectral sensitization efficiency can be obtained. Add the same or another type of spectral sensitizing dye that is the same as or different from the spectral sensitizing dye added from the time of the process to the end of the desalting process at any time from the end of the desalting process through the chemical ripening process to immediately before the coating process May be.

The silver halide emulsion of the present invention has been subjected to selenium sensitization using a selenium compound and tellurium sensitization using a tellurium compound. Conditions for selenium sensitization and tellurium sensitization,
For example, as pAg, temperature, time, and the like, conditions used for chemical sensitization generally performed in the art can be employed. A large effect can be obtained by selenium sensitization or tellurium sensitization of the silver halide emulsion.

Various selenium compounds can be used as the selenium sensitizer used in the selenium sensitization method. Regarding selenium sensitization, for example, US Pat.
944, U.S. Pat. No. 1,602,592, U.S. Pat. No. 1,623,499,
0-150046, JP-A-4-25832, JP-A-4-109240, JP-A-4-147
No. 250, etc.

Examples of selenium sensitizers useful in the present invention include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), and selenoureas (eg, 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, selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides ( For example, selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate), selenophosphates (eg, tri-p-triselenophosphate, etc.) ) And selenides (eg, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides and selenium ketones.

In the present invention, it is more effective to add the selenium sensitizer as a dispersion of solid fine particles than to add it as an organic solvent solution.

The tellurium sensitization method and tellurium sensitizer are described in US Pat. No. 1,623,499, US Pat. No. 3,320,069 and US Pat.
2,031, U.S. Pat. No. 3,531,289, U.S. Pat. No. 3,655,394, British Patent 235,211 and British Patent 1,12
1,496, British Patent 1,295,462, British Patent 1,396,696, Canadian Patent 800,958, JP-A-4-2046.
No. 40, JP-A-4-330430, and the like. In the present invention, the tellurium sensitization method and tellurium sensitizer described in the above-mentioned documents can be used.

Examples of tellurium sensitizers useful in the present invention 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) Lido),
Telluroamides (eg, telluroacetamide, N, N
-Dimethyltellurobenzamide), telluro ketones, telluro esters, isotellurocyanates and the like.

The technique for using the tellurium sensitizer is the same as the technique for using the selenium sensitizer.

Examples of the sulfur sensitizer and gold sensitizer include chloroauric acid, gold thiosulfate, and gold thiocyanate.
Examples include gold complexes of thioureas, rhodanines and other various compounds.

The amounts of the sulfur sensitizer and the gold sensitizer used are
Types of silver gemide emulsions, types of compounds used, ripening conditions
Although it is not uniform due to factors such as
1 × 10 per mole^-FourMol ~ 1 x 10^-9Mole
Preferably 1 × 10^-Five Mol ~ 1 x 10^-8In mole
You.

In the silver halide photographic light-sensitive material of the present invention, at least one of a layer containing a light-sensitive silver halide photographic emulsion and a constituent layer other than the light-sensitive silver halide photographic emulsion layer is subjected to development processing. When a dye capable of decoloring and / or flowing out is contained in the photosensitive material, a photosensitive material having high sensitivity, high sharpness, and little dye stain can be obtained. The dye used above is appropriately selected from dyes that can improve sharpness by absorbing a desired wavelength and removing the influence of the wavelength. Further, it is preferable that the dye is decolorized or flows out during the development processing of the silver halide photographic light-sensitive material, and that the color is not confirmed when the image is completed.

The preferred dyes used in the silver halide photographic light-sensitive material of the present invention are substantially insoluble in water at a pH of 7 or less, and substantially soluble in water at a pH of 8 or more.
The amount of addition can be changed according to the target of sharpness.
Generally speaking, the preferred dye loading is 0.2 mg
/ M ^{2 to 20} mg / m ² , more preferably 0.8
a ^{mg / m 2 ~15mg / m 2} .

The dyes used in the present invention are described, for example, in German Patent No. 616,007 and British Patent No. 5
No. 84,609, British Patent 1,177,429
No., JP-B-26-7777, JP-B-39
-22069, JP-B-54-38129,
JP-A-48-85130, JP-A-49-9962
0, JP-A-49-114420,
JP-A-9-129537, JP-A-50-28827, JP-A-52-108115, JP-A-57-1
85038, JP-A-2-282244, JP-A-4-30739, U.S. Pat.
No. 961, U.S. Pat. No. 1,884,035, U.S. Pat. No. 1,912,797, U.S. Pat. No. 2,098,891, U.S. Pat. No. 2,15
No. 0,695, U.S. Pat. No. 2,274,782, U.S. Pat. No. 2,298,731, U.S. Pat. No. 2,409,612, U.S. Pat.
61,484, U.S. Pat. No. 2,527,583
No. 2,533,472, U.S. Pat. No. 2,865,752, U.S. Pat.
No. 956,879, U.S. Pat. No. 3,094,41.
8, U.S. Pat. No. 3,125,448,
U.S. Pat. No. 3,148,187, U.S. Pat. No. 3,177,078, U.S. Pat.
No. 127, U.S. Pat. No. 3,260,601, U.S. Pat. No. 3,282,699, U.S. Pat. No. 3,409,433, U.S. Pat. No. 3,54
No. 0,887, US Pat. No. 3,575,704, US Pat. No. 3,653,905, US Pat. No. 3,718,472, US Pat. No. 3,8
No. 65,817, U.S. Pat. No. 4,070,352.
No. 4,071,312, PB Report 74175, PHOTO.ABS.1, 28 (21) and the like can be used.

The silver halide photographic emulsion according to the present invention includes:
Various photographic additives can be added. These additives are described, for example, in Research Disclosure (R
D) No. 17643 (December 1978), RD No. 1
8716 (November 1979) and RD No.30811
9 (December 1989). The types of compounds and the locations described in these three research disclosures are shown in Table 1 below.

[0107]

[Table 1] Further, the silver halide photographic material of the present invention contains a developing agent, for example, aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in a silver halide emulsion layer or other layers. Is also good.

As a support for the silver halide photographic light-sensitive material according to the present invention, for example, RD No. 17643 described above can be used.
Page 28 and RD No. 308119, page 1009.

As the support, a plastic film is preferably used. The surface of these supports is provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc., in order to improve the adhesion to the coating layer. Is also good. It is preferable that the undercoat layer contains an antistatic improver such as a colloidal tin oxide sol.

When the silver halide photographic light-sensitive material of the present invention is an X-ray medical light-sensitive material utilizing a phosphor emitting green light, a silver halide emulsion layer and a crossover cut layer may be provided on both sides of the support. A photosensitive material having high sensitivity, high sharpness, and excellent processability can be obtained.

In the silver halide photographic light-sensitive material of the present invention, a surface protective layer and other layers can be provided in addition to the silver halide photographic emulsion layer. The amount of gelatin in the silver halide photographic emulsion layer, the surface protective layer, and other layers is preferably in the range of 0.5 to 3.5 g / m ² , particularly 1.5 to 3 g / m ² on one side of the support. A range of 0.0 g / m ² is preferred.

A latex can be added to the silver halide photographic emulsion of the present invention. As these latexes, those having a latex surface that is photographically inactive and having very little interaction with various photographic additives are preferred. For example, it is difficult to adsorb dyes and dyes, it is difficult to adsorb development accelerators and development inhibitors that affect the speed of development, it is hard to affect sensitivity and fog, and the pH dependence of photographic liquid in which latex is dispersed Latexes having characteristics such as a small amount of water and little occurrence of coagulation and precipitation caused by the ionic strength are preferred.

An index called a glass transition point is often used for a resin. The higher the glass transition point, the harder the resin forming the latex becomes, and the resin cannot serve as a buffer. Conversely, if the resin has a low glass transition point, the resin tends to interact with each other, adversely affecting photographic performance. Therefore, in order to obtain good photographic characteristics, the composition of the resin, the amount used, and the degree of polymerization are selected.

As latex used for photographic light-sensitive materials,
Latexes using monomers such as styrene, butadiene, and vinylidene are well known. In addition, in the latex synthesis, it is said that when a monomer having a carboxylic acid group such as acrylic acid, itaconic acid, and maleic acid is introduced, the influence on the photographic properties is reduced,
Such syntheses are often attempted. Further, when a methacrylate unit is further introduced, the glass transition point can be changed. A specific example is disclosed in
No. 5335, the specification of Japanese Patent Application No. 5-119113,
The description in the specification of Japanese Patent Application No. 5-119114 is helpful.

In the present invention, the above-mentioned known latex can be used.

The silver halide photographic light-sensitive material of the present invention is subjected to imagewise exposure and then processed with a developing solution to form an image. After being processed with a developing solution, a fixing solution process for removing undeveloped silver halide is performed, followed by a washing or stabilizing process, followed by drying.

The light source used for exposure is not particularly limited, and examples thereof include a laser, a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, and a tungsten lamp.

When the silver halide photographic light-sensitive material of the present invention is an X-ray medical light-sensitive material, a phosphor that emits green light by X-ray irradiation is used.

In the method for developing a silver halide photographic light-sensitive material of the present invention, the total processing time is dry to dry.
For 30 seconds or less, and preferably 25 seconds or less.
The term "total processing time" as used herein refers to the total processing time including the steps of developing, fixing, washing and drying the photosensitive material.

The preferred development temperature is 25 to 50 ° C., more preferably 30 to 40 ° C. The preferred development time is from 3 to 15 seconds, more preferably from 3 to 10 seconds.

In the development, a processing agent is replenished to compensate for the processing agent fatigue and the oxidative fatigue equivalent. The replenishment of the developer can be performed, for example, by replenishing by width and feed speed described in JP-A-55-126243, by area replenishment described in JP-A-60-104946, or described in JP-A-1-149156. It can be carried out by replenishing the area controlled by the number of sheets continuously processed. The replenishment rate of the developer was 14 ml /
Preferably not more than four, more preferably
7 ml / quarter or less.

The fixing solution used in the method for developing a silver halide photographic light-sensitive material of the present invention contains a fixing material generally used in the art. The iodine content of the fixing solution is preferably 0.3 g / liter or less,
More preferably, it is 0.1 g / liter or less. The pH of the fixing solution is preferably 3.8 or more, more preferably 4.
2 to 5.5. The replenishing amount of the fixing solution is preferably 14 ml / quarter or less, more preferably 7 ml.
/ Not more than four. The fixing solution may contain a hardening agent for hardening. As the hardener, a compound capable of forming aluminum ions is preferable. For example, aluminum sulfate, aluminum chloride, and potassium alum are preferably used.

The fixing solution may contain, if desired, a preservative such as sulfite or bisulfite; a pH buffer such as acetic acid or boric acid; a mineral acid (eg, sulfuric acid, nitric acid / hydrochloric acid); an organic acid (eg, citric acid). Oxalic acid, malic acid, etc.); pH adjusters such as metal hydroxides (eg, potassium hydroxide and sodium); chelating agents having water softening ability; fixing accelerators (eg, JP-B-45-35754). No., Japanese Patent Publication No. 58-12
No. 2535, Japanese Patent Publication No. 58-122536, and a thiourea derivative described in U.S. Pat. No. 4,126,459.

The preferable fixing temperature is 20 ° C. to 50 ° C., and the preferable fixing time is 2 seconds to 8 seconds.

In the method for developing a silver halide photographic light-sensitive material of the present invention, a processing solution prepared using a solid processing agent is used.

The term “solid processing agent” as used herein refers to a solid processing agent, such as a powder processing agent, a solid processing agent such as a tablet, a pill, or a granule. Things.

The powder as used in the present invention refers to an aggregate of fine crystals. The term “granules” as used in the present invention refers to granules having a particle diameter of 50 to 5000 μm, which are obtained by adding a granulation step to powder. The tablet in the present invention refers to a tablet obtained by compression-molding a powder or a granule into a certain shape.

As a means for solidifying the processing agent, a concentrated liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily molded processing agent. Any means can be employed, such as forming a coating layer by spraying. These solidification techniques are described, for example, in the specification of Japanese Patent Application No. 2-13587, the specification of Japanese Patent Application No. 2-203165, and the specification of Japanese Patent Application No. 2-20316.
6, Japanese Patent Application No. 2-203167, Japanese Patent Application No. 2-203168, Japanese Patent Application No. 2-3004.
No. 09, which can be referred to.

It is preferable that the tableted solid processing agent is produced by granulating a powdered solid processing agent and compressing it. The tableted solid processing agent produced in this way has improved solubility and storage stability over the solid processing agent formed by simply mixing the solid processing agent components and forming a tablet, and obtaining the resultant. There is an advantage that the photographic performance is also stable.

Granulation methods for the powdered solid processing agent include known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation. Can be used. The average particle size of the granulated solid processing agent is 1
It is preferable that the average particle diameter be from 00 to 800 μm in that when the granulated material is mixed and compressed under pressure, non-uniformity of components, that is, so-called segregation hardly occurs. A more preferred average particle size is 20
0 to 750 μm. Further, it is preferable that 60% or more of the granulated particles have a deviation of ± 100 to 150 μm.

For the compression of the granulated solid processing agent under pressure,
Known compressors, for example, a hydraulic press, a single-shot tableting machine,
A rotary tableting machine and a briquetting machine can be used. The shape of the solid processing agent that is pressed and compressed is arbitrary, but from the viewpoint of good productivity and handling, and from the viewpoint of dust generated during use on the user side, a cylindrical tablet is preferable. .

Each component of the solid processing agent, for example, an alkali agent, a reducing agent, a preservative, etc., is granulated separately for each component prior to producing the solid processing agent by compressing under pressure. Is preferred.

Specifically, tablet-type solid processing agents are described, for example, in JP-A-51-61837 and JP-A-54-1.
JP-A-55038, JP-A-52-88025, British Patent No. 1,213,808 and the like can be used for the production. 2-109042, JP-A-2-109
No. 043, JP-A-3-39735 and JP-A-3-39939. The powdery solid processing agent can be produced by, for example,
-133332, British Patent No. 725,892, British Patent No. 729,862 and German Patent No. 3,733,861, etc. It can be manufactured by

[0134] The bulk density of the tablet type solid processing agent, in view of solubility, also, from the viewpoint of achieved sufficient effects, it is 1.0g / cm ³ ~2.5g / cm ³ Is preferred. If the bulk density is less than 1.0 g / cm ³ , the strength will be poor, and if it exceeds 2.5 g / cm ³ , the solubility will be insufficient. When the solid processing agent is in the form of granules or powder,
The bulk density is preferably 0.40 to 0.95 g / cm ³ .

The solid processing agent can be a developer, a fixing agent, a rinsing agent, and the like. When a solid processing agent is used as the developer, the effect of stabilizing photographic performance is large. Advantageously, the agent is a solid processing agent.

In the method for developing a silver halide photographic light-sensitive material of the present invention, a solid processing agent in which only a part of the processing agent is solidified may be used, but all components of the processing agent are solidified. Is preferred.

In the solid processing agent, each component of the processing agent may be molded as a separate solid processing agent and packaged integrally, or the separate components may be packaged in the order in which they are to be charged. It is also desirable.

In the method for developing a silver halide photographic light-sensitive material of the present invention, all of the processing agents to be replenished in each processing tank are processed in a solid state in accordance with a signal generated according to the processing amount of the silver halide photographic light-sensitive material. It is preferable to add as an agent. When the replenishing water is required, the replenishing water can be replenished based on the information of the processing amount or the information of the replenishing water control other than this. In this case, the liquid to be replenished to the processing tank can be only replenishing water. This way,
Even if there are a plurality of processing tanks that require replenishment of the processing agent, only one tank for storing the replenishing liquid is required, and the size of the automatic developing machine can be reduced. Further, the replenishment water tank may be placed outside or inside the automatic processor. Placing the replenishing water tank inside is preferable in terms of space saving and the like.

When the developer is a solid processing agent, it is a preferred embodiment that all of the reducing agent, alkali agent and the like are used as the solid processing agent. When the solid processing agent is a tablet, it is preferable that the amount is not more than three, and the most preferable embodiment is one. When the treatment agent is divided into two or more agents to form a solid treatment agent, it is preferable that the divided tablets and granules are in the same package.

When the solid processing agent is a tablet, for example, Japanese Unexamined Utility Model Publication No. 63-137783, Japanese Utility Model Application Laid-Open No. 63-9
No. 7522, Japanese Utility Model Laid-Open No. 1-85732, etc., can be supplied to the processing tank by a supply method described above, but any method can be used as long as the function of supplying tablets to the processing tank is provided at a minimum. Good. Examples of the supply method when the solid processing agent is a granule or a powder include a gravity method described in Japanese Utility Model Laid-Open No. 62-81964, Japanese Utility Model Laid-Open No. 63-84151, and Japanese Patent Application Laid-Open No. 1-292375. Dropping method and Japanese Utility Model Application Laid-open No. Sho 63-105159, 63-19
Although a method using a screw or a screw described in Japanese Patent No. 5345 is known, the present invention is not limited thereto.

As a supply means for supplying the solid processing agent to the processing tank, for example, the solid processing agent is weighed in advance, divided and packaged, and is used in accordance with the processing amount of the silver halide photographic material. There is a method of opening and supplying. Specifically, the solid processing agent is sandwiched and stored between at least two packaging materials in a predetermined amount, preferably in a single replenishing amount, so that the air permeability between the outside air and the adjacent solid processing agent is blocked. When used, the package is separated in two directions or a part of the package is opened so that the solid processing agent can be taken out. It is supplied by dropping naturally into the processing tank provided. The solid processing agent is guaranteed to be moisture-proof until opened.

In the above, if the periphery of the package of the solid processing agent is joined so as to be separable, the joining portion is separated by pulling the packaging material in different directions, and the solid processing agent is taken out. Will be able to Further, at least one of the packages of the solid processing agent can be opened by an external force. For example, the solid processing agent can be extruded by cutting a part of the package, making one of the packages openable, and applying a compressive force to the package. In addition, it is also possible to make it possible to take out the package by making a cut with a sharp blade in the package that can be opened.

In the method for developing a silver halide photographic light-sensitive material of the present invention, for example, by detecting information on the processing amount of the silver halide photographic light-sensitive material, a signal for starting the supply of the solid processing material is output. Supply is started. The supply is stopped by detecting information indicating that the supply of the predetermined amount has been completed. When the solid processing agent is packaged and needs to be separated or opened, when the supply start signal is issued, first, the driving means for separating and opening is operated, and then the supply is started. Is done.

The supply means of the solid processing agent may have a control means for supplying a fixed amount of the solid processing agent in accordance with the processing amount information of the silver halide photographic light-sensitive material. Injecting a certain amount of solid processing agent according to the processing amount information of the silver halide photographic light-sensitive material, in an automatic processor, is to maintain the component concentration in each processing tank constant and to stabilize the photographic performance. Is necessary for

The processing amount information of the silver halide photographic light-sensitive material includes, for example, the processing amount of the silver halide photographic light-sensitive material processed with the processing solution, the processing amount of the processed silver halide photographic light-sensitive material, It can be a value proportional to the processing amount of the silver halide photographic light-sensitive material, and indicates indirectly or directly the reduction amount of the processing agent in the processing solution. The processing amount information may be output at any timing before the photosensitive material is immersed in the processing solution, during the immersion in the processing solution, or after the photosensitive material is discharged from the processing solution. Furthermore, physical parameters such as the concentration of the composition of the processing solution, the change in the concentration, the pH and the specific gravity, etc. can also be used. Further, the amount may be the amount discharged to the outside after the treatment liquid is dried.

The solid processing agent may be charged into a processing tank, but is preferably connected to a processing section for processing a silver halide photographic light-sensitive material, and a processing liquid flows between the processing section and the processing section. It is preferable that the processing liquid is circulated between the processing unit and the processing solution, and the component in which the solid processing agent is dissolved moves to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

[0147]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1

Preparation of Silver Halide Fine Particle Emulsion (Emulsion A) An aqueous solution containing 114 g of silver nitrate and an aqueous potassium bromide solution were simultaneously added over 10 minutes while stirring 1300 cc of a 3.5% aqueous gelatin solution containing 4 g of acetic acid at 50 ° C. while stirring. . Meanwhile, the pAg was kept at 8.1. Then, gelatin 19
3 g were added to prepare a silver halide fine grain emulsion containing silver halide fine grains having a grain size of 0.08 μm.

Preparation of Silver Halide Fine Grain Emulsion (Emulsion B) In the preparation of Emulsion A, thiourea dioxide was simultaneously added with 2 × 10 ^-4 at the same time as the addition of the aqueous silver nitrate solution and the aqueous potassium bromide solution.
A reduction sensitized fine grain emulsion having a grain size of 0.08 μm was prepared by adding a potassium bromide aqueous solution containing mol / mol Ag at a constant flow rate.

Silver halide emulsion (emulsion C) 3.75 lime-processed bone gelatin was placed in a container equipped with a stirrer.
g, KBr 4.76 g, defoamer and pH at 39 ° C.
6 liters of water containing a sufficient amount of sulfuric acid to adjust the pH to 8 are added, and while stirring, an AgNO ₃ solution (containing 2.5 mol of AgNO ₃ ) and a KBr solution (containing 2.5 mol of KBr). Were added simultaneously to form nuclei. During nucleation, p
Br and pH were almost maintained at the values initially set in the solution in the reactor.

Next, the temperature was raised to 54 ° C. for 9 minutes, and after maintaining at this temperature for 9 minutes, the temperature was maintained at 54 ° C. to dissolve a solution obtained by dissolving 100 g of lime-processed bone gelatin in 1.5 liter of water. Was added.

Next, the pH was raised to 5.90 and KBr
The solution (containing 1 mole of KBr) was added to the reactor.
24.5 minutes after nucleation, the silver halide grain growth phase began. Meanwhile, the AgNO ₃ solution (containing 2.5 mol of AgNO ₃ ) and the KBr solution (containing 2.8 mol of KBr) maintain the pBr in the reactor at the value obtained by the above-mentioned addition of KBr. As such, it was added proportionally at a constant flow rate. The addition time was 53.33 minutes.

Thereafter, a KBr solution (containing 1.0 mol of KBr) was added to adjust the pBr to 2.20. continue,
AgNO ₃ solution (containing 2.5 mol of AgNO ₃ ), KB
r solution (containing 2.8 mol of KBr) and a suspension of AgI (Lippmann emulsion) (containing 0.148 mol of AgI) such that the segment initial flow rate: the segment final flow rate was 1: 12.6. Was added while increasing the addition flow rate. Upon addition, a KBr solution (containing 2.8 mol of KBr) and a suspension of AgI (Lippma
nn emulsion) (containing 0.148 mol of AgI) was added at a controlled flow rate to maintain the pBr in the reactor at 2.20.

The obtained silver halide emulsion had silver iodobromide grains having a silver iodide content of 0.3 mol%.

Subsequently, the silver halide emulsion was subjected to coagulation washing,
Emulsion C was prepared by adjusting the pH to a storage value of 6 and the pBr to a storage value of 2.5.

In the obtained silver halide emulsion, tabular silver halide grains accounted for more than 99.5% of the total grain projected area. The average equivalent circle particle size is 1.
The average thickness was 0.22 μm.

Silver halide emulsion (Emulsion D) 24.5 minutes after nucleation, thiourea dioxide was added in an amount of 1 × 10 ^−5.
Emulsion D was prepared in the same manner as Emulsion C except that mol / mol Ag was added.

Silver halide emulsion (Emulsion E) 54.5 minutes after nucleation, thiourea dioxide was added to 1 × 10 ^−5.
Emulsion E was prepared in the same manner as Emulsion C except that mol / mol Ag was added.

Silver halide emulsion (emulsion F) Emulsion F was prepared in the same manner as in the preparation of emulsion C except that silver halide fine grain emulsion A was added at 5 × 10 ^-2 mol / mol Ag 24.5 minutes after nucleation. Prepared. However, adjustment was made so that the total silver amount was the same.

Silver Halide Emulsion (Emulsion G) Emulsion G was prepared in the same manner as in the preparation of emulsion C, except that 54.5 minutes after nucleation, silver halide fine grain emulsion A was added at 5 × 10 ^-2 mol / mol Ag. Prepared. However, adjustment was made so that the total silver amount was the same.

Silver halide emulsion (emulsion H) Emulsion H was prepared in the same manner as in the preparation of emulsion C, except that 5 × 10 ^-2 mol / mol Ag of silver halide fine grain emulsion B was added 24.5 minutes after the nucleation. Prepared. However, adjustment was made so that the total silver amount was the same.

Silver Halide Emulsion (Emulsion I) Emulsion I was prepared in the same manner as in the preparation of emulsion C except that silver halide fine grain emulsion B was added 5 × 10 ^-2 mol / mol Ag 54.5 minutes after nucleation. Prepared. However, adjustment was made so that the total silver amount was the same.

Silver halide emulsion (emulsion J) Emulsion J was prepared in the same manner as in the preparation of emulsion C, except that 10 × 10 ^-2 mol / mol Ag of silver halide fine grain emulsion B was added 24.5 minutes after nucleation. Was prepared. However, adjustment was made so that the total silver amount was the same.

(Selenium Sensitization) After the emulsions C to J prepared as described above were heated to 47 ° C., adenine and silver iodide fine particles were added, and after 10 minutes, the spectral sensitizing dye (A) and the spectral A solid particulate dispersion of the sensitizing dye (B) is added, and then a mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate and a dispersion of a selenium sensitizer (triphenylphosphine selenide) are added. Aging was performed for a total of 2 hours and 30 minutes. At the end of aging, a stabilizer [4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI)].

The obtained selenium-sensitized silver halide emulsions are referred to as emulsions (C) to (J).

The amount of the above additive (AgX 1
Per mole).

Spectral sensitizing dye (A) 5,5′-Dichloro-9-ethyl-3,3′-cy- (sulfopropyl) oxacarbocyanine sodium salt anhydride 390 mg Spectral sensitizing dye (B) 5, Anhydrous sodium 5-di- (butoxycarbonyl) -1,1'-di-ethyl-3,3'-cy- (4-sulfobutyl) benzimidazolecarbocyanine 4 mg Adenine 10 mg Sodium thiosulfate 3.3 mg Ammonium thiocyanate 50 mg chloroauric acid 2.0 mg Silver iodide fine particles 5 mmol For selenium sensitizer dispersion 4.0 mg Stabilizer (TAI) 1000 mg The term "silver iodide fine particles" used herein means 3% by weight of gelatin used during emulsion growth. And silver iodide grains (average grain size
m).

The solid particulate dispersion of the spectral sensitizing dye (A) and the spectral sensitizing dye (B) and the dispersion of the selenium sensitizer were prepared as follows.

(Preparation of Solid Fine Particle Dispersion of Spectral Sensitizing Dye) The dispersion was prepared by a method according to the method described in Japanese Patent Application No. 4-99437. That is, it was prepared by adding a predetermined amount of the spectral sensitizing dye to water previously adjusted to 27 ° C. and stirring with a high-speed stirrer (dissolver) at 3.500 rpm for 30 to 120 minutes.

(Preparation of Selenium Sensitizer Dispersion) Triphenylphosphine selenide (120 g) was added to 50 kg of ethyl acetate (30 kg), stirred and completely dissolved to obtain a selenium sensitizer solution. Separately, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25% by weight aqueous solution of sodium dodecylbenzenesulfonate was added to obtain a gelatin solution. Next, these two liquids were mixed and dispersed at 50 ° C. for 30 minutes at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm. Thereafter, the mixture was rapidly stirred under reduced pressure, and ethyl acetate was removed until the residual concentration of ethyl acetate became 0.3% by weight or less. Thereafter, this dispersion was diluted with pure water to prepare 80 kg.

(Chemical sensitization without selenium sensitizer) After the emulsions I and J were heated to 47 ° C., adenine and silver iodide fine particles were added. After 10 minutes, the spectral sensitizing dye (A) and the spectral sensitization were used. The solid particulate dispersion of the dye (B) was added, and then a mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate was added, and aging was performed for a total of 2 hours and 30 minutes. At the end of ripening, 4-hydroxy-6-
Methyl-, 3,3a, 7-tetrazaindene (TAI)
Was added in an appropriate amount.

The amount of sodium thiosulfate added was 5.6 mg (per mole of AgX), and the amount of dyes and other additives (per mole of AgX) was the same as that for the selenium sensitization.

The obtained silver halide emulsions are called emulsion (I) 'and emulsion (J)'.

An undercoating liquid comprising an aqueous dispersion of a copolymer composed of three monomers of 50% by weight of glycidyl methacrylate, 10% by weight of methyl acrylate, and 40% by weight of butyl methacrylate diluted to a concentration of 10% by weight. A silver halide photographic light-sensitive material was prepared by forming the following dye layer, emulsion layer and protective layer on both sides of a support consisting of a polyethylene terephthalate film base colored blue to a density of 0.13 for an X-ray film of 175 μm for a 175 μm X-ray film. Samples 1 to 10 were prepared.

The emulsion layer and the protective layer were simultaneously coated on both sides of the support at a speed of 80 m / min by using two slide hopper type coaters, and dried for 2 minutes and 20 seconds.

The silver content of the emulsion layer was 1.6 g / m ² per side,
The amount of gelatin added was 2.5 g / m ² per side.

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 deer (average particle size 0.014 μm) 10 mg / m ²

Second Layer (Emulsion Layer) The following various additives were added to each of the emulsions obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (Molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3 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) ₂ 350 mg / m ² Compound (M) 5 mg / m ² Compound (N) 5 mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.2 g / m ² Dextrin (average molecular weight 1000) 0 0.2 g / m ² dextran (average molecular weight 40,000) 0.2 g / m ² gelatin 1.2 g / m ²

Third layer (protective layer) Gelatin 0.8 g / m ² matting agent composed of polymethyl methacrylate (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-vinylsulfonyl methyl 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) 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) 7 mg / m ² Compound (K) 15 mg / m ² Compound (O) 50 mg / m ² Compound (S-2) 5 mg / m ² C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₁ H 3 mg / m ² C ₈ F _{17 SO 2 N (C 3 H} 7) (CH 2 CH 2 O) 15 H 2mg / m 2 C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2 O) 4 - (CH 2) 4 SO ₃ Na 1 mg / m ²

[0181]

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[0182]

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[0183]

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Sample 1 of the obtained silver halide photographic material
10 to 10 were evaluated.

The sample was placed on two sheets of fluorescent intensifying screen SRO-250.
(Manufactured by Konica Corporation), and a tube voltage of 80 kVp, a tube current of 100 mA, and X for 0.05 seconds through an aluminum wedge.
The film was exposed to light and exposed to light, and the film was subjected to a developing process under the following developing process 1 and developing process 2 conditions.

(Developing Process 1) For the running process, an automatic developing machine SRX-701 (manufactured by Konica Corporation) was used which was equipped with a solid processing agent charging member and was modified so as to be able to process at a processing speed of 15 seconds. .

At the start of processing (start of running), a solution obtained by adding 330 ml of the following starter to 16.5 l of a developer prepared by diluting a developing tablet with dilution water was used as a start solution (pH 10.45). The developing tank was filled, and a fixing solution prepared by diluting the fixing tablet with diluting water was used as a start solution (pH 4.2) to fill the fixing tank and processing was started.

During the running process, the developing tank was replenished with ^{two of the following} replenishing tablets A and B, and 76 ml of water per 0.62 m ² of the photosensitive material. When each of the A agent and the B agent was dissolved in 38 ml of water, the pH was 10.70. Further, in the fixing tank, ^two fixing replenishing tablets C and one fixing replenishing tablet D per 0.62 m ² of the photosensitive material,
74 ml of water was supplemented.

The water starts almost simultaneously with the addition of the treating agent,
The agent was added at a constant speed approximately in proportion to the dissolution rate of the treating agent.

Development Processing Conditions Development 39 ° C. 5.0 seconds Fixing 36 ° C. 3.5 seconds Washing 35 ° C. 2.5 seconds Squeeze 1.5 seconds Drying 50 ° C. 2.5 seconds Total 15 seconds

(Developer Starter) Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make 1 liter.

(Preparation of Tablet A for Replenishment of Development) 3000 g of hydroquinone (developing agent) is pulverized in a commercially available bandam mill until the average particle size becomes 10 μm. 3000 g of sodium sulfite, 2000 g of potassium sulfite,
Add 1000 g of Dimaison S, mix in a mill for 30 minutes, and use a commercially available stirring granulator for about 10 minutes at room temperature.
After granulating by adding 0 ml of water, the granulated product was dried at 40 ° C. for 2 hours in a fluidized bed drier to remove the moisture of the granulated product almost completely. 100 g of polyethylene glycol # 6000 was added to the granules thus prepared, and the mixture was uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. The obtained mixture was treated with Kikusui Seisakusho Co., Ltd., Tough Presto Collect 1527.
Using a tableting machine modified from HU, the filling amount per tablet is 3.
Compressing and tableting were carried out so as to obtain 84 g, whereby 2500 replenishing tablets A were prepared.

(Preparation of Tablet B for Development Replenishment) DTPA 1
The above development was performed using 00 g, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of potassium hydroxide, and 200 g of N-acetyl-D, L-penicillamine. Granulation was carried out in the same manner as the granulation means shown in the preparation of the refilling tablet A, followed by drying. Using the granulated material thus prepared, 100 g of polyethylene glycol # 6000 was added, and the mixture was added at 25 ° C.
Using a mixer in a room conditioned to 40% RH or less
Mix uniformly for minutes. The obtained mixture was subjected to compression tableting by the same compression tableting method as described in Preparation of tablet A for development replenishment except that the filling amount per tablet was 1.73 g, and 2500 Each tablet B for replenishment of development was prepared.

(Preparation of Fixing Replenishment Tablet C) Ammonium thiosulfate / sodium thiosulfate (70/30 weight ratio)
Using 4000 g and 1500 g of sodium sulfite, the mixture was pulverized by the same method as the pulverization method shown in the preparation of the tablet A for replenishment of development, and then uniformly mixed by a commercially available mixer. Next, granulation was carried out in the same manner as in the preparation of the tablet A for development replenishment described above, except that the amount of water added was changed to 500 ml. The granulated product was dried at 60 ° C. for 30 minutes. The moisture of the material was almost completely removed. 4 g of sodium N-lauroylalanine was added to the thus-prepared granules and uniformly mixed for 3 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. The resulting mixture is
Except that the filling amount per tablet was 6.202 g, compression tableting was carried out by the same means as the compression tableting means shown in the preparation of the above-mentioned tablet A for development replenishment. It was created.

(Preparation of Fixing Replenishment Tablet D) Boric acid 100
0 g, 1500 g of aluminum sulfate / 18-hydrate, 3000 g of sodium hydrogen acetate (dried by mixing glacial acetic acid and sodium acetate in equimolar amounts), and 200 g of tartaric acid. And then homogeneously mixed with a commercially available mixer.
Next, except that the amount of water was changed to 100 ml, granulation was carried out by the same method as the granulation means shown in the preparation of the tablet A for development replenishment, followed by drying at 50 ° C. for 30 minutes. Almost completely removed. To the granulated material adjusted in this way,
4 g of sodium N-lauroylalanine were added and 5
The mixture was mixed for 3 minutes using a mixer in a room conditioned at 40 ° C. and 40% RH or less. The resulting mixture was compressed and compressed in the same manner as in the preparation of tablet A for replenishment described above, except that the filling amount per tablet was 4.562 g. Fixing replenishment tablets D were prepared.

(Developing process 2) As an automatic developing machine, SRX-
701 (manufactured by Konica Corporation) and DF
A developing treatment was carried out in the same manner as in the developing treatment 1 except that the following developing treatment conditions were employed as the developing treatment conditions using a -71-30 treating solution (both manufactured by Konica Corporation).

[0197]

The fog, sensitivity, and gamma of the samples obtained in development processing 1 and development processing 2 were measured. The sensitivity is the exposure amount E (E is a unit; lux
Expressed in seconds. ) Was calculated as the reciprocal logarithm, and expressed as a relative sensitivity where the sensitivity when the silver halide photographic material sample 1 was subjected to the development processing in the development processing 2 was 100. Gamma was determined by measuring the slope of the logarithm of the amount of exposure that gives densities of 1.0 and 2.0.

Table 2 shows the obtained results.

[0200]

[Table 2] Example 2

Silver halide photographic material (Emulsion K) 24.5 minutes after nucleation, 1 × 10 ^{−5 of} thiourea dioxide was ^added.
Preparation of Emulsion C described in Example 1 except that mol / mol Ag was added, potassium thiocyanate 3 × 10 ^-2 mol / mol Ag was added as a 2N solution after grain growth, and the mixture was stirred for 5 minutes at pAg 7.8. Emulsion K was prepared in the same manner as described above.

(Preparation of Comparative Emulsion L) 24.5 from nucleation
One minute later, 1 × 10 ⁻⁵ mol / mol Ag of thiourea dioxide was added, and at the stage when 53.33 minutes had elapsed since the start of particle growth, sodium ethylthiosulfonate was added at 3 × 10 ⁻⁵ mol / mol Ag. Emulsion L was prepared in the same manner as in the preparation of Emulsion C described in Example 1 except for the above.

(Preparation of Comparative Emulsion M) The same as the preparation of Emulsion K, except that sodium ethylthiosulfonate was added at 3 × 10 ⁻⁵ mol / mol Ag when 53.33 minutes had elapsed since the start of grain growth. To prepare Emulsion M.

(Preparation of Emulsion N of the Present Invention)
After 4.5 minutes, 5 × 10 ^-2 mol / mol Ag of silver halide fine grain emulsion B was added, and after grain growth, 3 × 10 ^-2 mol / mol Ag of potassium thiocyanate was added as a 2N solution to give pAg of 7.8. Emulsion N was prepared in the same manner as in the preparation of Emulsion C described in Example 1, except that the mixture was stirred for 5 minutes.

Adjustment was made so that the total silver amount was the same.

(Preparation of Emulsion O of the Present Invention)
After 4.5 minutes, 5 × 10 ⁻² mol / mol Ag of silver halide fine grain emulsion B was added, and after the grain growth started 53.
Example 1 was repeated except that sodium ethylthiosulfonate was added at 3 × 10 ⁻⁵ mol / mol Ag after 33 minutes.
Emulsion O was prepared in the same manner as in the preparation of Emulsion C described in above.

The total silver amount was adjusted to be the same.

(Preparation of Emulsion P of the Invention) Preparation of Emulsion O except that sodium ethylthiosulfonate was added at 3 × 10 ⁻⁵ mol / mol Ag at the stage when 53.33 minutes had elapsed since the start of grain growth. Emulsion P was prepared in the same manner as described above.

[0209] Adjustment was made so that the total silver amount was the same.

The same procedures as in (Selenium sensitization) of Example 1 were carried out except that emulsions K to P prepared as described above were used as silver halide emulsions. In the same manner as in Example 1, silver halide photographic materials 11 to 16 were prepared.

Sample 1 of the obtained silver halide photographic material
The photographic characteristics of 1 to 16 were evaluated in the same manner as in Example 1. The sensitivity was 100 when the silver halide photographic light-sensitive material sample 1 of Example 1 was subjected to development processing in development processing 2.
Relative sensitivity.

Table 3 shows the obtained results.

[0213]

[Table 3]

[0214]

According to the silver halide emulsion of the present invention, high sensitivity, low fog and high gamma can be obtained even if the development processing including the development, fixing and drying steps is performed for 30 seconds or less. Can be

Claims (6)

[Claims] 1. A silver halide photographic emulsion prepared by adding silver halide fine grains whose inside and / or surface has been reduced and sensitized during and / or after the formation of silver halide grains, and A silver halide photographic emulsion characterized in that the silver halide photographic emulsion is selenium sensitized and / or tellurium sensitized. 2. The silver halide photographic emulsion according to claim 1, wherein 2 × 10 ^-3 mol or more of a thiocyanate compound per mol of silver is present on the surface of the silver halide grains. 3. The silver halide photographic emulsion according to claim 1, wherein an oxidizing agent for silver nuclei is added during the preparation of the silver halide photographic emulsion. 4. The method according to claim 1, wherein at least one layer is provided on the support.
4. A silver halide photographic light-sensitive material comprising a silver halide emulsion layer formed of the silver halide photographic emulsion according to any one of the above items. 5. A silver halide photographic light-sensitive material comprising subjecting the silver halide photographic light-sensitive material according to claim 4 to development processing including development, fixing and drying steps in a total processing time of 30 seconds or less. Material development processing method. 6. A method for continuously developing the silver halide photographic material according to claim 4 in a development step including development and fixing steps, wherein at least one of the steps is a solid A method for developing a silver halide photographic light-sensitive material, wherein the method is carried out using a processing solution prepared using a liquid processing agent.